Internally Circulating Fluidized Bed Membrane Reactor

for High-Purity Hydrogen Production

by
D A V I D A N T H O N Y B O Y D
B . A . S c . (Department of Chemic al Engineering) University of British Columb ia, 1990
A T H ES I S S UB M I T T ED I N P A R T I A L F UL F I L L M EN T O F
T H E R EQ UI R EM EN T S F O R T H E D EG R EE O F
D O CT O R OF P H I L O S O P H Y
in
T H E F A C U L T Y OF G R A D UA T E S T UD I ES
Chemic al and Bi ol ogi c al Engineering
T H E UN I V ER S I T Y OF B R I T I S H C O L UM B I A
February 2007
David Anthony Boyd, 2007
Abstract
A novel reactor configuration, the internally circulating fluidized bed membrane reactor (I CFBMR),
was studied in an experimental program for the steam reforming (SMR) of natural gas to produce
hydrogen. This work builds on previous fluidized bed membrane reactor (F B MR ) research, in which
H
2
-selective membranes were located within a fluidized bed of catalyst to produce a H
2
stream-
directly from the reactor, thereby shifting the chemical equilibrium of the reforming reaction forward.
The I CF B MR advances this concept by modifying the reactor geometry in order to induce circulation
of catalyst solids up a central core draft assembly, which house vertical planar H
2
membranes, and
down an outer annular region. The catalyst solids circulation has a number of benefits, especially
when the reactor is applied to autothermal reforming (ATR), where the endothermic reforming heat is
supplied by direct addition of air to the reactor. In this case, the circulating solids transfer heat from
the upper oxidation zone to the core reforming zone, with very little circulation of the nitrogen
entering with the oxidation air.
The hydrodynamics of the I CF B MR geometry were studied using a Plexiglas cold model.
Dimensionless variables were used in an attempt to match key scaling parameters between the cold
model, which used air and fluidized catalytic cracking (FCC) solids, and the hot reformer. Solids
circulation was studied as a function of the main and annular gas feed rates for three different
membrane panel geometries. It was found that solid membrane panels, which prevented
communication between the core flow slots, led to maldistribution of solids and gas. Helium tracer
studies confirmed that only a small portion (-10%) of the N
2
in the oxidation air fed to the upper '
reactor transferred to the reactor core with the returning solids. Solids circulation was found to
increase linearly with the main feed rate up to a core superficial gas velocity of -0. 3 m/s, and tended
to level off after a superficial gas velocity of -0.5 m/s. The experimental data were used to find-
predictive equations for solids circulation that could be used for the hot reformer design.
Double-sided planar H
2
membranes (each 83 x 280 x 6 mm) were prepared using 50-um thick
palladium alloy foil using techniques of Membrane Reactor Technologies Ltd. Six membranes were
installed in a pilot reactor (diameter 0.135 m, height 2.3 m) and a number of pilot reforming
experiments were performed. The reformer was successfully operated up to 650C and 1,500 kPa
with a feed of natural gas and steam, under both S MR (external heat) and A T R (direct air addition).
Helium tracer studies were performed on the hot reformer, and internal solids circulation was
measured to be 0.21 kg/s at a typical operating condition, closely matching the value predicted from
cold model experimentation. Pure H
2
(>99.999%, excluding N
2
) was produced for the first -180
i i
hours of testing, after which the H
2
purity from two of the six membranes dropped to -99.7%for the
remaining -150 hours of hot operation. The highest hydrogen production from the pilot reactor was
-1.06 Nm
3
/h. The highest measured ratio of permeate H
2
to feed natural gas was 1.17 Nm
3
/Nm
3
, well
below the value required for economic operation (-2.5), highlighting how the reactor performance
was limited by the installed membrane area. ATR operation showed that permeate H
2
production is
only marginally affected by the rate of air addition. Two types of catalyst powders, a SMR (NiO)
catalyst and a novel ATR catalyst, were used in the pilot reformer. Low catalyst activity affected a
number of the experimental runs.
The ICFBMR reactor was simulated using a commercial process simulator (HYSYS) to study the
influence of a number of variables on a reactor producing 30 Nm
3
/h of H2. The simulation ignored
reaction kinetics, a reasonable assumption for this reactor configuration as reactor performance is
overwhelmingly controlled by membrane performance and reactor geometry, with reactor gases near
equilibrium. Simulations indicate that the predicted solids circulation rate is sufficient to maintain the
core temperature drop to below 30C, and that there would be limited reduction in membrane area if
the circulation rate were to be increased. The reactor model was incorporated within a simulation for
the complete system, leading to a predicted overall energy efficiency of 69%, based on utility
consumption and the higher heating value of reactants. An economic evaluation of the ICFBMR
system was performed and compared with published data from a conventional small-scale SMR
system. Results indicate that the ICFBMR can achieve higher process efficiencies, but that membrane
cost and longevity are critical to making the process economically viable.
i i i
Table of Contents
Abstract . ii
Table of Contents -iv
List of Tables vii
List of Figures bx
Nomenclature xiv
Acknowledgements xvii
Chapter 1. Introduction.... 1
1.1 Hydrogen -. 1
1.1.1 Hydrogen Economy 2
1.1.2 Small-Scale Thermal Processes for H
2
Production 4
1.2 Steam Methane Reforming '.. 6
1.2.1 S MR Catalysis 8
1.2.2 Limitations of Conventional S MR 9
1.2.3 Small-Scale S MR 10
1.2.4 Membrane Reforming .-. 11
1.2.5 Fluidized Bed Membrane Reactor 12
1.3 Internally Circulating Fluidized Bed Membrane Reactor 15
1.4 Research Objectives 18
1.5 Thesis Outline 19
Chapter 2. Hydrogen Selective Membranes 21
2.1 Background 21
2.1.1 Oxygen Permeable Membranes 22
2.1.2 Types of Hydrogen Permeable Membranes 24
2.1.3 Ceramic Hydrogen Permeable Membranes 25
2.2 Metallic Hydrogen Membranes 27
2.2.1 Dense Palladium-Based Membranes 27
2.2.2 Dense Palladium-Based Membranes: Mechanical Issues 31
2.2.3 Composite Membranes /. 33
2.2.4 Palladium Membranes in S MR 34
2.3 I CF B MR Membranes 34
2.3.1 Planar Membrane Design.. 36
2.3.2 Membrane Fabrication 38
2.3.3 Membrane Costs 42
2.4 Membrane Characterization 43
2.4.1 Effect of Hydrogen Partial Pressure 44
2.4.2 Effect of Temperature 47
2.4.3 Variation between Membranes 49
2.5 Conclusions 50
iv
Chapter 3. Cold Model Testing . 52
3.1 Introduction 52
3.2 Fluidized Beds 53
3.3 Cold Model Hydrodynamics 54
3.3.1 Scaling Parameters 54
3.3.2 Catalyst Powder Characteristics 56
3.4 Experimental Apparatus 60
3.4.1 Reactor Geometry 60
3.4.2 Instrumentation 67
3.5 Experimental Results 69
3.5.1 Fluidization Observations 70
3.5.2 Solids Circulation 71
3.5.3 Pressure Data 76
3.5.4 Helium Tracer Experiments 80
3.6 Discussion '. 86
3.6.1 Solids Circulation 86
3.6.2 Other Geometry Aspects 89
3.6.3 Design Implications 91
Chapter 4. ICFBMR Pilot Plant 93
4.1 Introduction 93
4.2 I CF B MR Reactor 94
4.2.1 Process Design 94
4.2.2 Reactor Layout ........96
4.2.3 Membrane Assembly Layout 100
4.2.4 Reactor Instrumentation ; 103
4.3 Pilot Plant Description 104
4.4 Pilot Plant Operation 106
4.5 Catalyst 106
4.6 Pilot Plant Experiments without Membranes 108
4.7 Pilot Plant Experiments with Membranes I l l
4.7.1 Membrane Performance : 111
4.7.2 S MR Operation (External Heating Only) 115
4.7.3 A T R Operation (Air Addition) 119
4.7.4 Solids Circulation Tests 121
4.8 Catalyst Testing 124
4.8.1 S MR Catalyst Testing. 125
4.8.2 A T R Catalyst Testing .' 126
4.9 Discussion '. 128
4.10 Conclusions 132
Chapter 5. Post-Run Membrane Testing.. 133
5.1 Membrane Removal and Observations 133
5.2 Membrane Flux Testing '. 135
5.3 Permeate Purity..: 136
5.4 Foil Analysis with S EM / ED X 137
5.5 Discussion 142
v
Chapter 6. Process Simulation and Economics , 144
6.1 Introduction 144
6.2 Reactor Simulation 145
6.2.1 Simulation Base Case 149
6.2.2 Effect of Reactor Variables 153
6.3 Design of a 30 Nm
3
/h H
2
Unit 157
6.3.1 Design Basis 158
6.3.2 Process Simulation 159
6.3.3 Reactor Layout 162
6.3.4 Economics 166
6.4 Discussion 169
Chapter 7. Conclusions and Recommendations 171
7.1 Conclusions 171
7.2 Alternative Reactor Applications 173
7.3 Recommendations 174
References 176
Appendix 1: Introductory Details 185
Appendix 2: Membrane Details ..187
Appendix3: Cold Modeling
A3.1 Cold Model Installation Instructions 192
A3. 2 Cold Model Testing Details 195
Appendix 4: ICFBMR Pilot Reactor
A4.1 I CF B MR Reactor Details 205
A4. 2 I CF B MR Assembly Procedure 233
A4. 3 I CF B MR Operating 242
A4. 4 Catalyst Microreactor 249
A4. 5 Commissioning 251
A4. 6 I CF B MR Pilot Plant Data 253
A4. 7 Microreactor Data 261
A4. 8 T G A Analysis of Ni O Catalyst 263
A4. 9 X R D Analysis of N i O Catalyst 265
Appendix 5: Post-Run Membrane Testing Details 266
Appendix 6: Process Simulation and Economics
A6.1 Simulation Details 273
A6. 2 30 Nm
3
/h Cash Flow Analysis 281
A6. 3 Alternate 30 Nm
3
/h I CF B MR Cost Analysis
;
287
vi
List o f Tables
1.1 Hydrogen unit equivalence of 100 S L M : 4
1.2 Selected thermal processes to produce hydrogen 5
1.3 Common S M R reactions 7
2.1 Parts list for I CF B MR panel.. 37
2.2 Summary of membrane panel areas 41
2.3 Approximate I CF B MR membrane panel costs 42
2.4 Calculated effective membrane areas for I CF B MR panels 50
3.1 Cold model and pilot reactor properties and characteristics 59
3.2 Cold model scaling parameters at a core superficial velocity of 0.1 m/s 60
3.3 Comparison of cold model and I CF B MR reactor geometries 65
3.4 Summary of cold model helium tracer results 84
4.1 Summary of I CF B MR experimental runs 109
4.2 Permeate purity from membranes operating in I CF B MR pilot reactor 113
4.3 Calculated effective permeation area of the membranes installed in the pilot reactor 114
4.4 Local measured and corresponding equilibrium temperatures 124
4.5 Equilibrium methane conversions for Figure 4.19 127
5.1 Calculated effective membrane permeation area, before and after pilot runs 136
5.2 Permeate purity post-pilot runs 137
6.1 I CF B MR base case simulation 150
6.2 Stream summary for 30 Nm
3
/h reactor base case simulation 151
6.3 Stream table for 30 Nm
3
/h flowsheet 161
6.4 P F D stream summary for 30 Nm
3
/h design 162
6.5 Figures of merit for 30 Nm
3
/h H
2
I CF B MR and conventional S MR production units 170
A l . l Steps employing catalysts in S MR 185
A1. 2 S MR reactions with oxygen input 185
A1. 3 S MR reaction rates ; 186
A l .4 S MR reaction rate parameters '. 186
A2.1 Permeation rig components 189
A2. 2 Gas chromatograph details 189
A2. 3 Hydrogen permeation data for Panel A - effect of hydrogen partial pressure 190
A2. 4 Effect of temperature on permeation for Panel A 191
A2. 5 Effect of temperature on permeation for Panels 1-8 191
A3.2.1 Cold model feed air rotameters 197
A3. 2. 2 Cold model pressure transducer data 198
A4.1.1 I CF B MR thermocouples , 223
A4. 1. 2 I CF B MR pressure transducers 223
A4. 1. 3 I CF B MR pressure taps and sample points 223
A4. 1. 4 Equipment list for I CF B MR pilot plant 225
vi i
A4. 1. 5 Natural gas analysis . 232
A4.3.1 Operator task checklist 248
A4. 6. 1 Gas chromatograph analyses from I CF B MR helium tracer testing 253
A4. 6. 2 Membrane flux testing during run #5 253
A4. 6. 3 Membrane flux testing during run #6 254
A4. 6. 4 Summary of selected I CF B MR pilot tests 255
A4. 6. 5 Calculation of solids circulation in pilot reactor from helium tracer tests 258
A4. 6. 6 Data from A T R experiments with 0
2
: CH
4
molar ratio varied from 0 to 0.6 258
A4. 6. 7 Temperature profile of the reactor core during high temperature A T R tests 259
A4.7.1 Microreactor catalyst test data 261
A4. 7. 2 Data from virgin A T R microreactor tests 262
A4.8.1 T G A S MR catalyst samples. 263
A4.9.1 X R D samples 265
A5. 1 Flux data for I CF B MR panels #6 and #8 after service in pilot plant 272
A6.1.1 H Y S Y S simulation details 273
A6. 1. 2 Stream table for 30 NmVh base case reactor simulation 276
A6. 1. 3 30 Nm
3
/h process inputs 278
A6. 1. 4 Pinch analysis summary 279
A6.1.5 System losses for 30 Nm
3
/h design 279
A6.2.1 Equipment list for 30 Nm
3
/h I CF B MR design 283
A6. 2. 2 Assumptions for Net Present Value analysis 284
A6. 2. 3 Net Present Value calculations for 30 Nm
3
/h I CF B MR design 285
A6. 2. 4 Summary of N P V analysis for 30 Nm
3
/h I CF B MR design 286
A6.3.1 Cost basis 287
A6. 3. 2 Process basis 287
A6. 3. 3 Conventional S MR vs. I CF B MR cost comparison 288
vi i i
List of Figures
1.1 World hydrogen market summary 1
1.2 Cost of delivered H
2
of various technologies 3
1.3 Carbon emissions from current H
2
technologies 3
1.4 Equilibrium methane conversion in S MR as a function of temperature and pressure 7
1.5 Conventional S MR process schematic 8
1.6 Equilibrium methane conversion in S MR as a function of temperature and in-situ
hydrogen removal 12
1.7 Simplified process schematics for conventional S MR, membrane S MR and
membrane A T R 14
1.8 I CF B MR schematic : 17
1.9 I CF B MR plan view 18
2.1 Types of hydrogen permeable membranes 24
2.2 Hydrogen permeation through dense metallic and porous inorganic membranes 25
2.3 Four-layer alumina membrane 26
2.4 Relative permeability of hydrogen in various palladium alloys at 350C and 2.2 MPa. . . . 30
2.5 Thermal expansion coefficients of palladium and various membrane support materials.. 32
2.6 Fabrication techniques of supported palladium membranes 33
2.7 Membrane panel cross section 36
2.8 I CF B MR panel assembly drawing 37
2.9 Membrane bonding apparatus schematic 39
2.10 Three membrane panels in preparation for bonding 40
2.11 Finished membrane panel (Panel A) 41
2.12 Membrane permeation rig schematic 43
2.13 Hydrogen flux on Panel A as a function of difference between square root of
hydrogen partial pressures 46
2.14 Permeation of Panel A at three different upstream pressures with permeate at 101 kPa. . 47
2.15 Arrhenius plots of hydrogen permeation on Pd
75
Ag25 Panel A (475-564C) at three
different upstream pressures with permeate at atmospheric pressure 48
2.16 Flux data for six membrane panels as a function of temperature 49
3.1 Gas-solid flow regimes 54
3.2 Cumulative size distributions for the three catalyst powders studied.... 57
3.3 Cold model pressure drop vs. superficial air velocity for the F CC 57
3.4 Cold model system schematic 62
3.5 Plan view of cold model core box and panels (solid panels shown) 63
3.6 Front views of cold model panels 64
3.7 Details of bottom section of cold model column 66
3.8 Helium tracer system for cold model column 69
3.9 Average downward solids velocity in the annular regions with solid panels as a
function of main column flow and secondary air flow 73
3.10 Average downward solids velocity in the annular regions with horizontally slotted
panels as a function of main column flow and secondary air flow 74
3.11 Average downward solids velocity in the annular regions with vertically slotted
panels as a function of main column flow and secondary air flow 74
3.12 Average downward solids velocity in the annular regions with a secondary air flow
of 20 S L M for all three panel geometries 75
ix
3.13 Average solids internal circulation rate with a secondary air flow of 20 S L M for the
three panel geometries 76
3.14 Absolute pressure measurements from the middle of the core channels with solid
panels (480 S L M main air, 20 S L M secondary air) 77
3.15 Absolute pressure measurements from the middle of the core channels with
horizontally slotted panels (480 S L M main air, 20 S L M secondary air) 78
3.16 Pressure drop across channel 4 in cold model core with solid panels 79
3.17 Pressure drop across channel 4 in cold model core with vertically slotted panels 79
3.18 Measured helium concentration at various points in the cold model with 0% and
3.28% helium in the main feed for the vertically slotted panels 81
3.19 Measured helium concentration at different sample points in the upper core box after
10 min. continuous injection of helium into the bottom of channel 4 (vertically
slotted panels) 85
3.20 Measured cold model solids flux in core draft box (G
p
,
core
) for horizontally slotted
and vertically slotted panels vs. product of superficial gas velocity in core ,
(U
core
) and particle density (p
p
), with an annular air flow of 20 S L M 87
3.21 Sketches showing solids entrainment in the wake of a rising bubble 89
3.22 Some alternative I CF B MR layouts 90
3.23 Alternate annular distributors 91
3.24 Effect of solids circulation on core reactor temperature drop and normalized
membrane area 92
4.1 Process flow diagram (external heating) 97
4.2 Process flow diagram (direct air addition) 98
4.3 I CF B MR pilot reactor 99
4.4 Location of membranes in I CF B MR reactor 101
4.5 Plan view of I CF B MR reactor internals 102
4.6 End view photograph of final membrane assembly 103
4.7 Pilot plant schematic 104
4.8 Purity of combined hydrogen permeate (excluding N
2
) and core reactor temperature
over the duration of the I CF B MR pilot reactor testing 113
4.9 Permeate hydrogen recovery relative to gas feed rate as function of reactor
temperature and N
2
sweep . 116
4.10 Permeate hydrogen recovery relative to natural gas feed rate as function of reactor
temperature and sweep gas 117
4.11 Permeate hydrogen recovery relative to natural gas feed rate as function of steam-
to-carbon molar ratio reactor temperature and sweep gas 117
4.12 Hydrogen recovery as a function of natural gas feed rate for all data in Table A4. 6. 4. . . . . 118
4.13 H
2
partial pressure in a well-mixed reactor for A T R experimental conditions predicted
by equilibrium model 119
4.14 Effect of air addition on H
2
flux 120
4.15 Permeate hydrogen flow (with and without sweep gas) with varying air addition rate.... 121
4.16 I CF B MR helium tracer test schematic 122
4.17 Measured helium concentration and methane conversion from helium tracer tests 123
4.18 C H 4 conversion in microreactor with S MR catalyst 125
4.19 C H 4 conversion in microreactor with virgin A T R catalyst 127
4.20 Microreactor testing of diluted (10%) A T R catalyst after use in I CF B MR pilot plant 128
4.21 Alternate I CF B MR reactor layout 131
5.1 I CF B MR internals being removed from horizontal pilot plant reactor 134
5.2 I CF B MR membrane assembly after service in pilot plant reactor 135
x
5.3 Post-pilot run flux test data for membrane panels #6 and #8 at 560C 136
5.4 Peeling palladium alloy foil from membrane panel #1 138
5.5 S EM of fresh P d
7 5
A g
2 5
foil at x300 magnification 139
5.6 S EM of scaled membrane foil (front) at x300 magnification 139
5.7 S EM of polished membrane foil (front) at x300 magnification 140
5.8 S EM of back of membrane foil at x300 magnification 140
5.9 S EM of back of membrane foil at x 1000 magnification 141
5.10 Summary of ED X analyses of used membrane foil 142
6.1 I CF B MR simulation schematic 146
6.2 Permeation stage temperature and reactor hydrogen partial pressure (base case) 152
6.3 Calculated permeation stage area (base case, 50 yaa. Pd
7 5
Ag2 5 membrane) 153
6.4 Effect of reactor pressure and steam-to-carbon ratio on normalized base case
membrane area 154
6.5 Effect of hydrogen recovery on normalized base case membrane area 154
6.6 Effect of membrane operating temperature on normalized base case membrane area 155
6.7 Effect of feed preheat temperature on normalized membrane area 156
6.8 Effect of normalized solids circulation rate on normalized base case membrane area 156
6.9 Effect of permeate H
2
partial pressure on normalized base case membrane area 157
6.10 Process flow schematic for 30 Nm
3
/h production rate 160
6.11 Plan view of option 1 layout - 30 Nm
3
/h reactor (U
core
= 0.22 m/s) 163
6.12 Plan view of option 2 layout - 30 Nm
3
/h reactor {u
core
= 0.12 m/s).. 164
6.13 Elevation drawing for Option 2 - 30 Nm
3
/h reactor (U
core
= 0.12 m/s) 165
6.14 Estimated bare equipment cost components for 30 Nm
3
/h unit 167
6.15 Breakdown of variable operating costs for 30 Nm
3
/h I CF B MR (base case) 168
7.1 Sorption enhanced I CF B MR concept : 174
A l . 1 Equilibrium methane conversion in S MR as a function of steam-to-carbon ratio
and temperature 185
A2.1 Palladium pricing 1992-2007. 187
A2. 2 Crease defects in I CF B MR membrane panels after bonding 188
A3.1.1 Cold model assembly schematic 194
A3.2.1 Cold model primary and secondary air distributors 195
A3. 2. 2 Cold model viewed from bottom flange 195
A3. 2. 3 Cold model main distributor plate 196
A3. 2. 4 Elevation view of cold model oxidant distributor.. 196
A3. 2. 5 Pressure drop over cold model main distributors 197
A3. 2. 6 Pressure drop over cold model secondary and oxidant distributors 197
A3. 2. 7 Plan view of cold model pressure tap connections with vertically slotted panels. 198
A3. 2. 8 Elevation view of cold model pressure tap connections (looking east) 199
A3. 2. 9 Cold model pressure drop vs. superficial air velocity for S MR (NiO) catalyst 200
A3.2.10 Cold model pressure drop vs. superficial air velocity for A T R catalyst 200
A3.2.11 Calibration of FI-06 used for helium injection in cold model testing at 207 kPag as
measured against a mass flow meter operating with helium 201
A3.2.12 Typical calibration curve of thermal conductivity detector (TCD) with helium used in
cold model system 201
A3.2.13 Ratio of maximum to minimum quadrant solids velocity for cold model data 202
A3.2.14 Pressure drop over channel 4 in cold model core with horizontally slotted panels 202
xi
A3.2.15 Gage pressure at mid-height of cold model channel 4, 20 S L M air to annulus 203
A3.2.16 Pressure of annulus vs. pressure in channel 4 in with vertically slotted panels 204
A4.1.1 I CF B MR main distributor drilling pattern 205
A4. 1. 2 I CF B MR distributor pressure drop 205
A4. 1. 3 Photograph of I CF B MR main and annular distributor assembly 206
A4. 1. 4 I CF B MR external pressure vessel drawing (1) 207
A4. 1. 5 I CF B MR external pressure vessel drawing (2) 208
A4. 1. 6 I CF B MR support steel drawing..; 209
A4.1.7 I CF B MR internal vessel drawing (1) 210
A4.1.8 I CF B MR internal vessel drawing (2) 211
A4. 1. 9 I CF B MR main distributor mechanical drawing 212
A4.1.10 I CF B MR internal preheater 213
A4.1.11 I CF B MR draft core box 214
A4.1.12 Membrane assembly general arrangement .215
A4.1.13 Dummy membrane panel. 216
A4.1.14 Membrane backing strips and full-length dummy panel 217
A4.1.15 Membrane connector piece 218
A4.1.16 P&J D for pilot plant (gas cylinders) 219
A4.1.17 P &I D for pilot plant (feeds and condensers) 220
A4.1.18 P&ED for pilot plant (external preheater) 221
A4.1.19 P &I D for new I CF B MR reactor 222
A4.1.20 I CF B MR instrument locations '. 224
A4.1.21 I CF B MR pilot plant control screen #1 226
A4.1.22 I CF B MR pilot plant control screen #2 227
A4.1.23 I CF B MR pilot plant control screen #3 228
A4.1.24 I CF B MR pilot plant control screen #4 ..: 229
A4.1.25 I CF B MR pilot plant control screen #5 230
A4.1.26 I CF B MR dummy internals for commissioning 231
A4.1.27 I CF B MR off-gas filter pressure drop 232
A4.2.1 I CF B MR block positions 239
A4.2.2 I CF B MR preheater 240
A4.2.3 Inserting I CF B MR internals into horizontal reactor 240
A4. 2. 4 I CF B MR internal reactor shell and heaters 241
A4. 2. 5 Raising the I CF B MR reactor 241
A4.4.1 Microreactor flow schematic : 249
A4. 4. 2 Microreactor geometry 250
A4.5.1 Original pilot I CF B MR secondary distributor (dimensions in mm) 251
A4. 5. 2 Original pilot I CF B MR air distributor 251
A4. 5. 3 Calibration of helium rotameter (CHE 4251C) at 1,380 kPag.... 252
A4.6.1 Measured and predicted methane conversion as a function of reactor temperature 259
A4. 6. 2 Methane conversion as function of steam-to-carbon ratio, reactor temperature and
sweep gas... 259
A4.6.3 Hydrogen flux as a function of natural gas feed rate for all data in Table A4. 6. 4 260
A4.8.1 Temperature profile of T G A tests : 263
A4. 8. 2 T G A weight profiles of Ni O samples, normalized to initial sample weight 264
A4. 8. 3 T G A differential weight profiles of sample #1 (fresh Ni O catalyst) 264
A4.8.4 T G A differential weight profiles of sample #3 (after final I CF B MR run) .264
A4.9.1 X R D analysis of fresh Ni O catalyst (sample #1, top spectra) and used catalyst 265
xii
A5. 1 Post-pilot run membrane panel refrigerant leak test observations 266
A5. 2 S EM of fresh Pd
75
Ag25 foil at xlOOO magnification 267
A5. 3 S EM of scaled membrane foil (front) at xlOO magnification 267
A5. 4 S EM of scaled membrane foil (front) at x3000 magnification 268
A5. 5 S EM of polished membrane foil (front) at xlOOO magnification 268
A5. 6 S EM of polished membrane foil (front) at x3000 magnification 269
A5. 7 S EM of back of membrane foil at x3000 magnification 269
A5. 8 ED X scan #1 of scaled front of membrane 270
A5. 9 ED X scan #2 of polished front of membrane 270
A5. 10 ED X scan #3 of smooth zone of back of membrane 271
A5.11 ED X scan #4 of scaled zone of back of membrane 271
A6.1.1 HYSI S reactor simulation flowsheet (Sheet 1: Left hand side) 274
A6.1.2 HYSI S reactor algorithm schematic 278
A6. 1. 3 Pinch analysis diagram for 30 Nm
3
/h design 279
A6. 1. 4 HYSI S 30 Nm
3
/h process simulation flowsheet 280
A6.2.1 Simplified P &I D for 30 Nm
3
/h 281
xiii
Nomenclature
Letters
A am,
A
ef
f
A
gap
A
Ar
Ar
A B
C,,C
2
Cm
CHI
C
0
D
D
H
D
AH
d
n
,
d *
Fr
g
^p, core
JH
Area [m
2
]
Total cross-sectional area of annular regions [m
2
]
Open cross-sectional area of membrane core box [m
2
]
Effective permeable area of membrane [m
2
]
Cross-sectional area of gap at annular turn into core draft box [m
2
]
Area of membrane [m
2
]
Archimedes number (Ar = d = -r-
5
) [-]
P
Archimedes number boundary between Geldart's group A and B particles [-]
Constants in equation 3.5 [-]
Concentration of atomic hydrogen on high concentration side of membrane [mol/m
3
]
Concentration of atomic hydrogen on low concentration side of membrane [mol/m
3
]
Discharge coefficient in equation 3.11 [-]
Reactor internal diameter [m]
Hydraulic diameter [m]
Atomic hydrogen diffusivity [m
2
/s]
Particle diameter [m]
Particle diameter for a certain size fraction [m]
-, 1/
Dimensionless particle diameter (J* = d
p
P/(P
P
-Pf)g
P
)[-]
Activation energy for hydrogen permeation [J/mol]
Particle Froude number (Fr
Ml
)[-
Bubble wake fraction [-]
Acceleration due to gravity (9.81) [m/s
2
]
Mass flux of solids [kg/s m
2
]
Mass flux of solids up the ICFBMR core based on area open to flow [kg/s m
2
]
Hydrogen flux through membrane [mol/s m
2
]
Permeation flux constant [mol/s m Pa
0 5
]
x i v
K
s
Sievert's constant [mol/m
3
Pa
05
]
L Generic bed dimension [m]
Wp.core Net solids circulation rate up reactor core (kg/s)
MW
X
Molecular weight of species x [g/mol]
n Exponent for hydrogen partial pressure in flux equation [-]
P
H
h Partial pressure of hydrogen on high-pressure (reactor) side [Pa]
PHeh Partial pressure of helium on high-pressure (reactor) side [Pa]
PHI Partial pressure of hydrogen on low-pressure (permeate) side [Pa]
PHei Partial pressure of helium on low-pressure (permeate) side [Pa]
Q
b
Bubble volumetric flow [m
3
/s]
Qcore Gas volumetric flow in reactor core [m
3
/s]
Qg.ann Gas volumetric flow dragged down in annulus [m
3
/s]
Q
H
Hydrogen permeation rate [mol/s]
r Square of ratio of hydraulic diameter of the gap and hydraulic diameter of annulus in
equation 3.11 [-]
R Gas constant (8. 314) [J/mol K]
p
f
U
m;
d
Re
m
/ Particle Reynolds number at minimum fluidization (Re
m/
=
1 m j
/ ) [-]
M
s Reactor space velocity [h"
1
]
T Temperature [K]
U Superficial gas velocity [m/s]
U
ann
Superficial gas velocity in the annulus [m/s]
U
c
Superficial gas velocity at which pressure fluctuations in a fluidized bed reach a
maximum [m/s]
U
core
Superficial gas velocity in reactor core based on area open to flow [m/s]
U
mf
Superficial gas velocity at minimum fluidization [m/s]
U, Terminal particle settling velocity [m/s]
U* Dimensionless terminal particle velocity (U* = U,
V
p
Particle velocity in annulus [m/s]
V Catalyst volume [m
3
]
X i Mass fraction for a certain size fraction [-]
M(P
p
-Pf)g
3
XV
Greek Letters
AP Pressure difference between annulus and core, equation 3.11 [Pa
Bed voidage [-]
Bed voidage at minimum fluidization [-]
n
Energy efficiency [-]
p
Gas viscosity [Pa s]
Pann Bed density in annulus region [kg/m
3
]
Pf
Gas density [kg/m
3
]
PP
Particle density [kg/m
3
]
X
Thickness of palladium membrane layer [m]
Volumetric flow of reactants [m
3
/h]
t
Particle sphericity [-]
Abbreviations
ATR Autothermal reforming
EDX Energy dispersive x-ray
FBMR Fluidized bed membrane reactor
FCC Fluidized catalytic cracking
ICFBMR Internally circulating fluidized bed membrane reactor
MRT Membrane Reactor Technologies Ltd.
Pd Palladium
PID Piping and instrumentation drawing
ROG Non-permeate reactor off-gas
SEM Scanning electron microscope
SLM Standard liters per minute
SMR Steam methane reforming
XVI
Acknowledgements
The genesis of this project arose from collaboration between Membrane Reactor Technologies Ltd.
(MRT) and Noram Engineering and Constructors Ltd. This project would not have been possible
without the generous assistance and expertise of the engineers and scientists of MRT for membrane
preparation and pilot plant operations, especially from Dr. Anwu Li, Ali Gulamhusein and Hongbin
Zhao.
I am very grateful to my co-supervisors, Dr. John Grace, Dr. Jim Lim and Dr. Alaa-Eldin Adris, for
helping me to further their previous research in this area. The staff and my fellow graduate students
of my department made my stay at UBC very enjoyable and helped me survive the pilot plant wjrk.
I am thankful for the direct financial and material support received from NSERC, BC Science
Council, UBC UGF, MRT and Noram Engineering.
Finally, my greatest source of support has been my parents and my family, Jen, Gavin, Morgan and
Jocelyn, who have been extremely patient during my extended stay at UBC. Without their love and
inspiration, completion of this project would have been impossible!
xvi i
Chapter 1. Introduction
This chapter presents the background and motivation for the present research;
improvement of the conventional steam methane reforming (SMR) process with a novel
membrane reactor for small-scale production of high-purity hydrogen. Previous high-
temperature membrane reactor research is discussed. The concept for a newreactor, an
internally circulating fluidized bed membrane reactor (ICFBMR), is also presented.
1.1 Hydrogen
Hydrogen is one of the basic building blocks of the chemical and petroleum industry. It is produced
in large quantities for a variety of processes, with ammonia production and fuel upgrading being the
largest consumers (Figure 1.1A). The world's annual hydrogen production is currently estimated at
approximately 50 million tonnes (Stoll and von Linde, 2000). Canada's current annual production is
estimated at 3.8 million tonnes, and is growing rapidly to meet demand in heavy oil upgrading
(NRCan, 2005).
gas
A. Global H
2
demand (SRI, 2004) B. Feedstocks for global H
2
supply (NAE, 2004)
Figure 1.1: World hydrogen market summary (2003)
1
Hydrogen can be produced by a wide range of processes, including electrolysis of water, many
thermo-chemical processes and some anaerobic biological systems. However, the majority of the
world's hydrogen demand is supplied by steam reforming of hydrocarbons, principally of natural gas
(Figure 1 .IB), and is likely to remain so for the foreseeable future.
1.1.1 Hydrogen Economy
As oil reserves dwindle and the effects of global warming become evident, there has been
considerable interest in employing hydrogen as an energy carrier. When used in a fuel cell, hydrogen
produces electricity, with water being the only emission. Other fuel cell feedstocks, such as methanol,
have also been extensively studied, but hydrogen currently remains the most practical fuel source.
The promise of hydrogen powered fuel cell vehicles has yet to be commercially realized, and some
are pessimistic that it ever will (e.g. Roram, 2004). However, many believe that switching to a
"hydrogen economy" is needed to satisfy the world's future energy requirements in an
environmentally sustainable manner (e.g. see National Academy of Engineering, 2004, Sperling and
Ogden, 2004).
There has been considerable debate on where the hydrogen needed to power fuel cell devices will
come from (Ewan et al., 2005). Many researchers agree that "green"hydrogen produced from a
renewable energy source such as hydro or wind-powered water electrolysis and biomass gasification
is desirable in the long term, while a lesser number advocate coal or nuclear-derived hydrogen.
However, hydrogen production from hydrocarbons, such as natural gas, is likely to remain the most
practical and economic solution in the near term (i.e. Thomas et al., 1998, NAE, 2004).
Figure 1.2 presents delivered hydrogen cost estimates for a variety of technologies, at the present and
projected into the future, for large and small-scale facilities. The reforming technology studied in this
work falls under "small scale natural gas - future"in Figure 1.2, and highlights the potential to
provide distributed hydrogen reformed from natural gas at an economically attractive price, both in
the short and longer terms. "Gasoline"in Figures 1.2 and 1.3 is the gasoline equivalent for a hybrid
vehicle compared to a H
2
-powered fuel cell vehicle.
2
12 -
Ol
10
jc:
55
3
8

8
Hi
C
O

6 -
c
0>
Ol
o
4 -
a
>s
X
2
0
Large scale Midsize Distributed - small scale
Q current
Hf uture
I
o
O
1 a
(0
o 3
O cr
> -
OL
Technology
o
CO
ro
O
Figure 1.2: Cost of delivered H
2
of various technologies
(NAE 2004, gasoline values adjusted for hybrid vehicle efficiency, "PV" = photovoltaics)
Figure 1.3 presents estimated carbon emissions for a number of the current hydrogen technologies
presented in Figure 1.2. Grid-based technologies show relatively high emissions due to the current
electrical generation supply in the US. If the electrical supply were less reliant on carbon fuels, the
C0
2
load of the grid-based technologies would be lower (Ewan et al., 2005).
x
o
15 3
a
n
2. 2
o
oi
* 1
Large scale Midsize Distributed - small scale
H indirect release
thro ugh electicity
O direct release
i
CO
o
O
c
x: g
1 g
to
ro <n
o n
E
g
bo
CO CD
>. to
S
LU 3
1 o
f
2
> -
a.
CD
C
O
W)
ro
Technology
Figure 1.3: Carbon emissions from current H
2
technologies
(NAE, 2004, gasoline values adjusted for hybrid vehicle efficiency)
One of the technical challenges in commercializing the proton exchange membrane (PEM) fuel cell
has been hydrogen purity. Very low levels of impurities, specifically carbon monoxide (<1 ppm), are
required to prevent catalyst poisoning. High purity hydrogen is also needed in other applications,
such as semiconductor manufacturing. This study investigates a new reactor to produce high-purity
3
hydrogen with the SMR process. It is envisioned that this process could be a viable option for small-
scale hydrogen production, such as hydrogen fuelling stations, or as an on-site alternative for liquid
hydrogen consumers.
In the literature and industry, hydrogen production figures are quoted in a wide variety of units. In
this work, hydrogen flows are given in NrnVh or standard liters perminute (both referenced to 0C,
101.3 kPa). Table 1.1 below presents some of the more common units for the nominal hydrogen
design rate for the ICFBMR pilot reactor (100 SLM). Large-scale SMR plants typically produce
hydrogen in the range of 25,000 to 100,000 NmVday. Small-scale reformers for distributed hydrogen-
fuelling stations are envisioned to be in the range of 100 to 1,000 NmVday, sufficient to supply a fleet
of 900 to 9,000 fuel cell cars (Ogden, 2001). 1 Nm
3
of hydrogen is equivalent in energy to
approximately 0.3 liters of gasoline.
Table 1.1: Hydrogen unit equivalence of 100 SLM
1
Molar Basis
Mass Basis
100 SLM (0C basis)
0.0089 kg/min
6.0- Nm
j
/h (0C basis)
0.536 kg/h
144 NtrrVd 12.9 kg/day
1.1.2 Small-Scale Thermal Processes for H
2
Production
Steam methane reforming, or other thermal processes based on hydrocarbons, is an appropriate
technology for developing a distributed hydrogen infrastructure. Reformers can be readily installed at
service stations using conventional utilities such as natural gas and water, and are cheaper to operate
than electrolyzers. Although SMR is the benchmark technology, several other thermal processes are
being considered for small-scale distributed hydrogen production (Armor, 2005). See Ogden (2001)
for a review of commercial-ready technologies and suppliers and Pena et al. (1996) for a review of
new catalytic routes to H
2
. Table 1.2 summarizes the main chemical reactions of the processes listed.
Steam methane reforming (SMR): See reaction #1 in Table 1.2. SMR is the most commercialized
of the listed technologies. Further details on the conventional SMR process are given in the next
section.
Autothermal reforming (ATR): In autothermal reforming, the SMR process is modified by adding
air or oxygen to oxidize a portion of the methane (reaction #2 in Table 1.2), thus supplying the
endothermic heat for the SMR reaction and allowing the reactor to run adiabatically. This
1
In this document "NmVh" and " S L M " conditions are referenced to 0C, 101 kPa. Unless otherwise specified,
pressure units in this report are absolute.
4
eliminates many of the heat transfer constraints of the SMR process, potentially making the
process more compact and reducing capital costs.
Table 1.2: Selected thermal processes to produce hydrogen
Reaction
>
AH
2 9 8
(kJ/mol) Notes
1 C H 4 + 2H
2
0 <-> C0
2
+ 4H
2
165 Methane reforming with water gas shift
2 C H 4 + '/
2
0
2
> CO + 2H
2
-36 Partial oxidation of methane
3 C H 4 > C + 2H
2
67 Methane cracking
4 C H 3O H + H
2
0 <- C0
2
+ 3H
2
49 Methanol reforming with water gas shift
5 NH
3
> V2N2 + V/2H2 -46 Ammonia cracking
Partial oxidation (POx): See reaction #2 in Table 1.2. Methane, or other hydrocarbons, can react
with oxygen (with and without steam) to form hydrogen at high temperatures. The process can be
performed non-catalytically, but a catalyst is commonly used in commercial units. The process
can be operated adiabatically, thus eliminating many of the heat transfer steps present in the SMR
process. The POx process is also compact and has fast response times. However thermal
efficiency is generally lower than for SMR (Ogden, 2001).
Thermocatalytic cracking of methane: See reaction #3 in Table 1.2. Methane can be catalytically
decomposed to hydrogen and carbon at high temperatures. Catalyst fouling with carbon and low
conversion are the main barriers to commercialization.
Methanol steam reforming: See reaction #4 in Table 1.2. Methanol can be readily reacted with
steam at around 300C to form hydrogen over copper or zinc-based catalysts. The major
advantage of methanol is that it is a liquid fuel, allowing existing fuel distribution infrastructure
to be readily utilized. The chemical processing conditions for methanol reforming are also less
severe than for SMR. A significant disadvantage of methanol for distributed hydrogen production
is that it is produced from reforming of natural gas, and the extra processing steps make it more
expensive and less thermally efficient that SMR. Methanol reforming provides an approximate
net production of only 1.7 moles of H
2
per mole of CH4 (Stott and von Linde, 2000). Methanol
has also been studied for on-board reforming to power fuel cell vehicles.
Gasification of coal: Coal or biomass can be gasified with oxygen and steam to produce synthesis
gas rich in H
2
. This process can potentially produce large amounts of H
2
very cheaply, but with
large carbon emissions unless coupled with C0
2
sequestration.
5
Ammonia cracking: See reaction #5 in Table 1.2. Ammonia can be catalytically cracked to
nitrogen and hydrogen. However, once again methane is conventionally used to make ammonia,
so the use of ammonia is likely to have lower thermal efficiency than SMR.
1.2 Steam Methane Reforming
In addition to hydrogen production, the SMR process is important for production of synthesis gas for
production of methanol, Fisher-Tropsch synthesis and other economically important petrochemical
operations (Rostrup-Nielsen, 2002). The steam reforming process has been employed for many years
to produce hydrogen, originally using naphtha as a feedstock, but now more commonly with natural
gas. In the SMR process, natural gas (methane) is reacted with steam over a catalyst, generally
nickel-based, to form reformate, a gaseous mixture of CFL, H
2
, CO, C0
2
and water. Reviews of the
steam reforming process have been published by Rostrup-Nielsen (1984) and Ridler et al. (1996).
The SMR process is highly endothermic. The first three reversible reactions presented in Table 1.3
are the most common reactions in the SMR process. Note that only two of the first three reactions are
independent. Formation of elemental carbon (reactions 4 and 5) is possible, but is generally avoided
by operating with a sufficiently high steam-to-carbon molar ratio. Reactions 6 to 9 are not applicable
in conventional SMR reactors, as there is no oxygen. However, air was added to the reformer in this
work to supply heat in-situ (autothermal reforming).
As the intrinsic reaction kinetics are rapid in the presence of reforming catalysts, the conventional
SMR process generally operates close to chemical equilibrium. As it is an endothermic process, high
temperatures favour conversion. Typical SMR reactor operating temperatures are in the range of 750
to 900C. From the net reforming reaction (reaction 3 in Table 1.3), it can be seen that extra moles of
gas are produced, and thus by Le Chatelier's principle, increasing pressure tends to favour the reverse
reaction. In practice, conventional reformers are operated at pressure (typically 2 MPa, but ranging
from 1 to 4 MPa) in order to produce a compressed product and to reduce the size of the processing
equipment. When operated for hydrogen production, a steam-to-carbon molar feed ratio between 2.5
and 3 is commonly used (Armor, 1999). Figure 1.4, produced with a commercial process simulator
(HYSYS, Gibbs free energy minimization), presents the SMR equilibrium methane conversion as a
function of temperature and pressure. This highlights the need for elevated operating temperatures in
conventional primary reformers to achieve high methane conversion.
6
Increasing the steam-to-carbon ratio increases the equilibrium methane conversion modestly, as
shown in Figure A 1.1, Appendix 1. However, increasing steam usage tends to decrease overall
energy efficiency.
Table 1.3: Common SMR reactions (all species are gaseous)
Reaction ' AH
2 9 8
(kJ/mol)
Notes
1 CH, + H
2
0 <-> CO + 3H
2
206
Methane reforming
2 CO + H
2
0 ~ C0
2
+ H
2
-41 Water gas shift
3 CH
4
+ 2H
2
0 <-> C0
2
+ 4H
2
165 Net SMR reaction
4 2CO ^ C + C0
2
-172 Disproportionation
5 CH4 <-> C + 2H
2
75 Decomposition
6 CH 4 + V2O2 CO + 2H
2
-36 Partial oxidation
7 CH, + 1V2O2 - CO + 2H
2
0
-519 Partial CH 4 combustion
8 C H 4 + 20
2
-* C0
2
+ 2H
2
0 -802 Total CH
4
combustion
9 H
2
+ '/
2
0
2
- H
2
0 -242 Hydrogen combustion
0 I , r , '
500 600 700 800 900
Temperature ( C)
Figure 1.4: Equilibrium methane conversion in SMR as a function of temperature and pressure
(steam-to-carbon molar ratio = 3; no inert gases or oxygen present)
Conventional SMR catalysts are sensitive to sulfur, and thus a gas desulfurization step is performed
prior to feeding the reformer. The endothermic reaction heat is supplied to banks of reactor tubes,
typically ~12 m long, located within a fired furnace. The gas produced in the reformer contains
significant amounts of CO and therefore shift reactors are installed after the primary reformer to
convert CO to C0
2
and H
2
(water gas shift, reaction 2 in Table 1.3). Hydrogen is then separated from
7
the gas mixture in a pressure swing adsorption (PSA) system or an amine scrubber. A methanation or
preferential oxidation reactor may also be installed to convert trace CO to C O 2 (Cromarty and
Hooper, 1996). Figure 1.5 presents a SMR process schematic for a typical large-scale facility.
Feed pretreatment Reformer High temperature Low temperature Hydrogen
1r . \ shift reactor shift reactor purification
] r U 6 l / A i r y j j j
I Steam
Figure 1.5: Conventional SMR process schematic (adapted from Stitt et al., 2000)
Depending on the heat recovery scheme and accounting for gas burnt in the furnace and steam export,
conventional SMR systems produce approximately 2/2 moles of H
2
per mole of methane consumed
(Stoll and von Linde, 2000). Steam is typically exported from the SMR system, as it is difficult to
utilize all of the waste heat due to temperature pinches in the process. The energy efficiency of a
modern large-scale SMR plant can reach 85%-90%when the export steam is credited, but values in
the range of 75%are more common (Ogden, 2001). Thermal efficiency is significantly lower (-60%)
if only the energy value of the product hydrogen is compared to the feed natural gas (Spath and
Mann, 2001).
1.2.1 SMR Catalysis
Armor (1999) lists nine steps in the SMR process that use catalysts (see Table A 1.1 in Appendix 1).
In the reformer proper, the most common type of catalyst is nickel (12-20%as NiO) supported on
alumina or ceria. A variety of promoters, including potassium and calcium, are often used to reduce
carbon formation. The catalyst is commonly formed into rings or spoked wheels in order to minimize
pressure drop and enhance mass and heat transfer within the fixed bed. SMR catalysts are an
established, cost-effective product, but have some drawbacks including Ni sintering, carbon
formation and heat and mass transfer constraints (Rostrup-Nielsen, 1984). The NiO catalyst must be
8
reduced prior to use. This is typically carried out industrially in a H^/steam or CFL/steam mixtures at
elevated temperature. Tables A 1.2 to A 1.4 in Appendix 1 summarize a number of the SMR kinetic
equations proposed by Xu and Froment (1990).
For autothermal reforming, Ni-based catalysts have been shown to lose activity through sintering and
other mechanisms (Qi et al., 2005). An autothermal SMR catalyst must be capable of supporting the
SMR reaction (reduction) and be able to withstand oxidation conditions. New catalysts are being
developed, mostly based on noble metals such as Pt, Pd, Rh and Ru, supported on alumina or ceria.
Both a conventional SMR catalyst (NiO) and a new ATR (proprietary noble metal) catalyst were used
in the ICFBMR pilot work. However, as the main objective of this study was investigation of the
reactor configuration, and in view of the proprietary nature of the ATR catalyst, details on the
catalysts in this thesis are limited.
1.2.2 Limitations of Conventional S MR
Although it is a mature and common technology, there are several areas where the SMR process
could be improved, including (Roy, 1998):
Catalyst performance: Improved catalysts have been studied to reduce the potential for carbon
formation and increase resistance to sulphur poisoning.
Fixed bed reactor: The conventional SMR reformer consists of large number of long, thin reactor
tubes arranged in parallel in a fired furnace. The tubes are filled with high-voidage catalyst pellets
in order to limit the reactor pressure drop to a reasonable value.
o Catalyst effectiveness: Because of mass transfer constraints within the pellets, catalyst
effectiveness is very low, with up to 95%of the catalyst reported not utilized (Soliman et
al., 1988). Chen et al. (2005) demonstrated the advantages of fluidized bed catalysts over
fixed bed catalysts.
o Reactor heat transfer: Heat transfer from the furnace to the fixed bed reformer bed is
relatively low. In order to keep the temperature profile relatively constant within the
reformer, small diameter (50-125 mm) reactor tubes are required, resulting in a large
number of parallel tubes.
Unit operations: The SMR process involves a number of sequential reactors and other operating
units. This results in a large plant footprint and higher capital costs, especially for smaller scale
plants.
9
Thermodynamic limitation of the SMR process: In order to achieve acceptable methane
conversion, the reformer must operate at high temperatures. However, this poses some technical
challenges, including:
o Materials of construction: The reformer tubes run very hot, requiring expensive, high-
nickel steel, resulting in finite service life.
o Heat recovery: High operating temperatures reduce the amount of heat that can be
internally recovered from the process, and thus steam must be exported to achieve high
thermodynamic efficiency. Although this may be practical at an integrated refinery or
chemical plant, it is not usually feasible for a stand-alone or small-scale plant.
o Carbon formation: Increasing the reformer temperature increases the potential for
formation of carbon on the catalyst. Relatively poor heat transfer within the fixed reactor
bed increases the potential for hot spots, and thus carbon formation.
Hydrogen purity: The hydrogen purity from a typical PSA system is 99.95%, though higher
purities are possible at the expense of hydrogen recovery (Biegler et al., 2004). PEM fuel cell
applications require higher purity, especially with respect to CO impurities.
The novel reactor investigated in this study attempts to address the above limitations, with the
exception of catalyst performance.
1.2.3 Small-Scale SMR
Scaling down the conventional SMR process to production rates less than about 1,000 Nm
3
/day is
possible and is commercially offered. However, the high operating temperatures and high capital
costs of this approach are often thought not to be the best solution for distributed hydrogen fuelling
stations (Ogden, 1996, Thomas et al., 1997). Many industrial and academic groups have developed
new SMR-based systems for small-scale production, often incorporating some of the following
design approaches:
Less severe operation conditions: Operating the reformer at lower temperature (<700C) permits
lower-cost materials and can improve the overall system heat recovery. However, the reactor
pressure must be reduced significantly to achieve acceptable conversion.
Alternative reactor geometries: Rather than the traditional fired tubular reactor, other reactor
geometries have been proposed, including fixed bed annular reactors and plate-type
configurations.
Autothermal reforming: In order to avoid the problems and costs of reactor heat transfer,
autothermal reforming has been studied for small-scale SMR. An oxidant, usually oxygen or air,
10
is added to the reactor to allow adiabatic operation. Both direct oxidant addition and 0
2
-
permeable membranes have been studied.
CO2 removal: An adsorbent such as calcined limestone or dolomite can be incorporated to trap
CO2 within the reactor (Yi et al., 2005). The spent absorbent can be regenerated, potentially
producing a high-purity G0
2
stream that would be appropriate for one of several sequestration
options, thus removing the carbon penalty of the SMR process. In-situ C0
2
removal can also shift
the reaction equilibrium forward. Fluidized bed reactors may be used to move absorbent particle
between a reformer and regenerator (Johnsen et al., 2006).
H2 membranes: Hydrogen-permeable membranes have been extensively studied in the SMR
process. One approach is to simply replace the conventional H
2
purification stage (PSA) with H
2
perm-selective membranes. This reduces the footprint of the plant and produces a high-purity
hydrogen stream (Edlund, 1999).
H
2
membrane reactor. A more interesting approach (from a chemical engineering
perspective) to the previous option is to place the H
2
perm-selective membranes directly in
the reaction zone, creating a "membrane reactor". In addition to producing high-purity
hydrogen, removal of hydrogen from the reaction zone shifts the chemical equilibrium
forward (Adris et al., 1994). Benefits of this approach are detailed in the next section.
1.2.4 Membrane Reforming
Selectively adding a reactant or removing a product to a reacting system with a species-selective
membrane can significantly enhance the reactor characteristics for some processes.
Thermodynamically limited reactions, such as SMR, are often candidates for membrane reactors, as
addition or withdrawal of a species can favourably shift the chemical equilibrium. Removal of
hydrogen from the SMR reactor significantly enhances the equilibrium conversion of methane, as
illustrated in Figure 1.6, prepared from output from a commercial process simulator (HYSYS, Gibbs
free energy minimization). The lower curve is the SMR equilibrium with no hydrogen removal. The
upper curves represent equilibrium conversion for several hydrogen recoveries, represented as the
molar ratio of hydrogen removed to methane in the reactor feed. As progressively more hydrogen is
removed from the reacting system, conversion of methane is increased, permitting high conversions
at significantly lower operating temperatures than in conventional SMR.
Ceramic-based and dense metallic membranes are the most common types of hydrogen permeable
membranes employed in SMR research. The membranes used in this study are thin metallic
membranes based on palladium. Dense palladium membranes have the ability to produce ultra-pure
11
H
2
, as only atomic hydrogen can diffuse through the metal lattice. Details on H
2
-permeable
membranes are provided in Chapter 2.
SMR membrane reactors constitute an active field of research (see recent review by Uemiya, 2004).
Most work has focussed on fixed bed reactor configurations. Reviews of past palladium-based
membrane reactor research are given by Shu et al. (1995), Gryaznov (2000), Paglieri and Way (2002)
and Dixon (2003). The most prominent commercial membrane reformer demonstration to date was
undertaken by Tokyo Gas, who recently operated demonstration fixed bed reformer units in Japan
with a hydrogen production capacity of the order of 40 Nm
3
/h (Mitsubishi Heavy Industries Ltd.
www.mhi.co.jp/mcec/product/membrane.html; Yasuda et al., 2004). Their design appears to be based
on fixed catalyst bed monolith sandwiched between planar, palladium-alloy membranes.
0.0 I : 1 1 !
500 600 700 800 900
Temperature ( C)
Figure 1.6: Equilibrium methane conversion in SMR as a function of temperature and in-situ
hydrogen removal (1,000 kPa, steam-to-carbon molar ratio = 3; no inerts or oxygen present)
H
2
-permeable membranes eliminate the need for shift reactors and hydrogen purification. Figure 1.7
contrasts simplified process flow schematics for (a) conventional SMR, (b) a SMR membrane reactor
and (c) an autothermal membrane reactor. Compression is required for the membrane reactor
configurations to bring the product hydrogen pressure up to conventional SMR levels. Further
compression is required for all three configurations to raise the hydrogen pressure to current fuel cell
vehicle storage standards (> 3,000 kPa).
1.2.5 Fluidized Bed Membrane Reactor (FBMR)
Fluidized bed reactors have some characteristics that are favourable for implementing a membrane
reactor in SMR service (Adris et al., 1996, Grace et al., 2005, literature review by Deshmukh et al.,
12
2007). A single reaction vessel can be used, rather than the multiple reactor tubes in the conventional
SMR process. Other advantages of fluidized bed reactors over fixed bed configurations are:
Higher external heat transfer coefficient: The SMR process is highly endothennic and significant
amounts of heat must be transferred to the reactor, even for small-scale units. Fluidized beds have
higher surface-to-bed heat transfer coefficients, typically in the range of 250 to 400 W/m
2
K
(Kunii and Levelspiel, 1991), approximately an order of magnitude better than for the same
particles in fixed beds. The average heat flux in a modern tubular reformer is less than 100
W/m
2
K (Usami et al., 2003). The higher heat flux in the fluidized bed can reduce the heat transfer
area and temperature driving forces as compared to fixed bed reactors.
Reducing temperature gradients: Due to the high rate of particle mixing and high particle surface
area, temperature gradients in fluidized beds tend to be very low. This reduces hotspots in the
reactor, decreasing the potential for coke formation. For autothermal reforming, the heat released
by direct oxidant addition can be rapidly dissipated in the fluidized bed, reducing local
temperature gradients. Another feature of fluidized beds is their ability to effectively move heat
in the reactor through movement of catalyst particles.
Catalyst effectiveness: In order to fluidize the catalyst bed at reasonable gas velocities, catalyst
particles are small (typically 75 to 250 um diameter). Such small catalyst size virtually eliminate
the internal diffusion limitations of fixed bed catalysts. Pressure drop over the fluidized catalyst
bed is also typically very low.
High bed to membrane mass transfer: Analogous to high heat transfer, fluidized beds exhibit
high bed-to-surface mass transfer, preventing bulk mass transfer from being a significant
resistance in fluidized bed membrane reactors.
Disadvantages of applying fluidized beds to small-scale SMR include:
Fluidized beds tend to be best suited to large scale applications.
Bubbling fluidized bed reactors tend to deviate from plug flow, potentially leading to inefficient
contacting of reactants.
Entrainment of catalyst fines from the reactor must be addressed.
Wastage of vessel internals, such as hydrogen permeable membranes, through particle abrasion
can be problematic.
Catalyst attrition can occur due to particle-particle and particle-wall collisions.
13
Natural gas>-
Water ^>-
Sulfur
remo val
Heat exch. /
steam gen.
Burner
P S A purge gas
Heat "1
Ref o rmer Shift reacto rs
A. Conventional SMR
H2 separatio n
(PSA)
- Flue gas^>
- Steam exporfr
H2 producT)>
Natural gas>-
Water ^>
Oxidant
Natural gas>-
Water
>
(start-up only?)
Sulfur
remo val
Sulfur
remo val

Heat exch. /
steam gen.
Burner
Heat Reactor off-gas
Ref o rmer
Membrane permeate
H2
co mpressio n
B. Membrane SMR
Heat
X
Burner

Reactor off-gas
Heat exch. /
steam gen.
Refo rmer
Membrane permeate
H2
co mpressio n
C. Autothermal membrane SMR
Flue gas ^>
H2 pro duct^
Flue gas ^
H2 pro duct^
Figure 1.7: Simplified process schematics for conventional SMR, membrane SMR and membrane A T R
Recognizing the benefits of combining a SMR fluidized bed with membranes, Adris (1994)
undertook a pilot plant study, using dense palladium tubes immersed in a bubbling fluidized bed
reactor. High purity hydrogen was produced and a small equilibrium shift was demonstrated.
Subsequent modelling showed the potential benefits of the process (Adris and Grace, 1997, Abba et
al., 2003, Abashar et al., 2003). The process was also patented (Adris et al., 1994, Adris et al., 2002).
Roy (1998) utilized the same pilot reactor as Adris to study thinner, higher-flux membrane tubes.
Direct injection of oxygen into the fluidized bed was also tested and found to be practical and safe.
Direct oxidant addition (autothermal reforming) permits the SMR reactor to run adiabatically,
eliminating external heat transfer. An economic evaluation of the process was also performed (Roy et
al., 1998).
Following the work of Adris and Roy, a company called Membrane Reactor Technologies Ltd. was
started to commercialize the FBMR technology. MRT is developing an autothermal fluidized bed
membrane reactor in the capacity range of 15-50 Nm
3
/h (Klassen, 2005), the configuration of which
differs from the internally circulating geometry studied in this work.
Others, e.g. Jarosch et al. (1999) and Elnashaie and co-workers (Prasad and Elnashaie, 2002, Chen
and Elnashaie, 2005), have proposed circulating fluidized bed membrane reformer designs. In these
configurations, catalyst solids circulate between a reforming reactor containing hydrogen permeable
membranes and a second vessel where heat is added. Patil et al. (2005) proposed a bubbling bed
reactor with separate membranes to add oxygen and remove hydrogen. Patil (2005) published
experimental data from a fluidized bed reactor with tubular Pd membranes, though operation coupled
with oxygen membranes was not performed.
1.3 Internally Circulating Fluidized Bed Membrane Reactor
The fluidized bed system has some distinct advantages for membrane SMR compared to fixed bed
configurations. The work of Adris (1994) and Roy (1998) demonstrated the feasibility of
incorporating membranes into a fluidized bed SMR reactor, and indicates that oxygen addition may
be practical. In considering ways of developing a larger-capacity, potentially commercial process,
some challenges in the existing FBMR configuration were identified:
Separation of oxidant addition and membranes: Although heat is dissipated quickly in fluidized
beds, high temperatures are present locally when oxidation gas is injected as jets. As palladium-
based membranes havea practical upper operating temperature of ~650C, it is desirable to keep
the membranes well away from the oxidation zone.
15
Internal heat transfer: Membranes within the reactor impede the movement of catalyst and gases,
leading to larger temperature gradients within the fluidized bed. This becomes more acute with
larger reactor diameters and increased packing of membranes within the bed.
Nitrogen in oxidant air: Oxygen can be used as an oxidant for autothermal reforming, but an
oxygen separation unit would then be required, adding complexity and cost for small-scale
hydrogen installations. If air is the oxidation gas, the nitrogen entering with the air can
significantly dilute the reactor gases. If the system is well mixed, this reduces the hydrogen
partial pressure in the reactor and thus decreases the membrane flux of hydrogen. For autothermal
operation with air addition, nitrogen could account for almost 50%of the gases leaving the
reactor. For a well-mixed reactor, this nitrogen represents a significant reduction in the H
2
driving
force over the membrane, and more membrane area would be required to achieve the desired
hydrogen flux.
Tubular membranes: The sealing, manifolding and mechanical support of many small diameter
palladium tubes are challenging.
This study extends the research of Adris and Roy by proposing a new reactor configuration, the
internally circulating fluidized bed membrane reactor (Boyd et al., 2005). A patent on this reactor
concept has been granted (Grace et al., 2006).
When adding oxidant to the fluidized bed membrane reactor, there are two distinct reaction zones
within the bed, a reforming/hydrogen permeation zone and an oxidation zone. It is desirable to keep
these zones separate to protect the membranes, but heat must then be transferred from the oxidation
zone to the reforming/permeation zone. However, it is undesirable for nitrogen from the oxidation air
to reach the reforming/permeation zone, as the reduced hydrogen partial pressure would diminish the
membrane flux.
The challenge of separating two distinct reaction zones within a fluidized bed system is not unique
and is often addressed by moving catalyst solids between two vessels, for example in fluid catalytic
cracking (Kunii and Levenspiel, 1991) and fluid coking. Internally circulating beds for non-
membrane reactors have also been studied (e.g. Jung et al., 2004). The reactor concept presented here
is an internally circulating fluidized bed reactor. To achieve this, the reactor internals of the fluidized
bed membrane reactor were significantly modified (Figure 1.8):
Planar membranes are employed instead of tubular membranes.
The planar membranes are oriented vertically within an open-ended draft box in the core of the
reactor.
16
Oxidant air is added to the fluidized bed above the draft box, well away from the membrane
panels.
Effluent Gases
Fluidized
catalyst bed
Co re draft box
Planar membrane J - -[*^
mo dules
Permeate H2
I
Oxidatio n air
External heat
(if used)
t Reactants
(natural gas & steam)
Figure 1.8: I CF BMR schematic
The steam and methane reactants are fed to the core draft box via the reactor windbox. The reforming
reaction proceeds in the core box and hydrogen is produced. The membranes withdraw hydrogen
from the reactor as it is produced, shifting the reforming reaction forward. The upward flow of gas in
the core box induces internal circulation of catalyst up the core box and down the annular regions, as
indicated in Figure 1.8. Ai r is introduced to the fluidized bed above the core draft box and reacts with
the residual reformate, releasing heat. The partially oxidized reformate disengages from the catalyst
particles in the freeboard and leaves the reactor through a fdter or cyclone.
Circulating hot catalyst particles from the oxidation zone carry the heat from the oxidation zone to the
core reforming zone via the outer annular zone, which acts like a downcomer. If desired, external heat
can also be transferred to the circulating solids through the reactor wall, as shown in Figure 1.8. If the
performance is as anticipated, the catalyst returning in the annular regions should drag very little gas
17
downward, ensuring that the nitrogen entering the reactor with the oxidation air does not significantly
dilute the gases in the core reforming/permeate zone.
Figure 1.9 presents a plan view of the reactor. The square draft box allows a simple layout for the
planar membranes, but other configurations, such as a circular draft tube, could also be implemented.
Reactor shell
Doubl e-si ded
membrane panels
Core draft box
Downward
catalyst flow in
annular region
Upward catalyst / gas
flow in core slots
H2 permeation
through membranes
Figure 1.9: I CF B MR plan view
Planar membranes made from thin palladium alloy foil were used in this study. These metallic
membranes theoretically permeate only atomic hydrogen, producing a high-purity hydrogen product.
The planar membranes were fabricated by techniques developed by Membrane Reactor Technologies
Ltd. Background on hydrogen perm-selective membranes is given in Chapter 2.
1.4 Research objectives
The overall objective of this study is to evaluate the potential of the I CF B MR concept for production
of high-purity hydrogen at a scale appropriate for the developing distributed hydrogen market.
Specific objectives include:
Investigate the hydrodynamics of the I CF B MR concept using a cold model.
Fabricate novel planar membranes from thin palladium alloy foil.
18
Pilot the ICFBMR process at a semi-industrial scale. Investigate reactor and membrane
performance under both SMR and autothermal reforming conditions.
Simulate the ICFBMR process in sufficient detail to permit the design of an industrial-scale
system.
Evaluate the economics and commercial potential of the ICFBMR process.
1.5 Thesis outline
Chapter 2 introduces the various types of hydrogen permeable membranes, and provides more details
on dense, palladium-based membranes. The design and fabrication of seven, double-sided membrane
panels using proprietary techniques of Membrane Reactor Technologies Ltd. are then described. The
hydrogen flux characteristics of the membrane panels were determined prior to their installation in
the ICFBMR pilot reactor.
Efforts to simulate the hydrodynamics of ICFBMR reactor in a cold Plexiglas model are described in
Chapter 3. Fluidization characteristics and scaling parameters for the particles tested in the cold
model and ICFBMR pilot reactor are discussed. The cold model Plexiglas reactor was assembled,
filled with FCC particles and fluidized by air. Internal solids circulation rates were determined as a
function of air flow and membrane panel geometry. Design equations are developed to correlate
circulation rate as a function of fluidization velocity.
The process and mechanical design basis for the new ICFBMR pilot reactor is presented in first part
of Chapter 4. Reactor fabrication details and assembly instructions are described, as are the
experimental methods and operating procedures for the modified pilot plant. The latter section of
Chapter 4 describes the results from seven ICFBMR pilot plant runs. Both SMR and ATR
experiments were performed. Despite operational challenges, high-purity hydrogen was produced
from the ICFBMR and catalyst circulation confirmed.
Observations from the dismantling of the ICFBMR reactor after operation are given in Chapter 5. The
six membrane panels were inspected for damage and tested for leaks. Flux test data from two
membrane panels are summarized, showing that permeation rates were slightly higher than before the
pilot reactor testing. The foil from one membrane was removed and analyzed. SEM images show
significant metallic scaling on the backside of the membrane foil, thought to be the main cause of the
reduction in hydrogen permeation below predicted values.
19
Chapter 6 presents process simulation and economic analyses of the ICFBMR process. The reactor
was simulated with commercial process software (HYSYS). The effects of major process variables on
the ICFBMR design were investigated. A design for a 30 Nm
3
/h ICFBMR system was developed and
costs are estimated. Economic analysis indicates that the H
2
permeable membranes are a significant
capital and operating cost expense.
Chapter 7 includes the main conclusions of our study, and recommendations for future work.
20
Chapter 2. Hydrogen Selective Membranes
This chapter provides background on various types of hydrogen permeable membranes,
including palladium-based membranes, which have the unique feature of being able to
produce ultrapure hydrogen. The design, fabrication and testing of the novel planar
palladium membranes used in the ICFBMR pilot reactor are then described. Seven
double-sided membrane panels were successfully prepared, each using 50 pm thick
palladium alloy (25%silver) foil The palladium alloy foil was bonded to a stainless steel
substrate using a proprietary bonding technique (patent pending) of Membrane Reactor
Technologies Ltd. (MRT). The hydrogen flux characteristics of each membrane panel
were measured before installation in the ICFBMR pilot reactor.
2. 1 Background
Membrane research is a rich and growing field of study, especially in the area of process
intensification, where membranes are employed to improve performance of reacting systems by
addition or withdrawal of selected chemical species. Applications of membrane reactors vary widely,
and include biological, electrochemical and high temperature catalytic processes. The form of
membrane systems differs significantly, depending on the permeate characteristics and the reactor
operating conditions.
The two types of membranes that have been most commonly applied S MR process are hydrogen
permeable membranes and, to a lesser extent, oxygen permeable membranes. In the S MR process,
selective removal of hydrogen favourably affects the thermodynamic equilibrium and produces pure
hydrogen directly. Oxygen permeable membranes have been studied as a means of supplying an
oxidant to support autothermal reforming.
In reviewing the variety of hydrogen permeable membranes that can be applied to the S MR process,
the following desirable characteristics and constraints should be considered:
21
Hydrogen selectivity: Ultrahigh purity or P EM-fuel -c el l quality hydrogen is preferred.
Permeability: Hi gh hydrogen permeability is desirable to lower membrane costs and to reduce
reactor volume.
Temperature: The conventional S M R process operates at 700 to 900C due to the equilibrium
constraints of the c hemic al equilibrium. B y using hydrogen permeable membranes, S M R
operating temperatures can be reduced. Nevertheless, membranes need to be able to withstand
operating temperatures in the range of 500 to 650C.
Pressure: The conventional S M R process is pressurized in order to reduce equipment costs and
produce a high-pressure hydrogen product. Due to an increase in the number of moles, high
pressure shifts the c hemic al equilibrium towards reactants. B y removing hydrogen in-situ, the
negative effect of pressure on the c hemic al equilibrium can be reduced. Hi gh pressure is often
preferred for membrane reactor operation, as it increases the hydrogen membrane flux for a given
reactor gas c omposition. Though the I CF B M R pilot plant is limited to 1,500 kPa, membranes for
the I CF B M R process woul d ideally be able to operate with higher trans-membrane pressures,
perhaps up to 3,000 kPa.
Chemi c al stability: The membranes must be c hemic ally stable to the main gas species present in
the S M R process, inc luding carbon monoxide and water, and to the fluidized S M R catalyst.
Susceptibility to trace gas components that might poison membrane surfaces, such as sulphur, is
an important consideration for long-term service.
The membranes used in this work were fabricated from palladium alloy foi l , and have the potential to
meet most, i f not al l , of the above criteria.
2.1.1 Oxygen Permeable Membranes
This work investigates hydrogen permeable membranes for both conventional S M R and autothermal
reforming. However, the published literature on high temperature oxygen permeable membranes is
also reviewed briefly, as the I CF B M R concept is especially suited to autothermal reforming and
could be modified to incorporate oxygen permeable membranes, rather than direct air injection as
studied in this work.
Oxygen permeable membranes operating at high temperature have been extensively studied, most
c ommonly for partial oxidation reactions, with several systems i nvol vi ng a fluidized bed reactor (i. e.
Ml ec zko et al. , 1996, Deshmukh, 2004). Both porous ceramic membranes and ion conducting
ceramic membranes have been proposed for methane oxidation and syngas production. A review by
L i n (2001) provides an overview of research in this area.
22
Fluidized bed membrane reactor concepts with both hydrogen and oxygen permeable membranes
have been recently proposed (Pradeep and Elnashaie, 2002, Patil et al., 2005). The potential
advantages of oxygen permeable membranes over than direct oxygen or air addition include:
If air is used, nitrogen in the oxidation air dilutes the reactor gases, reducing the hydrogen partial
pressure and permeation driving force over the hydrogen permeable membranes;
The reactor off-gas (i.e. non-permeate stream) would contain significant amounts of nitrogen,
making carbon dioxide sequestration difficult;
If direct oxygen addition is used, the need for upstream air separation is eliminated;
If an ion-conducting oxygen membrane is used, the need for compression of oxygen or air is
eliminated.
The ICFBMR reactor concept addresses the first point, as oxidation air is added to the top of the
reactor, thus greatly reducing the amount of nitrogen circulating to the hydrogen permeable
membranes. As membrane-assisted reforming is likely to be first commercialized on a small scale,
the carbon credits of sequestering the reformer off-gas are likely to be very modest. The most
tangible benefit of oxygen permeable membranes may be the last point, as a simple air fan can
potentially replace an expensive multi-stage air compressor, but this saving must be balanced against
the cost of the oxygen membranes.
Perhaps the most extensively studied oxygen ion-conducting membranes are perovskite-type, zirconia
and bismuth oxide based ceramics (Lin, 2001). In perovskite-type ceramics, oxygen permeates as an
ion, and the driving force is the difference in oxygen partial pressure over the membrane. Therefore
oxygen from an atmospheric air supply can permeate through the membrane into a high-pressure
reactor, if the oxygen is rapidly consumed in the reactor. There has been considerable patent activity
in this field since the early 1990s, much of it led by commercial interests (i.e. Amoco: Balachandran,
et at, 1997; Praxair: Dyer et al., 2000; Eltron: Schwartz et al., 2000).
The major drawback to integrating perovskite-type oxygen membranes into a SMR membrane reactor
is that these membranes typically operate at around 900C, significantly hotter than the practical
operating limit for palladium membranes (< ~650C). Combining two distinct temperature zones, one
for palladium (H
2
) membranes and the other for perovskite (0
2
) membranes, into one reactor, as
proposed by Patil et al. (2005), is challenging. Another drawback of oxygen membranes is the extra
reactor volume required to house the membranes. However, as development in oxygen permeable
23
membranes progresses, incorporation of oxygen permeable membranes in the I CF B M R design may
become practical.
2.1.2 Types of Hydrogen Permeable Membranes
Many types of membranes have been used for gas-phase hydrogen separation. These are broadly
summarized in Figure 2. 1. The hydrogen permeable membranes used in this work are dense (i.e. non-
porous) metal foils based on palladium, the most c ommonly studied metallic membrane material.
Hydro gen
permeable
membranes
I
Organic
(po lymeric)
1
Ino rganic
~ T ~
Pro to n Gaseo us H2
"Ceramic"
co nducting separatio n
"Ceramic"
Glass
(micro po ro us)
Metallic
(dense)
Co mpo site
micro po ro us silica
micro po ro us alumina
po lycrystalline zeo lites
perovskite (proton-
conducting)
Figure 2. 1: Types of hydrogen permeable membranes (Islam 1997, L i n 2001 and L i n et al. , 2002)
Polymeric hydrogen membranes, such as hollow fibre membranes have been c ommerc ialized, and
they have been applied to membrane reactors (Vankelec om et al. , 2000), but cannot be used at the
elevated temperatures required for the S M R process. In contrast, inorganic membranes have the
potential to be used at elevated temperatures for hydrogen separation, but until recently, have
remained mostly in the realm of research and development. O f the inorganic membranes,
microporous ceramic and metallic based membranes, or a combination of the two (composite
membranes), have been most widely applied to membrane reactors. Figure 2.2 schematically shows
the permeation mechanism of dense metallic membranes, as used i n this work, and microporous
membranes. Dense metal membranes permeate hydrogen as protons through the metal lattice
structure, and are therefore theoretically 100% selective for hydrogen. This ability to produce
ultrapure hydrogen is the major feature of dense metallic membranes.
24
Dense Metal Membrane Porous Membrane
Purified H2
Membrane] yV
Figure 2.2: Hydrogen permeation through dense metallic and porous inorganic membranes
(adapted from Uemiya, 2004)
2.1.3 Ceramic Hydrogen Permeable Membranes
Inorganic ceramic membrane research has been reviewed by Coronas et al. (1999) and Lin et al.
(2002). Inorganic ceramic membranes for hydrogen separation can be broadly grouped into three
classes (Lin, 2001):
Dense ceramic proton-conducting membranes.
Polycrystalline zeolite membranes.
Microporous amorphous membranes.
Dense, proton-conducting inorganic membranes, often ceramics mixed with metals (cermet), have
been proposed for hydrogen separation. These membranes have the benefits of near 100%hydrogen
selectivity as the membranes have no porosity (Morreale et al., 2005). However, microporous
amorphous membranes have been the most common type of ceramic membrane applied to high-
temperature reactors. These membranes feature very small pores, typically smaller than 2 nm, and
generally separate hydrogen from heavier gases based on molecular size. Many formulations have
been tested, with the most commonly on alumina, zirconia, silica and other metal oxides.
Some of the benefits of microporous ceramics compared to dense metallic membranes include
relatively high hydrogen permeance, much lower cost base materials and, in some cases, good
mechanical, chemical and thermal stability at high operating temperatures. The major drawback of
microporous ceramics is hydrogen selectivity, as a porous membrane always permeates some non-
hydrogen species. Sealing of brittle ceramic membranes, typically in tubular form, in a pressurized,
high temperature reactor can be a difficult, though surmountable, engineering task. Chemical stability
of some ceramics in the presence of water, as is abundant in the SMR process, has also been a
25
challenge (Imai et al., 1997). As a result, hydrogen permeable ceramic membranes have been more
commonly applied to membrane reactor processes where there is little or no water, such as in
dehydrogenation (i.e. Ziaka et al., 1993), dry reforming (i.e. Onstot et al., 2001, Galuszka et al., 1997)
and thermal decomposition of hydrogen sulphide (i.e. Ohashi et al.). Examples of ceramic
microporous membranes applied to the SMR process include works reported by Minet et al. (1992),
Nijmeijer (1999) and Tsuru et al. (2004).
Microporous amorphous ceramic membranes are commonly prepared as very thin films (typically
between 20 nm to 50 (xm), often silica-based, deposited on a porous support. The support is usually
inorganic, commonly alumina or zirconia, and provides the mechanical strength for the membrane.
Sol-gel techniques remain the most successful method for depositing the silica membrane layer,
typically on a high-quality sol-gel support. Figure 2.3 shows a common strategy of preparing a
ceramic membrane with layers of progressively smaller pore sizes capped with a thin final layer of
very small pore diameter material.
0"*
100
CO
E
3 99
o
>
u.
98
O
98
Q.
> 97
E
96
o
95
10 100
-
I
~>
I
-
-
t
Bulk
Me mb r a n e
Suppo r t
-
layer First
-
suppo rt
layer
_
Seco nd
s uppo r t
l
layer
i
1,000
Po re diameter (A)
10,000 100,000
Figure 2.3: Four-layer alumina membrane (from Lin et al., 2002, after Hsieh et al., 1988)
Gas transport through ceramic membranes may involve a mesoporous support (20-1000 nm thick),
where flow may be controlled by viscous flow, molecular diffusion or Knudsen diffusion. If Knudsen
diffusion is controlling, the ideal separation factor between two gases is the ratio of the square roots
of the molecular weight of the gas species (Kast and Hohenthanner, 2000):
Separation factor =
JMW
2
(2.1)
From equation 2.1, the ideal separation factor for hydrogen and methane under Knudsen diffusion is
therefore 2.8. Though fluxes through these types of ceramic membranes may be reasonably high,
hydrogen separation factors are certainly too low to produce fuel-cell-quality hydrogen from the
SMR process.
26
1
For very small micropores, perhaps less than ~5 nm diameter, transport is controlled by
configurational effects, such as molecular-sieving or adsorption processes (see Benes et al., 1999 and
Kast and Hohenthanner, 2000 for reviews of microporous transport), and higher gas separation
factors can be achieved. Achieving defect-free layers of this pore diameter is challenging. Despite
this, some groups have reported separation factors for H
2
:N
2
as high as 3,000 (Nam and Gavalas,
1989, Gavalas etal., 1989).
2.2 Metallic Hydrogen Membranes
Metallic membranes have been extensively studied for membrane reactor application due to their very
high gas selectivity. In theory, palladium has infinite selectivity for hydrogen, and its application in
high temperature membrane reactors is extensive (Shu et al., 1991). This selectivity to hydrogen is
important in the context of hydrogen production for PEM fuel cells, where carbon monoxide limits
are very low, on the order of 0.2 ppm. Other metals have been proposed for hydrogen separation,
such as niobium and tantalum (Buxbaum and Kinney, 1996), but surface oxides on these refractory
metals have generally precluded their use for hydrogen membranes. Palladium and its alloys are
currently the most practical metallic membrane materials for hydrogen separation (Uemiya, 2004).
However, the purity of hydrogen produced with palladium comes with a cost, as it is an expensive
material with limited mechanical strength at the temperatures present in the SMR process.
Maintaining high-purity hydrogen, but at a thinner layer of metal to reduce cost and increase flux, is
one of the major goals in palladium membrane research.
2. 2. 1 Dense Palladium-Based Membranes
Palladium has been known to absorb and permeate hydrogen since first observed in the mid-19
th
century. Application of palladium to membrane reactors accelerated in the late 1960's, initially
centred in the Soviet Union, and later in Japan, with hydrogenation and dehydrogenation reactions
being the most commonly studied processes. Extensive reviews of past and present palladium
membrane research have been given by Paglieri and Way (2002), Gryaznov (2000) and Shu et al.
(1991).
Hydrogen is transported atomically through dense metallic membranes through a solution-diffusion
mechanism. Hydrogen permeation is a multi-step process, generally acknowledged to include:
Gas transport of hydrogen molecules to the upstream surface of the metallic membrane;
Reversible chemisorption of hydrogen molecules on the metal surface;
Reversible dissolution of atomic hydrogen on the membrane surface into the bulk metal;
27
Diffusion of atomic hydrogen through the metal lattice of the membrane;
Reassociation of atomic hydrogen on the surface of the downstream metal surface;
Desorption of adsorbed molecular hydrogen from metal surface;
Gas transport away from the downstream surface of the membrane;
In theory, only hydrogen can be transported through palladium through the above diffusion
mechanism, and thus 100%selectivity is conceivable. The presence of other gas species in the
permeate gas from a palladium membrane generally indicates a fissure or pinhole in the palladium
layer or membrane seals. Producing defect-free palladium layers becomes increasingly difficult with
progressively thinner membranes.
For the thickness of the palladium alloy membrane used in this work (50 (xm), the rate-controlling
step for hydrogen permeation is expected to be bulk diffusion of atomic hydrogen through the
membrane. Below a palladium thickness of perhaps 10 urn, other steps of the permeation process
appreciably influence the overall hydrogen flux (Ward and Dao, 1999). If bulk diffusion of atomic
hydrogen is the rate-controlling step, the steady-state flux (J
H
) can be approximated from Fick's Law
using the concentrations of atomic hydrogen in the palladium (C
H
h, CHI) on either side of a membrane
with thickness r and diffusivity of atomic hydrogen D
AH
(Shu et al. 1991).
J
H
= (C
H
h- C
H 1
) (2-2)
x
If atomic diffusion of hydrogen is rate-controlling, the concentration of atomic hydrogen at the
surface of the membrane can be assumed to be in near-equilibrium with molecular hydrogen in the
gas phase. The atomic hydrogen concentration at the surfaces can then be related to the partial
pressure of hydrogen in the gas with Sievert's equation (Shu et al., 1991):
C
Hh
= K
s
P
Hh
,C
Hl
= K
s
P
Hl
(2.3)
Ks is known as Sievert's constant and follows an Arrhenius relationship with temperature (7). The
overall flux can then be described by:
J
H
= ^e xp( ^) ( P
h
5
- P ,
5
) (2.4)
T RT
E
p
is the apparent activation energy for permeation and k
H
is the diffusion constant. The permeation
flow (Q
H
) can then be calculated by multiplying the specific membrane flux (J
H
) by the membrane
area (A
mem
). Reported values for E
p
and k
H
for palladium vary. The results of Holleck (1970) (22,000
28
J/mol) are commonly used (Ward and Dao, 1999). From equation 2.4, the effect of some important
variables on the hydrogen flux can be seen:
Thickness (r): Hydrogen flux is inversely proportional to membrane layer thickness, providing an
incentive to create thinner membranes. However, this must be balanced against the risk of
pinholes and cracks.
Temperature (J): Hydrogen flux increases with increasing temperature. Thus it is desirable to
operate palladium membranes at the highest practical temperature.
Hydrogen partial pressure: Hydrogen flux increases with increasing reactor hydrogen partial
pressure (Pm) and decreasing permeate hydrogen partial pressure (PHI)- Increasing the total
reactor pressure can therefore sometimes be effective. In order to reduce the partial hydrogen
pressure in the permeate, vacuum or an inert sweep gas can be used.
In practice, many researchers have found that the best-fit partial pressure exponent in equation 2.4 is
somewhat larger than the theoretical value of V i , and therefore equation 2.4 is often written with a
generic partial pressure exponent ():
J
H
=^
eX
p
{
Z^.)(P^-P^) (2.5)
t KI
Deviation of n from V i may be due to a number of factors, including rate-influencing surface
processes, external mass transfer resistances, blockages of membrane area with structural supports
and membrane leaks. A value for n of 1 would be expected if the rate-determining step were due to
surface effects. Intermediate values betweenV i and 1 are often reported (Ward and Dao, 1991).
Below the critical temperature of 293C, the palladium-hydrogen system can form two different
hydride phases (a and P). Palladium readily absorbs significant amounts of hydrogen at elevated
temperatures. Operating at temperatures and pressures where the two phases are present can lead to
embrittlement and severe distortion (Lewis, 1967, Shu et al., 1991), and for this reason, care must be
taken to purge pure palladium membranes with inert gas during heat-up and cool-down. To avoid this
phase transition issue, various palladium alloys, most commonly palladium-silver, often replace pure
palladium. The critical temperature of the o>p phase transition for Pd
77
Ag23 is near room temperature.
Many palladium alloys also demonstrate higher strength and hardness than pure palladium, and do
not exhibit some of the severe thermal cycling characteristics of pure palladium, which can result in
warping and cracking (Paglieri and Way, 2002).
29
Some palladium alloys show higher hydrogen permeation than pure palladium. Figure 2.4 presents
relative permeability data for a number of palladium alloys at 350C, a much lower temperature than
is required in the ICFBMR reactor. Not shown in Figure 2.4 are permeability data for alloys of
palladium with rhodium, ruthenium and platinum, which can also exhibit high hydrogen
permeabilities (Gryaznov, 2000).
0 10 20 30 40 50 60
Alloy component (wt%)
Figure 2.4: Relative permeability of hydrogen in various palladium alloys at 350C and 2.2 MPa
(after Shu et al., 1991 from data of Knapton, 1977)
Although Pd
6
oCu
40
is more difficult to apply to the SMR process due to temperature limitations, its
resistance to sulphur poisoning is reported to be significantly higher than palladium-silver alloys, and
it has been proposed for commercial hydrogen gas purifiers (i.e. Juda et al., 1999). As shown in
Figure 2.4 above, palladium-silver exhibits higher hydrogen permeation than pure palladium up to a
silver content of about 30%by weight, and reaches a maximum around 23 wt%due to variations of
hydrogen solubility (which increases with increasing silver content) and diffusivity (which decreases
with increasing silver content). For this reason, and the important practical mechanical issues
discussed above, palladium-silver (usually 23 or 25 wt%) is the most common palladium alloy
currently used in membrane reactor research. Pd
75
Ag
2
5 foil is used is this work. It should also be
noted that silver is a much cheaper metal than palladium, and thus silver alloys should have reduced
material costs compared to pure palladium of the same dimensions.
30
2.2.2 Dense Palladium-Based Membranes: Mechanical Issues
Support and sealing of thin palladium foil membranes present difficult engineering challenges,
especially when the size of the reactor increases and many membrane foils or tubes need to be
manifolded into a vessel, as in the ICFBMR pilot reactor. The form of the membrane (tubular or
planar) and the form of the membrane support, greatly influence the reactor design. Some practical
mechanical engineering issues that need to be addressed to utilise membranes in a larger scale reactor
include:
Membrane sealing: Membrane modules or tubes must be sealed, whether through welds, bonds or
gaskets. As ultrapure hydrogen is the major feature of dense metallic membranes, a small seal
leak could compromise product quality. Membrane tubes may be welded or braised to a header.
Planar membranes may be bonded, braised, welded or gasketed.
Support: The support of a network of membranes, especially small tubes, packed into a reactor
can be challenging.
Thin palladium-based foil is usually formed by cold rolling thicker sheet. This process can produce
defect-free foils down to perhaps 25 urn, though cold-rolled foils of 50 um thickness are more
common. Cold-rolled Pd
75
Ag25 foils of 15 um thickness are being now offered commercially
(Klassen, 2005). The rolling process can affect grain size and hydrogen permeation characteristics,
and annealing is often necessary (i.e. Tosti et al., 2000). Tubular membranes are typically formed by
welding or bonding cold-rolled foils.
Although stronger than pure palladium, Pd
75
Ag
2
5 still has low yield stress at elevated temperatures.
Given this low strength, use of unsupported tubes or foils becomes impractical for thin palladium
membranes if they are to be installed in a pressurized reactor. Due to mechanical strength, many
published palladium membrane reactor research papers have been conducted at relatively low
pressure. However, if thin (<75 urn) palladium-based membranes are to be used in practical,
pressurized reactors, they must be mechanically supported. For thin-walled, dense membrane tubes,
internal springs (Roy, 1998, 75 um, 3 mm OD) and porous ceramics (Gallucci et al., 2004, 50 urn
PdAg alloy, 10 mm OD) have been used to withstand external pressure. The internal supports in the
above examples were not physically bonded to the palladium membrane. Porous ceramics and
expanded metal (Tosti, 2003) have also been used to support planar foils. Whatever the mechanical
support, its inclusion into the membrane system can reduce hydrogen permeation through a number
of mechanisms, including:
Physically blockage of the permeation area;
31
Addition of a mass transfer resistance on the permeate side of the membrane;
Chemical modification of the palladium by diffusion of undesirable chemical species, for
example nickel, into the palladium from the support.
Another consideration for the dense membrane support is thermal expansion. As palladium
membranes operate at high temperatures in the SMR process, significant thermal growth is expected.
In addition, some swelling of the membrane is expected due to hydrogen absorption. Matching the
thermal growth characteristics of the support to that of the palladium can be difficult, but may be
important if the palladium foil is bonded to the membrane support, as is the case with the ICFBMR
membranes, hence metallic supports may be preferred. The thermal expansion coefficient of
palladium and various support materials is presented in Figure 2.5. As shown, the thermal expansion
coefficients of stainless steel and alumina are significantly higher than for palladium.
If the palladium foil is not bonded to the support, but rather is loosely overlaid, thermal expansion
may be less critical, and ceramics may be considered. Inconel 625, a high nickel alloy, has thermal
expansion coefficients very similar to palladium, and its use was considered for the membrane
substrate for the ICFBMR panels. However, it is expensive and has poor welding characteristics
compared to stainless steel. The 50 pm thick, palladium alloy foils used in this work were supported
by porous sheets of sintered 316 stainless steel, coated with a thin layer of alumina to prevent inter-
diffusion of the support metal with the palladium membrane.
300 400
Temperature (C)
700
Figure 2.5: Thermal expansion coefficients of palladium and various membrane support materials
(Sources: palladium: Touloukian et al., 1970; alumina: Pal et al., 1999; SS 316: 2004 ASME
boiler and pressure vessel code, part D; Inconel: Nicofer 6020hMo datasheet)
32
2.2.3 Composite Membranes
As discussed above, microporous ceramic membranes cannot produce a pure hydrogen product,
unlike dense metallic membranes. Dense metallic membranes typically suffer from lower fluxes than
ceramics, as sheets cannot be reliably formed with thicknesses much below 25 um. A compromise
between microporous ceramic and dense metallic membranes is the composite membrane, in which a
very thin layer of metal, typically palladium or palladium-silver alloy, is deposited on a porous
support. Both microporous ceramics and metallic supports have also been used. The thin palladium
layer, typically 0.5 to 15 urn thick, offers the potential of higher hydrogen fluxes and lower material
costs than thicker, dense metallic membranes, while providing higher hydrogen purities than ceramic
membranes.
Figure 2.6 summarizes some of the techniques used to prepare supported palladium membranes. The
three methods most commonly used to prepare metal fdms on porous supports are electroless plating,
chemical vapour deposition (CVD) and physical sputtering (Lin, 2001).
Co ld ro lling
Electro less plating
Electro less plating + electro plating
Reactive ion plating + electro depo sitio n
CVD
Magnetro n sputtering (RF, DC)
Flush evapo ratio n
Spray hydro lysis
So lvated metal ato m depo sitio n
0.01 0.1 1 10
Metal thickness (um)
100
Figure 2.6: Fabrication techniques of supported palladium membranes (from Uemiya, 2004)
Pagliari and Way (2002) reviewed previous research on composite palladium membranes, and
Rothenberger et al. (2004) give a good summary of past data from composite membrane research.
Although there has been significant progress in composite membranes research, major challenges
remain to incorporating this type of membrane into larger reactors such as the ICFBMR:
Selectivity: Composite membranes with very thin palladium layers tend to have small pinholes or
other defects, allowing passage of non-hydrogen gas species.
33
Thermal expansion: The metal layer in composite membranes is usually tightly bonded to the
underlying support, which may not have the same thermal expansion properties as the palladium
layer, leading to defects from thermal cycling.
Robustness: Very thin layers of palladium may be abraded or eroded in the reactor.
Despite these technical challenges, if palladium-based membrane reactors and purifiers are to be
commercially viable, development of robust, selective, thin-film (<10 um) composite membranes
may well be essential.
2.2.4 Palladium Membranes in SMR
Uemiya (2004) briefly summarized progress and issues with respect to dense and composite metal
membranes for steam reforming. In addition, there are technical issues for palladium alloy
membranes that are typically not addressed in short-term membrane reactor research, including:
Surface poisoning: Impurities in the feed, such as sulphur, halogen compounds or mercury, can
reduce hydrogen permeability of palladium membranes, sometimes irreversibly. Gas pretreatment
for these impurities is therefore necessary.
Robustness: Physical abrasion of membranes and repeated thermal cycling may damage
membranes.
Alloy segregation: It has been reported that palladium-alloy membranes in hydrogen service can
undergo compositional rearrangement, with palladium segregating at the membrane surface on
the high hydrogen concentration side, and silver on the low hydrogen concentration side (Shu et
al., 1993).
Despite several analyses (i.e. Aasberg-Petersen et al., 1998, Onstot et al., 2001) that outline the
challenging economic issues faced in applying palladium membranes to the SMR process, several
commercial enterprises are transforming membrane reactors into a practical reality.' The current work
does not attempt to answer the lingering questions of long-term application of palladium in the SMR
process, but rather to show the potential of coupling the ICFBMR concept with palladium alloy
membranes to produce high-purity hydrogen.
2.3 I CFBMR Membranes
The high operating temperatures (500-650C) and pressures of the ICFBMR pilot reactor provide
significant mechanical challenges for the membranes. As the permeate side of the membrane operates
at near atmospheric pressure, the membrane must withstand a very high trans-membrane pressure
34
gradient. The ICFBMR pilot reactor operates up to 1,500 kPa, but a commercially designed system
may operate up to -3,000kPa. The pressure differential over the membranes is only in one direction,
from reactor to permeate.
Previous research on the original FMBR pilot plant employed palladium-based tubes. Adris (1994)
utilized pure palladium tubes (4.7 mm OD, 200-um thick). Roy (1998) and Islam (1997) also used
commercial tubular membranes, believed to be fabricated from a noble-metal based alloy (3.2 mm
OD, 76-um thick). Roy inserted a spring inside the membrane tubes to provide sufficient mechanical
strength to withstand a trans-membrane pressure difference up to 1,330 kPa at 600C.
Although used in previous FMBR research, tubular membranes suffer from a number of
disadvantages, including sealing, manifolding, strength and support within the fluidized bed. A new
style of planar membrane, developed by MRT, replaced the earlier tubular membranes, and are
described in the next section. Based on the experience of MRT, palladium alloyed with 25 wt%silver
(Pd
75
Ag
25
) was selected as the membrane alloy material for the ICFBMR pilot work. This material is
available commercially from several suppliers.
Selection of the thickness of the palladium foil is a balancing act between the competing
requirements of high permeation and acceptable mechanical strength. For high hydrogen flux and
cost, thinner is clearly better. For example, a 25 um thick foil permeates essentially twice as much as
a 50 urn thick foil, with the palladium costs halved for the same membrane area, or decreased by a
factor of 4 for the same permeation rate. Since palladium costs are a significant component of a
membrane reactor, minimizing palladium usage is a key goal in membrane reactor research and
development.
Despite the incentive to use thinner foils, they are prone to mechanical failure and may develop
pinholes, permitting non-hydrogen gases to reach the permeate side of the membrane. 25 urn and 50
um thick Pd
75
Ag2 5 foils were considered for the ICFBMR pilot reactor. Experience from MRT
suggested that commercial 25 um foils sometimes contain defects, which could occasionally lead to
pinholes in the membrane. Rather than risk the hydrogen purity of the permeate stream, it was
decided to make all of the ICFBMR membranes for this project from 50 um thick Pd7
5
Ag25 foil.
There was concern that abrasion of the membrane surfaces with fluidized catalyst particles could lead
to membrane failures. A protective cover consisting of a thin ceramic felt and a metallic screen was
considered, but ultimately rejected, so that the ICFBMR membranes were used with the palladium
surfaces unprotected from the fluidized catalyst. It should be noted that the planar membrane surfaces
35
were installed vertically in the ICFBMR, parallel to the flow of fluidizing gas. Horizontally placed
tubes (or bends in vertical U-tubes) are much more prone to erosion than vertical surfaces (Zakkay,
1986). In addition, gas velocities were relatively low by fluidization standards, and palladium is a
relatively hard metal.
2.3.1 Planar Membrane Design
The membrane panel design was based on proprietary and patent-pending (Li, 2005b) procedures
developed by MRT. The novel features of the ICFBMR planar membranes are:
Pd
75
Ag
2
5 foil is bonded directly to a stainless steel support to form a leak-tight seal around the
edge of the membrane surface.
A thin sheet of porous sintered stainless steel is located under the membranes to support the thin
Pd foil against the high trans-membrane pressure gradient, allowing hydrogen to permeate.
The Pd foil is isolated from the stainless steel sintered metal support by a thin layer of alumina to
prevent metal inter-diffusion between the stainless steel and the Pd foil, which would reduce the
hydrogen permeability of the palladium.
A double-sided membrane is created by bonding Pd foil to both sides of the panel support.
Permeate hydrogen on the back side of both foils is collected in a serpentine groove cut into the
panel. Tube connections are installed for the inlet sweep gas and permeate outlet at opposite ends
of the serpentine groove to generate plug flow of the sweep gas on the backside of the membrane.
Figure 2.7 presents a cross-section (not to scale) of the membrane and highlights the main
components of the panel assembly. Figure 2.8 below shows a cut-away assembly of the ICFBMR
membrane panels. Items 1 to 4 are welded to form the completed stainless steel panel support, to
which item 5, the Pd
75
Ag25 foil, is bonded.
bo nding regio n
/ Pd f o il (2)
SS substrate
permeate flo w
channel
Y//////y/////////////////////////y/w
alumina layer (2)
SS sintered
metal suppo rt (2)
Figure 2.7: Membrane panel cross-section (not to scale)
36
The membrane panels in the ICFBMR pilot reactor are installed vertically inside an open-ended core
box. As the inner dimension of the core box was 86 mm, the width of the membrane panel was fixed
at VA" (83 mm). This width also suited the palladium foil as it was supplied in sheets of 11"x 6"
(279 mm x 152 mm), allowing the sheet to be cut in half lengthways with no palladium wastage. The
length of the panel was set at 12"(305 mm) to suit the foil length.
Figure 2.8: ICFBMR panel assembly (see Table 2.1 for identification of numbered components)
Table 2.1: Parts list for ICFBMR membrane panels (numbers refer to Figure 2.8)
Item Qty Description
1 1 Membrane panel (304 SS)
2 2 Sintered membrane substrate (316SS)
3 1 Sweep gas inlet (0.125"OD SS tube)
4 1 Permeate gas outlet (0.1875"OD SS tube)
5 2 Pd
75
Ag
25
foil (11"x 3")
37
2.3.2 Membrane Fabrication
2.3.2.1 Substrate Fabrication
Preparation of the stainless steel membrane substrate involves a number of fabrication steps.
Although each step is relatively straightforward, preparation of a defect-free substrate was the most
challenging task in preparing the membrane assemblies, partly due to the number of different
workshops involved in preparing each panel.
The panel base is (6.4 mm) thick stainless steel sheet, type 304. Each sheet was sized to the
overall panel dimensions of 12"x 3%" (305 mm long x 83 mm) by machining or water-jet cutting.
Next a recess for the sintered metal sheet was machined on each face. Two different methods were
used to cut the
l
A" (6.4 mm) thick serpentine slot. In several panels the serpentine was machined,
while other panels were water-jet cut. Both methods proved successful, though vibration of the
unsupported tines proved to be troublesome for the machining process. The ports for the 0.125"(3.2
mm) sweep gas inlet tube and the 0.1875"(4.8 mm) permeate outlet tube were also machined.
The sintered metal sheets were cut to size, placed in machined recesses in the base panel, and then
welded. Obtaining a weld that was crack-free was challenging due to the thinness and the poor
thermal heat transfer characteristics of the sintered metal. The sweep gas inlet and permeate outlet
tubes were welded on opposite ends of the membrane panel. After the panels were welded, the
sintered metal seal weld was ground smooth.
Several panel substrates were rejected at this stage due to gouges in the sintered metal caused in
grinding or cracks in the sintered metal weld. Seven substrate panels were judged to be acceptable
and were bonded with palladium foil.
2.3.2.2 Palladium Bonding
The palladium alloy foil was bonded to the stainless substrate using a proprietary and patent-pending
technique of Membrane Reactor Technologies Ltd (Li, 2005). The details that follow outline the
general steps used in bonding the membrane:
The polished membrane support panel was cleaned with in an ultrasonic bath to remove dirt and
polishing wax. A thin alumina layer was deposited on the surface of the porous sintered metal
using a sol-gel technique.
38
Palladium alloy foil (25%Ag, 50 urn thick) was purchased from a commercial supplier (Alfa
Aesar, stock #42682, Lot# G30N14). The foil was supplied in sheets of 11"x 6"(280 mm x 152
mm), cut in half longitudinally to form sheets of 11"x 3"(280 mm x 76 mm).
The foils were then laid onto both sides of the support panel. The bonding border around the
palladium foil was approximately 9 mm. The bonding border on the foil was first covered with
alumina paper gasket, then a graphite gasket. The membrane panel was placed between two steel
end plates and bolted tight. The entire assembly was inserted into the bonding reactor, a stainless
steel vessel with external heaters. Figure 2.9 shows a schematic of the bonding vessel apparatus.
Details of the bonding process are proprietary to MRT.
Figure 2.9: Membrane bonding apparatus schematic
Figure 2.9 illustrates the bonding assembly of a single membrane panel. In practice, several
membrane panels can be bonded concurrently by stacking the panels between the steel endplates.
Figure 2.10 shows a stack of three membrane panels being assembled prior to being placed in the
bonding vessel.
39
Figure 2.10: Three membrane panels in preparation for bonding
As stainless steel ferrule fittings are known to leak at the temperatures of the reformer pilot plant,
extension tubes were welded to both the sweep and permeate tube connections. This ensured that all
permeate connections within the reactor were welded.
Both sides of the membrane were checked for leaks using a refrigerant leak detector (Bacharach
Instruments, model H-10PM) and a refrigerant (Dupont Suva 134a, 1,1,1,3 tetrafluoroethane). This
procedure proved to be a quick and reliable method for detecting cracks or pinholes in the palladium
membranes. The refrigerant supply was connected to the 0.125"(3.2 mm) inlet tube and the 0.1875"
(4.8 mm) outlet tube dipped in a small beaker of water. A small flow of refrigerant was started to the
backside of the membranes, confirmed by bubbles in the outlet beaker. The leak detector wand was
then slowly run over the membrane surfaces and tube welds. No leaks were detected in any of the
membrane surfaces of the seven panels. Several leaks detected in the stainless tube welds were
subsequently repaired and confirmed to be leak-free. A photograph of one of the finished membrane
panels is presented in Figure 2.11.
Surface defects on the palladium surfaces were noted on several of the bonded panels (see Figure
A2.2 in Appendix 2). A few of the panels had small linear indentations due to small cracks in the
underlying stainless steel substrate. Others had creases in the palladium foil, most commonly along
the long edge of the membrane. These creases were likely due to insufficient bolting force on the long
edge of the panels, permitting the palladium foil deform in during bonding. As can be seen in Figure
2.11 above, the end plates used to bond the membranes were oversized, likely resulting in warping of
the endplate and uneven bolt torque.
40
Figure 2.11: Finished membrane panel (Panel A)
The total foil area installed on one panel is 426 cm
2
. The area open to hydrogen permeation is
significantly less than the total foil area due to the sealing zone around the edge of the foil, and is
estimated to be 258 cm
2
, 61%of the palladium surface. The reduction in permeation area would be
less for larger panels and it may be possible to decrease the palladium bonding area in future designs.
However, the reduction in palladium effectiveness in the ICFBMR panels is significant. This has
been addressed by MRT in their recent membrane designs.
Table 2.2: Summary of membrane panel areas
Component area
Dimensions
(mm)
Area per
panel (cm
2
)
Fraction of
foil area
Pd
75
Ag25 foil area
279 x 76 426 100%
Sintered metal substrate 260 x 57 296 69.9%
Sintered metal substrate unaffected by seal weld
(H
2
permeation area)
254x 51 258 60.6%
Six of the fabricated seven membrane panels were installed in the ICFBMR pilot reactor. During
initial testing in a permeation rig (see below), all panels were proven to be leak free up to a
differential pressure of 1,200 kPa at a temperature of 550C. Higher pressure testing was not
attempted. MRT has found that similarly constructed 50 pm Pd
75
Ag25 panels can withstand a trans-
membrane pressure difference of 2,500kPa (Li, 2003). The ultimate rupture pressure of the ICFBMR
membranes is not known.
41
2.3.3 Memb rane Costs
Palladium is a very expensive material and can be a significant cost component of a membrane
reactor. Palladium peaked at over $l,000US/oz ($32US/g) in 2001, but has averaged $260US/oz over
the last five years (2002 to 2007, source: Johnson Matthey, Figure A2.1 in Appendix 2). Minimizing
palladium costs by using thinner membranes is a key goal for many researchers.
The cost of each ll"x 6"(280 mm x 152 mm) Pd
75
Ag
2
5 foil sheet used to make each ICFBMR
membrane panel was roughly $600CAD. If the foil cost is converted to a weight basis, the cost of the
palladium in the foil is approximately $800US/oz, roughly four times the base metal cost. Lower foil
costs may be possible for larger quantity orders.
Costs for manufacturing the ICFBMR panels are estimated in Table 2.3. The value of the individual
components may appear high, as the panels were built in a one-off manner, but it is instructional to
see that the palladium foil is by far the largest single cost component. The palladium foil in the
membrane can, in theory, be recovered and recycled after use. If we assume that 80%of the
palladium in the ICFBMR membrane can be recycled, and that the value of the recycled palladium is
$100US/oz, the value of recycling the palladium is only about $70CAD/panel.
Table 2.3: Approximate ICFBMR membrane panel costs
Description
Unit cost ($CAD)
50'umPd
7
5Afesfoil(H"x6") "
$600
Sintered stainless metal sheet (0.05"thick)
$50
Supply, cut and machine V" stainless sheet support (12"x3V4")
$150
Cut, weld and grind sintered metal sheet to base support
$50
Labour to polish and clean metal substrate prior to bonding
$100
Labour to bond Pd
75
Ap,
25
foil to base support
$100
Total
$1,050
Active membrane area cost
$40,700/m
2
Limited data on membrane costs has been published, but the palladium component is expected to
dominate the cost of dense foil or tubular membranes. Composite membranes, made by depositing
palladium on a mechanical support, have been prepared with significantly thinner palladium layers,
typically less than 15 urn. At very low palladium loadings, the palladium material cost will likely be
dwarfed by the membrane fabrication cost.
Tong et al. (2005) estimated that the cost of fabricating a 0.5-urn thick Pd
75
Ag
2
5 composite wafer
(0.15 x 0.15 m) to be $340 USD (ca. $18,000CAD/m
2
). Clean-room costs were estimated to be the
most significant cost component of this membrane. Palladium and silver materials represented less
than 3%of the total fabricated cost. This membrane had roughly 50 times the permeation rate of the
4 2
ICFBMR membranes, but did not produce ultrapure hydrogen and broke under a trans-membrane
pressure difference of only 400 kPa, thus making it inappropriate for the ICFBMR process. However
this illustrates the cost reduction potential of composite palladium alloy membranes.
2. 4 Membrane Characterization
Seven double-sided membrane panels were manufactured, six of which were installed in the
ICFBMR pilot reactor. After fabrication, the membranes were then individually tested to establish
their hydrogen flux characteristics at elevated temperatures in the permeation rig shown in Figure
2.12. Table A2.1, Appendix 2 details the main components of the permeation rig, which included:
A heated pressure vessel, which could house up to three membrane panels at one time. The
temperature in the vessel was monitored by two thermocouples.
Two mass flow controllers (FIC-01), which set the feed flow of hydrogen or inert gas, either
argon or nitrogen, to the main vessel.
A mass flow controller (FIC-02) to set the flow of sweep gas to the membrane.
Vessel gas
to vent / GC>
Permeate
S weep gas
Argon or N2>[FIC-02.
V-10: S S vessel
(0.25 m diam x
0.64 m high)
Figure 2.12: Membrane permeation rig schematic
43
The membrane permeate stream could be operated at either atmospheric pressure or under
vacuum. If at atmospheric pressure, the permeate flow was measured with a bubble meter and
stopwatch. If under vacuum, permeate flow was measured with either a mass flow meter (FI-03)
or a rotameter (FI-04) before being sent to a vacuum pump.
Gas samples were piped directly to the sample valve of a Shimadzu model GC-8AIT gas
chromatograph equipped with a thermal conductivity detector. See "GC#1"in Table A2.2 in
Appendix 2 for analyzer details. The GC calibration was checked daily during permeation testing
using a certified standard gas mixture (1.00%0
2
, 3.09%N
2
, 4.01%CO, 11.0%C0
2
, balance H
2
).
The start-up procedure for the permeation rig was as follows:
Nitrogen was introduced to the membrane sweep inlet to purge the backside of the membranes.
The permeation vessel was purged with an inert gas, either argon or nitrogen, and heated to
250C at a maximum rate of 2C/min.
At 250C, hydrogen was introduced and the vessel temperature was then increased under a
hydrogen atmosphere to the desired operating conditions at a maximum rate of 3C/min.
Before permeation experiments started, the nitrogen sweep to the membrane was stopped. The
reactor gas composition was measured by gas chromatograph and confirmed to be 100%
hydrogen. A continuous flow of hydrogen was maintained to the reactor.
Operating conditions were then stabilized and flux testing started.
With an equimolar mixture of hydrogen and nitrogen in the permeation vessel at 545C, no nitrogen
was found in the hydrogen permeate for all seven membrane panels. It is believed that the nitrogen
detection limit of the gas chromatograph is approximately 0.001%(Li, 2005).
2.4.1 Effect of Hydrogen Partial Pressure
Experiments were conducted on the first membrane fabricated (panel A) to find the partial pressure
exponent that best described the hydrogen flux for the ICFBMR panels. From equation 2.5, the
hydrogen flux driving force is proportional to the difference in the hydrogen partial pressures to an
exponent, n:
As discussed previously, the theoretical value for the partial pressure exponent (n) is
l
A, assuming that
hydrogen diffusion through the metal is the rate-controlling step. This may not be the case for very
thin composite membranes, where external mass transfer and diffusion through porous pore supports
44
may contribute a significant resistance. Exponents close to 1 can be expected for very thin
membranes (Tong et al., 2005). Many researchers have found that an exponent of V i accurately
describes hydrogen permeation (e.g. Holleck, 1970). Despite this, deviation from Sievert's law (n =
V i ) has been reported, ascribed to such factors as surface effects, surface poisoning and grain
boundaries (Ward and Dao, 1999). Some previously reported values for the partial pressure exponent
in thick film palladium include 0.62 (Morreale et al., 2003), 0.68 (Hurlbert and Konecny, 1961) and
0.72 (Roy, 1998).
In order to find the partial pressure dependence of the ICFBMR membranes, experiments were
carried out in the permeation rig at 545C with high pure hydrogen (Praxair UHP 5.0) in the
permeation vessel. The hydrogen partial pressure driving force over the membrane was varied by
changing the vessel total pressure, which is also equal to PHh, or by adjusting the hydrogen partial
pressure on the permeate side, PHI. The permeate hydrogen partial pressure was varied using a
dilution sweep gas, or by lowering the permeate pressure with a vacuum pump:
No sweep gas: Initially, the permeate stream was pure hydrogen (no sweep gas) at atmospheric
pressure. The reactor pressure ( PHh) was then varied from 133 and 204 kPa.
Sweep gas: The vessel pressure was held at 170 kPa. The permeate stream was maintained at
atmospheric pressure, but nitrogen sweep gas was fed to the backside of the membrane to dilute
the permeate, thus reducing the hydrogen permeate partial pressure (PHI)- The hydrogen
concentration in the permeate was varied from 64 to 92%.
Vacuum, no sweep gas: The vessel pressure was held at 170 kPa. No sweep gas was used and
therefore the permeate was pure hydrogen. The absolute pressure of the permeate was reduced
using a vacuum pump to between 33 to 67 kPa.
Table A2.3 in Appendix 2 summarizes the flux test data. The flux on the panel varied between 0.78
and 3.18 SLM during the tests. The flux data are plotted as a function of the square root of the
hydrogen partial pressures in Figure 2.13.
45
0.003
0.002
o
E,
x
CM
I
0.001
0.000
y = 1.06E-05X
R
2
= 0.985
No sweep
A Vacuum
O Inert sweep
50 100 150 200 250
Partial H2 pressure, high
A
0.5 - Partial H2 pressure, low
A
0.5 (Pa
A
0.5)
Figure 2.13: Hydrogen flux on Panel A as a function of difference between square root of the
hydrogen partial pressures (545C, pure hydrogen in permeation vessel)
Linear regression of the above flux data gives good agreement, and it is tempting to conclude that the
data confirm a partial pressure exponent of V i . However, the data also fit a range of pressure
exponents, with values of 0.45 to 0.65 all giving good regression coefficients. The range of
differential pressures tested was too low to permit an adequate analysis, and it cannot be definitely
concluded from the above data that n = V i is valid. However, the range of hydrogen partial pressures
in the ICFBMR pilot reactor is close to the range in Figure 2.13, and it was therefore concluded that
an exponent of V i can be practicably applied. If a partial pressure exponent of V i is assumed, the slope
of above regression line is equal to:
slope =kH
A ,
- e xp( - ^)
R T
(2.7)
The membrane thickness, r, is 50E-6 m and the permeation temperature in the above experiments was
818K. If we assume values for k
H
and E
p
of 3.43E-7 mol/m s Pa
05
and 9,180 J/mol respectively (Li,
2003), a value for the permeation area,v4
mem
, can be calculated by rearranging equation 2.7. Using the
regression slope in Figure 2.13 of 1.06E-5 mol/s Pa
05
, the membrane area, A
mem
, is calculated at
0.0189 m
2
. This value is 73%of the sintered metal area previously calculated from the panel
geometry (0.0258 m
2
).
46
2.4.2 E f f e c t o f T e m p e r a t u r e
Panel A was flux-tested in the permeation rig to see the effect of temperature. For these tests, the
permeation vessel was under pressure (238-376 kPa) and contained pure hydrogen. The permeate
stream was at atmospheric pressure (101 kPa). The membrane flux was measured for a range of
temperatures (475-564C). Figure 2.14 summarizes the results of this testing (see Table A2.4,
Appendix 2 for data). As expected, the hydrogen flux increases with increasing temperature and
increasing reactor pressure.
0.003
3
0 0 0 2
o
E.
x
3
X 0.001
0.000

X

X
o
X

X
0376 k P a vessel pressure
XC307 k P a vessel pressure
0 238 k P a vessel pressure
.720 740 760 780 . 800
Temperature (K)
820 840 860
Figure 2.14: Permeation of Panel A at three different upstream pressures with permeate at 101 kPa
Flux data from Figure 2.14 are transformed into an Arrhenius plot in order to estimate the activation
energy (E
p
) and permeation constant (k
H
) for the membrane. From equation 2.7 with an exponent ()
of V i , the slope and intercept of regression lines in the Arrhenius plot are:
slope
:
R
A
intercept =l n[ k
H
- J =- ( P ^- P ^) ]
T
(2.8)
(2.9)
47
.7.0 J
1.15E-03 1.20E-03 1.25E-03 1.30E-03 1.35E-03 1.40E-03
Inverse temperature (1/K)
Figure 2.15: Arrhenius plots of hydrogen permeation on Pd
75
Ag
25
Panel A (475-564C) at three
different upstream pressures with the permeate at atmospheric pressure
Values for E
p
from the three slopes are calculated to be 13,600, 12,900, 14,800 J/mol, giving an
average of 13,800 J/mol. From the three regression lines in Figure 2.15, and assuming a panel
permeation area of 0.0189 m
2
, an average value for k
H
of 2.2E-7 mol/m s Pa
0 5
was obtained. It should
be noted that the span of the temperature range of the permeation data (475-564C) was quite limited,
and did not cover some of the higher temperatures tested in the ICFBMR pilot plant (up to 650C).
The quality of the data in Figure 2.15 above, especially for the lower curve, does appear to be slightly
inconsistent.
Many researchers have measured the hydrogen diffusion activation energy of pure palladium, with
values of 22 kJ/mol (Holleck, 1970) and 13.8 kJ/mol (Morreale et al., 2003) commonly utilized for
application to the temperature range of interest in the ICFBMR pilot reactor. There is considerable
spread in the activation energies reported for palladium and palladium alloys, likely due to hydrogen
diffusion being a multi-step process, in which small changes in surface chemistry and testing
conditions can significantly affect experimental results (Ward and Dao, 1999).
Values for the hydrogen diffusion activation energy in Pd
7
oAg
3
o of 2.2, 6, 6.3, 9.4 and 23 kJ/mol have
been reported (Amandusson et al., 2001). Holleck (1970) predicts E
p
= 23,500 J/mol for Pd
75
Ag
25
.
From literature reviews and testing, MRT has found the values k
H
= 3.43E-7 mol/m s Pa
05
and E
p
=
48
9,180 J/mol to reasonably describe hydrogen flux through their membranes fabricated with Pd
75
Ag
2
5
foil (Li, 2003).
Given the variability in the published data, it is perhaps not surprising that the experimental values
obtained for k
H
and E
p
differ from the values recommended by MRT. It should be noted that the
estimate for k
H
depends on the active permeation area (A
mem
), which is not known accurately for the
ICFBMR panels. The recommended MRT values for k
H
and E
p
were therefore employed in
subsequent permeation modelling.
2.4.3 Variation between Membranes
All seven ICFBMR panels were tested to establish their flux characteristics. Although fabricated in
an identical manner, it became apparent that the seven membranes displayed significant differences in
hydrogen permeation, despite being made in a near-identical manner. This is highlighted in Figure
2.16 below, which shows permeation data for six panels over the temperature range of 460 to 570C.
For these tests, the permeation vessel contained pure hydrogen and was held at 300 kPa. The
permeate streams were at atmospheric pressure, with no sweep gas.
5.0
4. 0
E
3.0
0. 0
Theoretical fl ux ( area = 0. 0258 m2)
Mem#1 XMe m# 3 + Me m# 4
Mem#5 AMe m# 6 OMe m# 8
450 475 550 575 500 525
Temperature (C)
Figure 2.16: Flux data for six membrane panels as a function of temperature
(vessel pressure at 300kPa, pure hydrogen, permeate at 101kPa, see Table A2.5 for data)
The measured H
2
permeation on the highest flux panel was more than twice that for the lowest flux
panel. There were no obvious reasons for the wide variation in permeation behaviour. The two most
likely factors are likely to be:
An insufficient thickness of alumina separating the palladium from the metal substrate may have
led to metal-to-metal interdiffusion and bonding, reducing the area available for permeation.
4 9
Surface poisoning from the bonding procedure. Subsequent work by MRT has demonstrated that
post-bonding oxidation with air can remove some reversible surface poisons (Li, 2005).
The permeation data in Figure 2.16 show similar dependence of flux on temperature for all six panels.
It was concluded that the best way to characterize the varying permeation of the ICFBMR panels was
to calculate an effective membrane area (A
e
jj) for each membrane based on permeation equation 2.4:
(2.10)
With values for r, k
H
and E
p
of 50E-6 m, 3.43E-7 mol/m s Pa
05
and 9,180 J/mol respectively, the
effective membrane area was calculated for each of the seven ICFBMR membrane panels. The
resulting values are summarized in Table 2.4 below. Also shown is the "batch number" in which each
membrane panel was bonded in the permeation bonding vessel. The six numerically labelled panels
were installed in the ICFBMR pilot reactor.
Table 2.4: Calculated effective membrane areas for ICFBMR panels
Membrane
j
Effective membrane area (m )
Fraction of expected
Batch
A
0.0189
73% 1
1
0.0121
47% 2
3
0.0101
39% 3
4
0.0075
29% 3
5
0.0142
55% 3
6
0.0059
23% 2
8
0.0101
39% 2
During subsequent ICFBMR experiments, the permeation characteristics of the six membranes were
periodically tested. The relative permeation of the six panels stayed roughly the same (as shown in
Chapter 6), but the absolute permeation values (or the calculated effective membrane area) did vary
somewhat.
2.5 Conclusions
Although ceramics have been studied for high-temperature hydrogen membranes, palladium and its
alloys have been more commonly used. Dense Pd-based foils have the potential to produce very high
hydrogen purity from membrane reactors.
A e f f ~
e x P ( - ^ ) ( P l
5
- P H ? )
50
50 um thick Pd
75
Ag2 5 foil was used to prepare seven planar membrane panels using MRT's
proprietary procedures. The membranes proved to be pinhole-free and produced a pure hydrogen
permeate in permeate rig tests. Sievert's law could accurately describe the measured membrane flux,
though the value of the partial pressure exponent QA) was not statistically proven over the
experimental pressure range. The measured hydrogen fluxes on the membranes were somewhat lower
than expected, and varied among the panels. Surface defects, such as wrinkles and bulges, were
present on a number of the membrane faces. Six of the membrane panels were subsequently installed
in the ICFBMR pilot plant, as detailed in Chapter 4.
51
Chapter 3. Cold Model Testing
As the hydrodynamics of the ICFBMR system were difficult to test in the pilot plant, a
Plexiglas cold model was build to simulate and test reactor operations. This chapter
discusses some of the hydrodynamic considerations for the ICFBMR design, including
particle characteristics and the scaling parameters between the cold model and the hot
reformer. Solids circulation rates in the ICFBMR were determined for a range of gas flow
rates and for three different membrane panel configurations. Testing clearly indicated that
slotted membrane panels are preferred to solid (non-communicating) panels. Data from
helium tracer experiments supported the circulation rates calculated from physical
observations. Calculations indicate that adequate solids circulation rates can be achieved
in the ICFBMR system to support reforming operations.
3.1 Introduction
Some limited hydrodynamic and gas distribution testing was attempted on the I CF B MR pilot plant
reactor. However given the complexity of the pilot reactor, it was difficult to undertake a systematic
hydrodynamic study on the effects of reactor geometry and flow conditions. A Plexiglas cold model
mock-up was therefore assembled and tested. Direct observations of internal solids circulation within
the column were possible with the Plexiglas system. Solids circulation is a key feature of the
I CF B MR concept, as this transports heat from the oxidation (exothermic) reactions in the top dense
zone and splash zone to the reforming (endothermic) reactions in the core permeation zone.
The cold model tests were carried out in a 0.285 m diameter Plexiglas column operating at ambient
conditions. A Plexiglas core draft box was installed in the column containing seven vertical panels to
represent hydrogen permeable membranes. The column was filled with fresh fluidized catalytic
cracking (FCC) catalyst and fluidized with compressed air. Solids circulation and gas distribution
were studied with three different panel geometries for a range of feed gas flow rates.
52
The objectives for the c old model work included:
Qualitative evaluation of fluidization and solids flow patterns;
Quantification of solids circulation as a function of gas flow and panel geometry;
Determination of whether membrane geometry (solid vs. or slotted panels) leads to flow
instability;
Evaluation of gas distribution using helium gas tracing.
3.2 Fluidized Beds
Fl ui di zed beds are used extensively in the c hemic al and process industries for reaction, drying,
particle contacting and numerous other applications. The I CF B M R is an example of gas-solid
fluidization, but there are also important industrial applications for liquid-solid and gas-liquid-solid
systems. Some of the reasons for using a fluidized bed for gas-solid catalytic reactions over a fixed
bed include improved heat transfer, good solids mi xi ng, lower pressure drop and the ability to move
particles within the reactor or between vessels. Gas contact time tends to be low in fluidized beds,
and therefore they are mainly applied to fast reactions. A major drawback of using a catalytic
fluidized bed reactor in many cases is the non-plug flow gas movement through the reactor.
The fluidization regimes for a gas-solid system (gas upflow) are shown in Figure 3.1. As gas flows
upward through a bed of particles, gas initially trickles through the bed with no movement of the
particles (fixed bed). A s the flow of gas is increased, the pressure drop over fixed bed increases, until
the pressure drop over the fixed bed matches the weight of the particles. A s flow is increased past this
point, bubbles form and rise through the bed (bubbling regime) and the bed behaves like a fluid. The
bubbles contain few particles. The gas flow in the bed is divided into the bubble phase and the dense
particulate phase, where the close-packed particles are supported by an upward flow of interstitial
gas. The amount of gas in the dense phase is approximately equal to the flow of gas needed for
minimum fluidization, with the balance of the gas flow partitioning to bubble phase. Particles are
entrained in the wakes of the rising bubbles, causing solids mi xi ng.
Bubbles tend to coalesce and grow as they rise through the bed. I f the rising bubble diameter is close
to that of the c olumn, slugging may occur. A s the gas veloc ity is further increased, the bubbling
regime gradually undergoes a transition to the turbulent regime, in whi c h the gas voids tend not to
look bubble-like, but rather are unstable, transient and streaky. I f the gas veloc ity is further increased,
the bed enters the fast fluidization regime, where a dilute suspension surrounds solids clusters.
53
BUBBLING AGGREGATIVE FLUIOIZATION
INCREASING U. c .
Figure 3.1 : Gas-solid flow regimes (Grace, 1986)
The previous FMBR work by Adris (1994) and Roy (1998) operated their fluidized bed in the
bubbling regime with superficial gas velocities of the order of 0.03 m/s. The ICFBMR concept
requires higher operating gas velocities in the reactor core, in the range of 0.1-0.5 m/s, in order to
generate a sufficient internal circulation of solids within the reactor.
3.3 Cold Model Hydrodynamics
3.3.1 Scaling Parameters
The pilot ICFBMR reformer operates at high temperatures and pressures, conditions that cannot be
duplicated in a Plexiglas system. The ICFBMR cold model attempts to simulate operation of the
ICFBMR pilot plant, but fluidization characteristics of a system operating at high temperature and
pressure can change considerably from ambient conditions and with different powders (Yates, 1996).
Scale-up of gas-solid fluidized beds is an area of considerable study (e.g. Kelkar et al., 2002,
Knowlton et al., 2005). Despite this, there remains a high degree of uncertainty in fluidized bed scale-
up, especially when applied to reacting systems (Matsen et al., 1997). Numerous researchers have
proposed dimensionless hydrodynamic scaling parameters for cold modelling of gas-solid fluidized
beds, including Glicksman (1984, 1993) and Horio et al. (1986).
The gas superficial velocity in the core of the ICFBMR pilot plant ranges from about 0.05 to 0.3 m/s.
At these velocities, the particle Reynolds numbers are low (<4). In this hydrodynamic region, viscous
forces are more significant than inertial forces. Starting with the Ergun equation, Glicksman et al.
(1993) recommended equivalence of the following seven dimensionless parameters for scale-up of
gas-solid fluidized beds at low Reynolds numbers:
54
U
2
P
P
U L
x
G
p
,(/> , dimensionless particle size distribution (3.1)
g
L
' P/'U
m
/ L
2
' p
p
U
Here L is a generic bed dimension. If L in the first term is replaced with d
p
, the particle Froude
number is obtained.
Roy and Davidson (1989) found that it was not necessary to match the particle-to-fluid density ratio,
the second term above, when scaling gas-solid fluidized beds with low Reynolds numbers. However,
this term is retained to extend the scaling to higher Reynolds numbers.
The fourth term represents the ratio of any two dimensions and hence geometry scaling. It (Li/L
2
)
could be applied as the ratio of bed height to particle diameter (H/d
p
) or bed diameter to the particle
diameter (D/d
p
) (He et al., 1997). As the cold model is geometrically similar to the pilot reactor, this
scaling term is subsequently ignored.
The fifth term includes the solids flux in the column (G
p
), and was originally envisioned for a
circulating fluidized bed. In a conventional bubbling bed, the solids flux is very nearly zero, and thus
this scaling term can be neglected. In the ICFBMR, however, there is a flux of solids up the core of
the reactor, and down the annulus, and therefore this term must be retained.
The sixth term in equation 3.1 is the particle sphericity. The sphericity of the three types of catalyst
particles used in the cold model and ICFBMR pilot reactor is not exactly known, but observations
through a microscope indicate a range between 0.6 to 0.8. The sphericity factor is ignored in further
scaling calculations. The particle size distributions of the three powders studied in this work are
included in the next section, and were judged sufficiently similar, that on a non-dimensional basis this
term could also be eliminated.
The three areas of vigorous fluidization in the ICFBMR concept are (i) above the distributor plate, (ii)
inside the reactor core box, and (iii) above the core box. The feed gas distributor is drilled to match
the cross-section of the core box, so that the superficial velocity above the distributor is similar to that
in the core box. The fluidized area above the core box, which includes the oxidant distributor, does
not significantly influence the key system hydrodynamic parameters of interest, such as solids
circulation and voidage in the core. Therefore the superficial gas velocity in the core (U
core
) is applied
where a velocity is needed in the scaling parameters.
With the above simplifications, the seven Glicksman scaling terms are reduced to the following four
terms for the ICFBMR cold model:
55
Ucore Pp Ucore ^'p.core
There are other considerations when using a cold model to simulate the hydrodynamics of a hot,
reacting system such as the steam reforming process:
Temperature entry effects: If cold gas is introduced into a hot reactor, thermal gradients may
develop that cannot be simulated in an isothermal cold model. In the ICFBMR pilot reactor, the
feeds are preheated to within 50-100C of the core reactor temperature (typically 550-650C) and
become quickly equilibrated with the circulating solids, so this is not likely to be a significant
concern for this system.
Change in molar flow rate: The volumetric gas flow in a fluidized bed reactor can change due to
changes in the number of moles due to reaction or absorption onto the bed solids. In the
conventional SMR process, three moles of feed gas react to form five moles, which results in an
increase in flow of 50% if a feed steam-to-carbon ratio of 3 is used. This represents a significant
increase in superficial gas velocity as the reaction proceeds, difficult to simulate in a cold model.
In the ICFBMR system however, hydrogen is removed from the reactor core through the
membrane surfaces. If 2/4 moles of permeate hydrogen per mole of feed methane were recovered,
there is actually a small decrease (-10%) in the number of moles in the reactor core, and
therefore a constant superficial velocity in the cold model is a reasonable assumption.
3.3.2 Catalyst Powder Characteristics
In order evaluate the relevance of the cold model testing to the operating conditions in the ICFBMR
pilot plant, hydrodynamic characteristics and scaling parameters are evaluated for the two catalyst
powders used in the ICFBMR pilot plant (crushed nickel oxide SMR catalyst and autothermal (ATR)
catalyst) as well as FCC catalyst used in the cold model work. The measured cumulative size
distributions for the three powders are shown in the Figure 3.2. The average particle diameters (d
p
) of
the SMR, ATR and FCC catalyst powders were found to be 107, 87 and 62 um respectively,
calculated from the average particle size (d
pi
) and mass fraction (*,-) on each sieve according to:
The SMR (NiO on alumina) material has a wider particle distribution than the other two catalyst
powders. This is not unexpected as this material was obtained by crushing and screening
56
conventional SMR catalyst pellets, whereas the ATR and FCC powders were designed and produced
to be fluidized bed catalysts.
300
Particle diameter (pm)
Figure 3.2: Cumulative size distributions for the three catalyst powders studied
The fluidization pressure drop vs. superficial velocity curve for the FCC catalyst in air is shown in
Figure 3.3. The corresponding curves for the SMR and ATR catalyst powders in atmospheric air are
shown in Appendix 3.2 (Figures A3.2.9 and A3.2.10). The minimum superficial fluidization
velocities (U
m
J) of the three catalyst powders in atmospheric air were found to be 6.0E-3, 3.0E-3 and
2.6E-3 m/s for the SMR, ATR arid FCC powders respectively.
o o
o 0
o o o
o
o
o
o
0 0.0025 0.005 0.0075 0.01
Superficial velocity (m/s)
Figure 3.3: Cold model pressure drop vs. superficial air velocity for the FCC
~ 1.5
n
0_
X.
a.
o
k.
a
o>
3
(A
<fl
CD
1.0
0.5
0.0
57
Table 3.1 summarizes a number of fluid and particle characteristics for the cold model (FCC) and the
pilot reactor operating with two different catalysts (SMR and ATR catalyst). The reformer operating
conditions were assumed to be 600C and 1200 kPa, typical operating parameters for the ICFBMR
pilot plant. The Archimedes number for the Geldart A-B powder boundary is calculated from an
equation propose by Grace (1986).
A r ^ = 1..03E6I
P
P
-Pf
-1.275
(3.4)
All of the catalysts had an Archimedes number below Ar
AB
boundary value, so all may be considered
Geldart Type A powders. The particle Reynolds number at minimum fluidization (Re
mf
) in air was
estimated from another equation proposed by Grace (1982).
Re
mf
yjc
2
+C
2
Ar - C,, where C, = 27.2, C
2
= 0.0408
(3.5)
For FCC, the calculated U
m
/ in air using the following equation matched the measured value.
However, the predicted U
m
f for the SMR and ATR catalysts in air was roughly twice the measured
value.
The Reynolds numbers at minimum fluidization are low for all of the powders, so the minimum
superficial fluidization velocity can also be estimated by simplifying the Ergun equation to a
relationship suggested by Kunii and Levenspiel (1991):
mf
150// l-
(3.6)
mf
Given the error in predicting the minimum superficial fluidization velocity of the SMR and ATR
catalysts in air from equation 3.5, U
mf
at reformer conditions were predicted by scaling the U
mf
measured in atmospheric air by the density and viscosity ratio using equation 3.6:
l ^/ \cFBMR L^V l
'(Pp-pf)
M
ICFBMR (Pp-Pf).
(3.7)
58
Table 3.1: Cold model and pilot reactor properties and characteristics
Variable Units ICFBMR Pilot Plant Cold
Model
P
a
r
t
i
c
l
e

d
a
t
a

Bed material - Ni oxide on
alumina
ATR on
alumina
FCC
catalyst
P
a
r
t
i
c
l
e

d
a
t
a

Particle density (p
p
) kg/m
3
2,150 2,090 1,600
P
a
r
t
i
c
l
e

d
a
t
a

Loose packed inter-particle voidage - 0.5 0.5 0.45
P
a
r
t
i
c
l
e

d
a
t
a

Average particle diameter (d
p
) m 107E-6 87E-6 62E-6
F
l
u
i
d

d
a
t
a

Temperature C 600 20
F
l
u
i
d

d
a
t
a

Pressure, absolute kPa 1,200 101
F
l
u
i
d

d
a
t
a

Fluidization gas - Reformate mixture Air
F
l
u
i
d

d
a
t
a

Gas molecular weight kg/kmol 15 29
F
l
u
i
d

d
a
t
a

Gas density (pj), assuming ideal gas kg/m
3
2.48 1.20 F
l
u
i
d

d
a
t
a

Gas viscosity (p) Pas 2.90E-5 1.74E-5
<
Archimedes number
- 76 40 15
<
Archimedes number for A-B powder
boundary, Eqn. 3.4
- 185 192 107
<
Geldart powder classification - A A A
Predicted Re
m /
ri n air, Eqn 3.5 - 0.077 0.040 0.011
U
mf
in atmospheric air (predicted) m/s 0.010 0.067 0.0026
U
m
f in atmospheric air (measured) m/s 0.0060 0.0030 0.0026
U
m
f at reforming conditions, Eqn. 3.7 m/s 0.0036 0.0018 -
Re
m
f at reforming conditions - 0.033 . 0.013 -
As the gas velocity in a bubbling bed is increased, the onset of the turbulent fluidization flow regime
may be reached (see Figure 3.1). The superficial gas velocity at the initial transition to turbulent
fluidization (U
c
) is defined as the point at which the standard deviation of pressure fluctuations
reaches a peak. Ellis (2003) found that the value for U
c
for FCC particles in the same 0.285 m ID
column used in the cold model testing, but with no internals, ranged from 0.35 to 0.6 m/s, depending
on the bed height. Core superficial gas velocities in this range were studied in the cold model testing,
though the system geometry is differed markedly from that in the cited work. The channels in the
cold model reactor core have a much lower hydrodynamic diameter that the main column. Decreasing
reactor diameter is reported to increase U
c
, but column internals may cause a decrease in U
c
(Bi et al.,
2000).
Table 3.2 indicates the values of the retained dimensionless Glicksman scaling parameters for the
reforming catalysts in the ICFBMR pilot plant and the FCC powder in the cold model, assuming a
superficial core velocity (U
core
) of 0.1 m/s. The first hydrodynamic scaling term is the Froude number.
At a core superficial velocity of 0.1 m/s, the Froude number for the cold model is slightly larger than
for the reforming catalysts. A core velocity of only 20%lower in the cold model would produce a
similar Froude number to the values for the reforming catalysts.
59
Table 3.2: Cold model scaling parameters at a core superficial velocity of 0.1 m/s
Scaling Variable
ICFBMR Pilot Plant
Cold Model
Term Bed material
Ni oxide on ATR on FCC catalyst
alumina alumina
-
Fluid
Reformate at 600C, 1,200 kPa Ambient air
1
Particle Froude number in core
9.5 12 16
2 Density ratio (p
p
l p
f
)
866
842 1,330
3
Velocity ratio (U
core
1U
m
j)
28
56 33
4 Gp,core / Pp U
core
TBD TBD TBD
The values for the density ratio, the second scaling term, for three powders are indicated in the Table
3.2 above. The cold model ratio (FCC / air) is greater than for the two reforming catalysts at reformer
operating conditions, but lower than would be the case if the cold model column was filled with
alumina. In any event, the low particle Reynolds numbers in these systems likely means that this
scaling term can be ignored (Roy and Davidson, 1989).
The minimum fluidization velocity (U
m
j) of FCC in air (2.6E-3 m/s) is close to the predicted U
m
fOf
the two reforming catalysts at the assumed ICFBMR operating conditions (3.6E-6, 1.8E-6 m/s).
Therefore the third scaling term (U
cor
JU
m
j) can be kept approximately constant if the same core
velocities are used in the cold model as used in the ICFBMR pilot reactor. The fourth term scaling
term could not be calculated with confidence at the outset as it includes the solids flux in the reactor
core. Finding the solids flux at different operating flow conditions was a key goal of the cold model
work.
From the above scaling parameter analysis, it is concluded that it is appropriate to use similar core
velocities in the cold model as those in the ICFBMR pilot plant.
3.4 Experimental Apparatus
3.4.1 Reactor Geometry
Figure 3.4 contains a schematic of the Plexiglas cold model system adapted from a column previously
constructed for work by Abba (2001) and Ellis (2003). The main section of the column had an inner
diameter of 0.285 m. There was a small disengagement section at the top of the column (0.4 m ID).
The core box was hung in the column by a rod and was centred with setscrews. Panels were installed
into the core box from the bottom, secured by grooves and bolts. There was a 100mm gap between
the main distributor and the bottom of the core box to permit circulation of solids from the annuli to
the core. The column was filled with approximately 95 litres of FCC solids to give a settled bed depth
of 25 mm above the top of the core box. In order to reduce electrostatic charges, approximately 0.5
60
wt%of Larostat 519, an antistatic agent, was added to the FCC solids. In addition, copper tape was
applied to the exterior of the column and then grounded, together with any installed metal fittings and
flange bolts. Assembly instructions and photographs of the cold model system are provided in
Appendix 3.1.
Compressed building air was used for fluidization. Air flow to the column was manually controlled
with throttle valves and measured by rotameters. The column operated at atmospheric pressure and
ambient temperatures. Air exited the column via two cyclones and a filter baghouse before being
vented to atmosphere. As in the ICFBMR pilot reactor, gas was introduced into the cold model
column through three separately controlled distributors:
Main feed distributor (0-750SLM)
Secondary feed distributor to four annulus sections, see Figure 3.4 (0-30 SLM in total)
Oxidant distributor to splash zone (0-280SLM)
There was a concern that solid panels (membranes) may lead to hydrodynamic instability within the
core box. If the panels are solid (i.e. there is no gap allowing communication among the channels),
gas and particles cannot move between the channels and the system is equivalent to the tube side of a
heat exchanger. If only gas were to flow up the core box, the pressure drop over the channels would
lead to a stable distribution of gas. As each of the channels in the ICFBMR reactor is identical, even
distribution of gas through the core would be expected if no solids were present. However, for a
fluidized gas-solid system, solids can distribute non-uniformly among the channels, leading to many
possible gas-solid flow patterns that could satisfy the system pressure drop (Bolthrunis et al., 2004).
Variable solids loading between the channels would then lead to a redistribution of gas between the
channels, making it unlikely that each channel would contain an identical flow of gas and solids. In
the extreme, solids could block one of more channels, leading to very uneven gas and solids flow.
Uneven flow of gas in the membrane core could lead to varying hydrogen partial pressures for
adjacent channels and still satisfy the pressure balance requirement. This could result in hydrogen
flux variations between the membrane panels, causing underutilization of the installed membrane
surface and reduced hydrogen recoveries.
61
Plexiglas co ld mo del co lumn
- 285 mm ID main sectio n
- 400 mm ID expanded
3260 mm
Building AJj>-
740 mm
04,
Oxidant
Feed
Annulus for
return of
particles
Seco ndary
distributo r (4)
Secondary
Feed
Main
distributo r
Cyclo nes
Baghouse
Column
Vent
Main
Feed
Cyclo ne bottom valves clo sed
Splash zo ne / f reebo ard
Oxidant distributo r
Unexpanded bed height
(25 mm abo ve co re box)
Plexiglas co re box
(178 mm square)
with 7 membrane panels
Channels (8) for passage of
gas and particles
e-
Multiple
pressure
transmitters
Pressure Data
Acquisition
Figure 3.4: Cold model system schematic
62
Figures 3.5 shows a plan view of the cold model column. The core box was centred in the column.
Seven panels were slotted into the core box, creating eight identical channels, in which the bulk of the
column gas flowed upward, carrying entrained solids. Solids return to the bottom of the column in the
four outer annular quadrants. In order to investigate fluidization stability within the core, three
different panels were separately tested in the cold model: solid (i.e. no gaps, slots or holes), vertically
slotted and horizontally slotted panels (Figure 3.6). The panels were 100 mm shorter than the outer
core box. This created a 50 mm long entry and exit zone within the core box, similar to the ICFBMR
pilot plant membrane assembly.
The area open to inter-channel flow for the vertically and horizontally slotted panels is the same, 9%
of the area of the solid plate. The horizontally slotted panel is similar to the membrane assembly in
the ICFBMR pilot reactor. The tabs on the vertically slotted panels are to hold the panel within the
grooves of the core box. The vertically slotted panels were installed in alternating direction (slot on
the right, slot on the left, etc.), creating a serpentine-line connection within the core box (Figure
A3.2.7, Appendix 3.2). After insertion into the core box, the width of the communicating slot in the
vertically slotted panels was 21 mm.
Figure 3.5: Plan view of cold model core box and panels (solid panels shown)
63
All dimensio ns in mm
All panels are 6.4 mm thick
k164H
1422
typ' fo r all
3 panels
164-
Vertical slo ts for
co mmunicatio n
between flow
channels
1
C
-139-4
51
typ'
A . S ol i d
(impervious)
panel
R 10-
-164H
Ho rizo ntal slot for
co mmunicatio n
between flow
channels
A
38
typ'
254 typ'
(SIS
typ'""
B. Vertically
slotted panel
C. Horizontally
slotted panel
Figure 3.6: Front views of cold model panels
The diameter of the cold model column (0.285 m) was approximately twice that of the ICFBMR pilot
reactor (0.135 m). A larger diameter column was selected for the cold model work in the hopes of
reducing the influence of wall effects and the numerous pressure impulse lines in the column annulus.
The cold model channel width and height were identical to those in the pilot reformer, but the
channels and channel lengths were doubled, with the result that the area in the core box available for
flow in the cold model was approximately four times greater in the cold model. The fractions of the
total column cross-section open to flow in the annulus and core were roughly the same in the cold
model and pilot reactor.
The "annulus turn" area indicated in Table 3.3 is the curtain flow area under the perimeter of the core
box, where solids from the annulus flow into the core region. Note that the annulus turn area is larger
than the annulus area by a factor of approximately 2 for the cold model and a factor of 4 for the
64
ICFBMR pilot plant. The hydraulic diameters in Table 3.3 are calculated from flow area and the
wetted perimeter:
4 A
D
H
= (3.8)
perimeter
Table 3.3: Comparison of cold model and ICFBMR reactor geometries
Cold Model Pilot Reformer
Column inner diameter (m), D 0.286 0.135
Core box height (m) 1.52 1.52
Channel width (m) 0.014 0.014
Channel length (m) 0.158 0.083
Channel height (m) 1.42 1.42
Number of channels 8 4
Free flow area in core box (m
2
), A
core
0.0188 0.0048
. j
Free flow area in annulus (m ), A
an

0.0354 0.0074

1
T
Flow area of annular gap (m ), A
gap
0.064 0.032
Fractional free core area of column 28% 31%
Fractional annulus area of column 53% 51%
Hydraulic diameter of channel (m) 0.026 0.025
Hydraulic diameter of annulus (m) 0.087 0.039
Hydraulic diameter of turn (m) 0.20 0.20
. ~
Solids volume in column (m )
0.095 0.020
Uniform flow of gas and solid within the core of the ICFBMR is very much desired in order to
maximize the hydrogen membrane flux and minimize temperature variations within the vessel. It may
be possible to design a gas distributor that would inject identical flows of gas into all core box
channels. However, this may still not lead to an even distribution of gas and solids among the eight
channels and implementing a complex design in a high temperature reactor would be challenging. A
simple gas distributor is very much preferred.
The distributor plate installed in the cold model is shown in Figure A3.2.3, Appendix 3.2. It is a
simple orifice plate distributor equipped with a mesh screen to prevent back sifting. The orifice holes
are 5.8 mm in diameter on a 39 mm triangular pitch. Only the distributor area directly under the core
box contains these holes, as this directs the main gas flow into the core box, rather than into the
annular region.
A small amount of secondary air aids in fluidizing particles descending in the outer region, increasing
the solids circulation. Aeration tubes were therefore installed near the centre of each of the four
65
annular quadrants. A photograph of the complete secondary distributor assembly is provided in
Figures A3.2.1 and A3.2.2, Appendix 3.2. The four quadrants of the column each had a 12 mm
diameter vertical tubular distributor, with twelve 0.8 mm diameter holes at three levels. The holes
were drilled at a steep angle to direct the air downward at an angle of 20 to the vertical. A fine metal
screen was then wired to the outside of the tube to prevent back sifting into the orifice holes. Figure
3.7 shows details of the bottom section of the cold model column.
The oxidant distributor was a 12 mm OD horizontal tube drilled with two opposing rows of 13 holes
(each 1 mm in diameter) oriented horizontally (see Figure A3.2.4 in Appendix 3.2). The distributor
rube was fed from both ends to improve gas distribution through the orifices. As in the ICFBMR pilot
reactor, the oxidant distributor was perpendicular to the core panel channels, and the gas distribution
interval was limited to the width of the core box. Pressure data drop for the three cold model
distributors (Figures A3.2.5 and A3.2.6) appear in Appendix 3.2.
Upper ho les
(two ro ws o f
4 x 0.8 mm)
Annular
no zzle (4)
Lo wer ho les
(4 x 0.8 mm)
Seco ndary
feed
Co re bo x
12>
115
4 5
1
' Mesh
screen |
100
-285 co lumn ID-
178
14
Panels (7)
Flo w channels (8)
V
Entry
regio n
Main distributor ~
Windbox
Annular
do wnf lo w
regio n
Main feed
All dimensio ns in mm
Figure 3.7: Details of bottom section of cold model column
66
3.4.2 Instrumentation
3.4.2.1 Pressure and Flow
The flows of air to the various parts of the column were measured with four rotameters (Table
A3.2.1, Appendix 3.2). Flow readings were manually recorded during experiments. The calibrations
of these feed rotameters were confirmed with a dry gas meter.
Absolute and differential pressure transducers (Omega PX140) were connected to various ports along
the wall of the cold model via V" (6.4 mm) impulse lines made from plastic or stainless steel tubing.
A fine stainless steel screen (38 pm) was glued to the tip of each impulse line to prevent solids back-
sifting. Impulse lines were connected to the core box to measure the pressure within the eight
channels at three elevations:
Bottom of core box (230mm above main distributor)- flow channels 4, 5.
Mid-height of core box (862 mm above main distributor) - flow channels 1 to 8.
Top of core box (1494 mm above main distributor) - flow channels 4, 5, 6.
Due to the cold model geometry, the core box impulse lines were very long (7-10 m). All of the core
box impulse lines were grouped together in the north and south annular quadrants. Pressure
transducer details and their locations within the cold model column are presented in Appendix 3.2
(Table A3.2.2, Figures A3.2.7 and A3.2.8).
The pressure transducers were connected to a computer via an A/D converter (DAS08-EXP32). The
pressure signals were monitored and logged on the computer by means of one of the two programs
listed below. The two data acquisition programs could not be operated concurrently.
An existing Visual Basic program logged pressure at a relatively low frequency (<1 Hz). These
data were used to provide trends of steady state pressure signals over longer periods of time,
usually five or more minutes. The program converted the pressure transmitter signals (0-5 VDC)
to pressure (kPa) with user-inputted calibration values.
An existing in-house program created in LabTECH by Dr. C.J. Lim logged data from the
pressure transducers at a higher frequency (48 Hz) for short periods of time, typically one minute.
These data were used to analyze dynamic pressure fluctuations within the column. The program
logged the pressure transducer voltage, which was then converted to pressure during post-run
analysis.
67
3.4.2.2 Heli um Traci ng
A number of steady-state helium tracer tests were carried out to investigate how gas was circulated
and distributed within the fluidized bed. Typically this involved continuous injection of helium into
one part of the bed, usually through the oxidant distributor, and determining its concentration at
points in the vessel through a thermal conductivity detector (TCD). The system is shown
schematically in Figure 3.8.
The helium flow to the column was measured with a rotameter (FI-05) at a supply pressure of 307
kPa. A calibration curve for the helium rotameter appears in Figure A3.2.11, Appendix 3.2. A
vacuum pump was installed to draw sample gas and atmospheric air through the TCD. As the TCD
signal was very sensitive to changes in flow, it was critical to maintain the same sample and air flow
when taking data. This was achieved by throttling the sample gas inlet valve to maintain the TCD
pressure, obtained by a water manometer, at the desired value. The sample and reference gas flows
were measured with two rotameters (FI-06 and FI-07). The TCD signal voltage was logged in the
system computer at a frequency of 0.2 Hz. The recorded TCD voltage was converted to the helium
concentration in the post-run data treatment.
Figure A3.2.12 (Appendix 3.2) shows a typical TCD calibration curve obtained during the testing.
The calibration generally produced a very linear response, so long as the flow rates of sample and
reference air were maintained at the same conditions for all tests. However, the TCD signal response
was not always reproducible from the previous day's work, and the TCD was therefore re-calibrated
each morning. The procedure for the TCD calibration was as follows:
The TCD system was warmed up for at least 90 minutes prior to starting calibration.
A constant flow of 250 LPM of air was maintained to the windbox to fluidize the column. No air
was added to the secondary or oxidant feed distributor at this stage.
TCD samples were taken from the column freeboard. The TCD signal was zeroed by adjusting
the amplifier and then monitored for 30 minutes to ensure a stable baseline.
Helium was introduced by increments into the main column feed upstream of the windbox to
produce a gas mixture of up to 15%helium in the column. The signal was allowed to stabilize for
10 minutes prior to recording the TCD signal.
A linear equation for the TCD response was developed and used for subsequent helium tracer
experiments. The zero of the TCD system was tested periodically throughout the day to check for
instrument drift.
68
Oxidant
distributor
Oxidant
f eed
Water
mano meter
I
< i >^ | - ( ^
TCD detecto r
- I X } -
Vacuum
Pump
Ref erence Air
Sample throttle
valve (multiple
sample points)
0-5 V DC

TCD Signal
Amplifier/
Co nverter
TCD Data
Acquisitio n
| Main
f eed
Figure 3.8: Helium tracer system for cold model column
3.5 Experimental Results
A series of experiments was carried out on the cold model column using the three different panel
geometries described above. The solid panels were tested first, followed by the horizontally slotted,
and finally the vertically slotted panels. The column solids were dumped after testing one panel
geometry, and then refilled once the core panels had been changed. All other system components
remained unchanged for the cold model tests. The main variables in the cold model experiments
were:
Main air flow to windbox
Secondary air flow to annular quadrants
69
Oxidant air flow to splash zone
Membrane panel geometry (solid, horizontally slotted and vertically slotted)
3.5.1 Fluidization Observations
Initially, the cold model column was filled with F CC solids to a depth of 50 mm below the top of the
core box, which contained the solid panels. It was observed that solids circulation did not start until
the total expanded bed height was above the top of the core box. In order to maintain solids
circulation at low feed rates, additional particles were added to the column to bring the settled bed
depth to 25 mm above the core box. This settled bed depth was maintained for all subsequent tests.
When the settled bed depth was initially below the top of the core box, it was observed that once the
flow of fluidization gas was stopped, several of the core channels were completely full and others
empty. This implied a poor distribution of gas and solids among the channels of the solid-panel core.
This maldistribution was subsequently confirmed by pressure data.
In general, the column operated very smoothly. As soon as the main flow of gas was initiated, gas
would flow up the reactor core and solids would start to circulate up the core and down the annular
regions. No net upward flow of solids in any of the annular regions was observable from the outside
in the range of column flows investigated. No significant bypassing of the main air flow to the
annular regions was noted during the testing. This implies that the simple orifice plate distributor of
the cold model was at least adequate for the system.
Circulation of solids improved significantly once a small flow of air was introduced to the bottom of
the annular regions through the secondary distributor. No bubbles were seen in the annular regions
until the secondary air flow reached ~10 S L M (0.6 NmVh). Assuming an even distribution of gas
throughout the annular region, 10 S L M corresponds to a superficial gas velocity in the annular region
of 0.005 m/s, roughly double the measured minimum superficial gas velocity (U
m
/) for the FCC
particles. Periodic bubbles were noted when the secondary air flow was increased to 20 S L M (1.2
NmVh), and more significant gas flow up the annulus was noted at 30 S L M (1.8 NmVh). Upward
bubble movement in the annulus was hindered by the downflow of solids, leading to occasional
stagnation and bubble flattening. No downward bubble flow in the annulus was observed. There was
very significant bubbling at a secondary air flow of 40 S L M (2.4 NmVh). The overall solids
movement at this flow was still downward in all quadrants, but there were regions where solids were
occasionally dragged upwards by air bubbles. The bubbles in the annulus region were visually
observed to be approximately 2 to 5 cm in diameter.
70
Numerous V " (6.4 mm) pressure impulse tubes were located in two of the annular quadrants (north
and south). In these quadrants, the solids flow was markedly lower than in the two empty annular
quadrants (east and west), sometimes even close to stagnant. It was also observed that impulse lines
in the north and south quadrants occasionally caused the gas bubbles to coalesce, allowing the
annular gas to bypass the particles and flow quickly upward.
The bed typically expanded by about 150-180mm above the initial settled bed depth, representing an
expansion of roughly 10%over the original settled bed depth. Bed expansion was slightly greater at
high feed rates, but was difficult to quantify due to the very vigorous fluidization in the splash zone
and adhesion of particles to the column wall.
Once the main feed flow increased to about 100 SLM, corresponding to a core gas superficial
velocity of 0.08 m/s, periodic sprays from the reactor core channels into the splash zone became
evident. At this feed rate, the height of the sprays above the expanded bed surface ranged from about
100 to 150 mm. As the main feed flow was increased, the frequency and height of the core sprays
also increased, with the spray height reaching up to 600mm above the bed surface at high feed rates
(> 600SLM, core gas superficial velocity > 0.48 m/s).
Solids carryover from the column only became significant when the total column flow exceeded
about 700SLM. At this feed rate, the superficial velocity in the main column was 0.18 m/s, and 0.09
m/s in the expanded column freeboard (0.4 m ID). The collected entrained solids appeared to be
mostly fines, however the particle size distribution was not analysed. The terminal velocity ((/,) of the
average diameter of FCC particles in the cold model was calculated to be 0.20 m/s, based on the
dimensionless terminal velocity (/,*) and dimensionless particle diameter (d
p
*) and an equation given
by Haider and Levenspiel (1989) for a particle sphericity of 1.
- l
18 0.591
2
+
/ J * \ 0 . 5
(d
p
y (d
p
)
(3.9)
3.5.2 Solids Circulation
A predictable, high solids circulation rate is key to the ICFBMR concept. Circulating solids transport
heat from hot zones, the reactor wall or oxidation zone in the upper reactor, to the reactor core. The
temperature decreases up the reactor core, as the main SMR reactions are endothermic. A high solids
circulation rate is therefore essential to ensure that the temperature gradient in the reactor core
remains low and that the temperature is sufficient for the reaction. Too low a temperature in the core
would reduce the hydrogen generation and recovery of the overall system:
71
Cooler reaction temperatures shift the SMR reaction equilibrium to the left (see Figure A 1.1,
Appendix 1), reducing the hydrogen partial pressure in the reactor.
Cooler temperatures reduce the rate of the reactions.
Cooler temperatures reduce the permeability of palladium alloys.
The solids circulation rate in the cold model column was estimated:
Through physical observations at the column wall, based on multiple measurements of the
downward solids velocity in each of the four annular quadrants at their widest section (north,
south, east and west);
Then averaging the annular solids velocity from the four quadrants;
Finally multiplying the average annular downward velocity by the total annular cross-sectional
area to obtain the solids flux.
The above assumes that the solids velocity throughout each annular compartment is uniform, i.e. the
same throughout the region as measured at the column wall. In reality, the solids flow was observed
to be slightly lower in the regions where the corners of the core box approached the column wall. The
solids flow is also likely slightly higher in the interior of the annular region, than at the column wall.
The overall error is likely to be small in view of these offsetting factors, probably <15%.
Solids circulation was not affected by flow of oxidant air added to the splash zone in the upper
reactor. Solids circulation was measured for the following three variables:
Panel type (solid, horizontally slotted and vertically slotted)
Main air flow to windbox (100-700SLM)
Secondary air flow to annular quadrants (10-40SLM)
The average downward solids velocity in the annulus was quite reproducible for a given set of
operating conditions. However, there was considerably variation in the solids velocity among the four
annular quadrants. Generally the east and west quadrants had significantly higher solids flow than the
north and south quadrants, presumably due to the presence of the pressure impulse lines in the north
and south quadrants. Figure A3.2.13 (Appendix 3.2) presents the ratio of the maximum to minimum
quadrant velocity for all data points taken during the cold model testing, plotted against the main air
flow to the column. The average maximum-to-minimum quadrant velocity of all the cold model data
points was slightly greater than 3.
72
Summary data of the solids circulation testing are presented in Figures 3.9 to 3.11 for solid,
horizontally slotted and vertically slotted panels. The lines on the three graphs are best-fit quadratics
and are shown to aid data viewing. The vertical error bars on these figures indicate the 95%
confidence interval (t-test) of the average annular solids velocity. It is possible that the error bars
underestimate the data variance, but the figures do show clear trends that are consistent for all three
panel types:
Solids circulation tended to increase linearly with the main feed flow up to about 300 SLM,
which corresponds to a superficial gas velocity in the core (U
core
) of 0.25 m/s.
Solids circulation tended to level off once the main feed reached -500 SLM (U
core
= 0.42 m/s).
Solids circulation increased significantly, even doubling in some cases, when the annular air flow
was increased from 10 to 20 SLM.
Solids circulation only increased slightly, or remained the same, when the secondary air was
increased from 20 to 30 SLM. Increasing the secondary air above 30 SLM did not increase the
solids circulation.
0.05
A
'o
o
ffi
>
</ >
u
Solid panels
<
o
o
100 200 300 400 500 600 700 800
Main air flow (SLM)
Figure 3.9: Average downward solids velocity in the annular regions with solid panels as a
function of main column flow and secondary air flow (Best fit quadratic line shown)
73
0. 05
E
0.04
o
o
CU
u> 0.03
!5
o
co
| 0.02
to
CD
D)
2 0.01
>
<
0.00
A 30 S L M annul ar ai r
20 S L M annul ar air
O 10 S L M annul ar air
Horizontally slotted panels
100 200
600 700 800
300 400 500
Main airfl ow (SLM)
Figure 3.10: Average downward solids velocity in the annular regions with horizontally slotted panels
as a function of main column flow and secondary air flow (95%confidence interval)
0. 05
1
0.04
u
o
cu
>
</) 0. 03
;o
o
I 0.02
c
c
CO
cu
CO
cu
>
<
0.01
0.00
30 S L M annul ar air
A 20 S L M annul ar ai r
0 1 0 S L M annul ar air
Vertically slotted panels
100 200 300 400 500
Main air flow (SLM)
600 700 800
Figure 3.11: Average downward solids velocity in the annular regions with vertically slotted panels
as a function of main column flow and secondary air flow (95%confidence interval)
Solids velocity data at an annular air flow of 20 SLM for the three different panel geometries are
plotted in Figure 3.12. The circulation for the vertically slotted panels was higher than for the other
two panels within the flow range of 200 to 600SLM. A best-fit quadratic curve for each panel type is
plotted.
74
0.050
so lid panels
O ho rizo ntally slo tted panels
0.000-I , 1 1 1 r- , , 1
0 100 200 300 400 500 600 700 800
Main air f lo w (SLM)
Figure 3.12: Average downward solids velocity in the annular regions with a secondary air flow of 20
S L M for all three panel geometries (95% confidence interval)
The data in Figure 3.12 are now transformed to an internal circulation rate in Figure 3. 13. The main
air flow is converted to a superficial gas veloc ity in the core, based on the total cross-sectional area
open to flow in the core (sum of the 8 separate channels) of 0.0188 m
2
. Annul ar solids velocity is
converted to a mass and volumetric flow, assuming a F CC bulk density of 880 kg/m
3
and an annular
cross-sectional area of 0.0354 m
2
. A s can be seen, the total internals solids circulation rate for the
vertically slotted panels reached a maximum of about 1.2 kg/s at a core veloc ity of about 0.5 m/s. The
circulation rates for the solid and horizontal slotted panels were slightly lower, and appear to have
levelled beyond a core veloc ity of 0.5 m/s.
75
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
Core superficial gas velocity (m/s)
Figure 3.13: Average annular solids flow rate with a secondary air flow of 20 SLM
for the three panel geometries
The curves in Figure 3.13 are nearly linear at relatively low superficial core gas velocities (<0.3 m/s).
The core gas velocities studied in the ICBFMR pilot plant fall within this range. The slope of the
linear section of the best-fit curves suggests that the volumetric flow of circulating solids is roughly
15 to 20%of the volumetric flow of the gas feed flow rate to the reactor core.
Excess air flow to the annular regions leads to more gas ascending in the outer quadrants, thus
bypassing the membranes in the reactor core. It is therefore desirable to minimize this flow, and the
above data suggest that 20 SLM annular air is an optimal value for the cold model configuration. 20
SLM evenly distributed over the annular area corresponds to a superficial gas velocity in the annulus
of 0.010 m/s, approximately four times the minimum fluidization velocity (U
m
j) for the cold model
system.
3.5.3 Pressure Data
A number of absolute and differential pressure transmitters monitored the cold model system. High
(48 Hz) and low (< 1 Hz) frequency pressure data were separately recorded for the three different
panel geometries at a variety of air flows. The low frequency data were used to investigate overall
bed properties, such as bed voidage and flow stability. The high frequency data were transformed into
76
the frequency domain to investigate hydrodynamic regime features such as slugging and onset of
turbulent fluidization.
3.5.3.1 Core Channel-to-Channel Flow Stability (Low Frequency Data)
Observations while operating the cold model with solid panels suggested that there were non-uniform
solids loadings among the core channels. Long-term pressure data from within the core channels
confirmed that the solid panel configuration led to unstable flow patterns among the 8 channels.
Some channels had much higher solids hold-up, or perhaps were plugged, compared to neighbouring
channels. This is demonstrated in Figure 3.14, where the absolute pressures in each of the eight core
channels were monitored over an extended period of time. The large number of data points makes
viewing of individual channel pressures difficult, but every channel is seen to have had episodes of
large pressure swings, representing significant variations in solids loading. This channel pressure
instability for the solid (impervious) panels was noted over all flow ranges studied. This instability is
quite different from Figure 3.15, which shows core channel pressure data for the horizontally slotted
panels at the same flow conditions. Note the substantial difference in ordinate scale of the two graphs.
3
o 5
in
channel 1
channel 3
- - channel 5
channel 7
channel2
-channel4
- channel6
-channel8
Solid panels, 480 SLM main, 20 SLM secondary air
10 15
Time (mins)
20 25 30
Figure 3
14: Absolute pressure measurements from the middle of the core channels with solid panels
(480 SLM main air, 20 SLM secondary air)
77
6. 5
o i
a
a.
o
<
5.5
/ ' w, . ' l
V
f V I '
V ';
t >
v

1
-A A .
w
V
V
Horizontally slotted panels, 480 SLM main, 20 SLM secondary air
10 15
Time (mins)
20 25 30
Figure 3.15: Absolute pressure measurements from the middle of the core channels with horizontally
slotted panels (480 SLM main air, 20 SLM secondary air)
When operating with the horizontally slotted panels, all channels were found to have nearly the same
pressure, with only small pressure fluctuations. The lower pressure curve, channel 5, is likely lower
than the others due to a small error in signal zeroing. Core pressure data for the vertically slotted
panels are not shown, but were very similar to those for the horizontally slotted panels. The slots
clearly improved flow distribution among the core channels compared to the non-communicating
solid panels.
3.5.3.2 Core Voidage (Low-Frequency Data)
It is important to estimate the voidage in the reactor core, as this aids in quantifying the catalyst
loading and volume available for reaction in the main reforming section of the ICFBMR. The voidage
in the core was estimated from the pressure drop within channel 4 over a height of 1.27 m for a
number of flow conditions. Figures 3.16 and 3.17 show the channel pressure drop as a function of the
main and secondary air flows for the solid panels and for the vertically slotted panels.
78
9
a
R
Q. o
Q .
O
t-
T3

k
3
in 7
in '
a>
a.
"aj
c
c
. c 6
O
03
Solid panels
y = -0.0027x + 8.18
R
2
= 0.900
m
i
A 30 SLM annular air
20 SLM annular air
O 10 SLM annular air
- Linear (20 SLM annular air)
100 200 300 400 500
Main Feed (SLM)
600 700 800
Figure 3.16: Pressure drop across channel 4 in c old model core with solids panels
(95% confidence interval)
8
a.
o
a
o
k.
3
cn 7
B) '
0>
L.
CL
~a
c
c
n
S 6
1
"
H
.
y = -0.0025x+ 9.06
^ R
2
= 0.992
tii
A
A 30 SLM annular air
20 SLM annular air
o 10 SLM annular air
Linear (20 SLM annular air)
Vertically slotted panels
100 200 300 400 500
Main Feed (SLM)
600 700 800
Figure 3.17: Pressure drop across channel 4 in c old model core with vertic ally slotted panels
(95% confidence interval)
The channel pressure drop data from the solid panel (Figure 3.16) are widely scattered and have
larger error bars compared to the vertically slotted panels due to periodic channel blockage and de-
79
blockage as described above. The data for the vertically slotted panels are much more consistent and
indicate that the voidage increased nearly linearly with the main gas feed flow. The channel pressure
drop decreased by 20%as the main air flow was increased to 700SLM, with the secondary air
maintained at 20SLM or 30SLM, corresponding to an increase in voidage. The voidage increased
slightly more (23%) over the same flow range when the secondary air was reduced to 10SLM. Data
for the horizontally slotted panels are presented in Figure A3.2.14 (Appendix 3.2) and are virtually
identical to the data for the vertically slotted panel presented in Figure 3.17 above.
3.5.3.3 Higher Frequency Pressure Data
Higher frequency pressure data were recorded from the cold model to investigate the fluidization
behaviour at various flow rates. Fast Fourier Transformation (FFT) was used to convert selected
pressure data from the time domain to the frequency domain. The frequency range of interest in
fluidized beds is usually 0 to 10Hz. As data collection below 0.5Hz is susceptible to signal noise, the
frequency range of interest for the cold model work was taken to be 0.5 to 10Hz. See Ellis (2003) for
a discussion of FFT data treatment of pressure signals.
Few significant conclusions could be drawn from the pressure-frequency data. Sample data are shown
in Figure A3.2.15 in Appendix 3.2. This figure presents absolute pressure spectra for core channel 4
with the solid and vertically slotted panels for a variety of flow conditions. No significant peaks are
noted for the vertically slotted panels. There is an increased frequency response for the solid panels at
approximately 1 Hz, perhaps indicating some degree of slugging in the channels. Because of the
ICFBMR geometry, the pressure impulse lines for the cold model pressure gauges were very long (7-
10 m), and this may have resulted in some dampening of the measured pressure fluctuations.
3.5.4 Helium Tracer Experiments
Helium tracer experiments were undertaken to investigate the movement of gas within the fluidized
bed for all three panels geometries types (solid, horizontally slotted and vertically slotted) under
different flow conditions. Two sets of tracer experiments were performed:
Helium was added to the oxidant air line and samples were extracted throughout the bed to
investigate recirculation of gases from the top to the bottom of the internally circulating fluidized
bed.
Helium was added to the bottom of a core channel and samples were then taken at various points
higher in the core to investigate gas mixing within the core.
80
The helium T CD response was very sensitive to flow, and thus care had to be taken to ensure that all
sampling was performed in a reproducible way. Even with this, there was considerable scatter in the
T CD results. Several tests were performed to check the reproducibility of the T CD system. Figure
3.18 shows the measured helium concentration at various locations within the c old model column
when the bulk helium concentration in the bed was zero and 3. 28%. There are deviations between the
measured and actual values beyond the standard deviation of the measured T CD signal. It was
concluded that the T CD data can be relied upon to detect trends, but that absolute values need to be
treated with a degree of caution. It should also be noted that the gas sample points in the core were at
the edge of the channel (see Figure A3. 2. 7 in Appendix 3.2), and therefore in some cases may not be
representative of the interior of the channel.
Figure 3.18: Measured helium concentration at various points in the c old model with 0% and 3. 28%
helium in the main feed for the vertically slotted panels
3.5.4.1 Helium Addition to Oxidant Distributor
In this series of tests, helium tracer was added to the c old model c olumn through the oxidant
distributor, located just above the top of the core box. The helium concentration in the oxidant air
supply ranged from 9 to 25%. Gas was then sampled to see how much helium was being circulated
from the top of the c olumn to lower points in the bed.
81
Gas from the annulus was sampled near the bottom of the four quadrants (225 mm above the
bottom of the core box).
Gas from the eight core channels was sampled near the bottom of the channels 4 and 5, mid-
height in channels 1 to 8 and near the top of the channels 4. to 6.
During the tracer tests, the main air flow was varied for all three panel geometries, whereas the
secondary air to the annulus was maintained at 20 SLM for all tests. A summary of all data is
presented in Table 3.4. Some notable trends include:
The concentration of helium in the annulus was typically close to the helium concentration at the
column exit, much higher than in the core. This is expected, as the air that is dragged down by the
annular solids is from the well-mixed zone in the upper column. In several of the tests with solids
panels and low air flows, the annular helium concentrations were close to the helium
concentration in the oxidant feed. Clearly gas mixing in the upper column was relatively poor in
these cases, and the gas dragged down by the annular solids was mostly from the oxidant supply.
Assuming that all of the main air feed reports to the core and knowing the average helium
concentrations in the annulus and core, the amount of gas dragged down by the annular solids
circulation can be estimated. The estimates are shown in Table 3.4. The average gas velocity in
the annulus should be less than the average particle velocity in the annulus by the value of U
m
fl
e
m
f. If bubbles in the annulus are ignored, the volumetric flow of gas (Qg,ann) dragged down by
the annular flow of particles is given by:
Q
s
,
ann
= U
ann
A
am
= (V
p
-^L)A
am
e
mf
(3.10)

mf
As U
m
f for the FCC (0.0026 m/s) is significantly lower than the range of measured particle
velocities (0.01 to 0.04 m/s), the effect of this gas slip is ignored. If a voidage of 50%in the
annular solids is assumed, the volumetric flow of gas dragged down in the annulus should be just
slightly less than the measured solids circulation, expressed in the same units. The helium tracer
data in fact supports this. In all but one run, the flow of annular gas circulation estimated from the
helium tracer data is within 30%of the solids circulation obtained by measuring the downward
velocity of the annular solids at the wall.
One key benefit claimed for the ICFBMR concept is that addition of air does not significantly
reduce the membrane flux, as the bulk of the nitrogen in the air quickly leaves into the freeboard
82
and beyond without affecting the hydrogen partial pressure in the reactor core where the
membranes are located. This feature is verified in the helium tracer data. In all but one run, the
amount of helium circulated to the core from the annulus was only approximately 10%of the
total helium added to the column. As the data from run #2 illustrate, however, it is clear that the
top of the column needs to be well mixed with uniform flow through the core to benefit fully
from this reactor feature.
The helium concentration measured at the top of the core channels tended to be higher than at the
middle. From this finding, it seems likely that some solids from above the core box were drawn
down into the upper regions of the core flow channels.
Measured helium concentrations in the core with solid panels tended to vary more than for the
slotted panels, especially for channels 1 and 8 at either edge of the core box. This is as expected,
as gases within the core channels can interchange with the slotted panels, but not with the solid
(impervious) panels. In addition, channels may plug when operating with the solid panels,
leading to uneven gas distribution, whereas the flow is much more uniform when adjacent panels
can "communicate"with each other.
83
Table3.4: Summary of cold model helium tracer results
(all %listed in table are vol%)
Core panel geometry Solid Danels Horizontally slotted panels Vertically slotted panels
Run number 1 2 3 4 7 6 8 9
Main airf l ow (SLM) 94 240 480 713 240 480 240 480
Seconday air flow (SLM) 20 20 20 20 20 20 20 20
Oxidant air flow (SLM) 70 70 140 210 90 155 70 140
Helium flow (SLM) 22. 7 22. 7 28.3 21.4 22.7 28. 3 22. 7 24. 2
Gas velocity in core (m/s) 0.09 0.23 0.46 0.68 0.23 0.46 0.23 0.46
[Helium] in oxidant supply 24 . 5% 24 . 5% 16. 8% 9. 3% 20. 1 % 15. 4% 24 . 5% 14. 7%
[Helium] in column exit 11. 0% 6. 4% 4. 2% 2. 2% 6. 1 % 4 . 1 % 6. 4% 3. 6%
Helium measurements [He] % St. dev. [He] % St. dev. (He] % St. dev. [He] % St. dev. [He] % St. dev. [He] % St. dev. [He]% St. dev. [He] % St. dev.
S
a
m
p
l
e

l
o
c
a
t
i
o
n

(
m
m

a
b
o
v
e

m
a
i
n

d
i
s
t
r
i
b
u
t
o
r
)

East quadrant - bottom (325) 27.91 2.20 20. 64 1.12 3.02 1.54 5.83 0.32 4.68 0.43 3.11 0.43 3.71 0.31 3.15 0.39
S
a
m
p
l
e

l
o
c
a
t
i
o
n

(
m
m

a
b
o
v
e

m
a
i
n

d
i
s
t
r
i
b
u
t
o
r
)

West quadrant - bottom (325) 33. 38 0.16 17.63 2.21 4.11 0.88 2.76 1.03 3.27 0.39 4.83 0.26 6.26 0.33 4.80 0.18
S
a
m
p
l
e

l
o
c
a
t
i
o
n

(
m
m

a
b
o
v
e

m
a
i
n

d
i
s
t
r
i
b
u
t
o
r
)

North quadrant - bottom (325) 29. 62 0.74 23. 40 0.29 5.70 0.71 5.06 0.41 4.00 0.21
S
a
m
p
l
e

l
o
c
a
t
i
o
n

(
m
m

a
b
o
v
e

m
a
i
n

d
i
s
t
r
i
b
u
t
o
r
)

South quadrant - bottom (325) 33. 59 0.08 19.08 2.29 4.61 4.11 5.11 0.40 3.03 1.44 0.96 0.31 4.68 0.36
S
a
m
p
l
e

l
o
c
a
t
i
o
n

(
m
m

a
b
o
v
e

m
a
i
n

d
i
s
t
r
i
b
u
t
o
r
)

Channel 4 - bottom (230) 15. 10 1.45 7.68 2.55 0.56 0.15
S
a
m
p
l
e

l
o
c
a
t
i
o
n

(
m
m

a
b
o
v
e

m
a
i
n

d
i
s
t
r
i
b
u
t
o
r
)

Channel 5 - bottom (230) 11.66 0.80 8.64 1.71
S
a
m
p
l
e

l
o
c
a
t
i
o
n

(
m
m

a
b
o
v
e

m
a
i
n

d
i
s
t
r
i
b
u
t
o
r
)

Channel 1 - mid height (862) 8.57 1.74 0.46 0.26 0.98 0.13 0.42 0.28 0.36 0.43 0.19 0.13 0.46 0.06
S
a
m
p
l
e

l
o
c
a
t
i
o
n

(
m
m

a
b
o
v
e

m
a
i
n

d
i
s
t
r
i
b
u
t
o
r
)

Channel 2 - mid height (862) 2.33 1.38 -0.58 0.16 0.02 0.23 1.46 0.11 0.18 0.07 0.10 0.09 0.13 0.14
S
a
m
p
l
e

l
o
c
a
t
i
o
n

(
m
m

a
b
o
v
e

m
a
i
n

d
i
s
t
r
i
b
u
t
o
r
)

Channel 3 - mid height (862) 5.48 0.33 0.62 0.19 0.21 0.04 0.41 0.05 0.60 0.14 0.60 0.09 0.71 0.08
S
a
m
p
l
e

l
o
c
a
t
i
o
n

(
m
m

a
b
o
v
e

m
a
i
n

d
i
s
t
r
i
b
u
t
o
r
)

Channel 4 - mid height (862) 2.90 0.40 0.39 0.22 0.16 0.04 0.56 0.15 0.37 0.09 0.35 0.09 0.36 0.12
S
a
m
p
l
e

l
o
c
a
t
i
o
n

(
m
m

a
b
o
v
e

m
a
i
n

d
i
s
t
r
i
b
u
t
o
r
)

Channel 5 - mid height (862) 5.10 0.76 0.54 0.19 0.58 0.12 0.32 0.13 -0.22 0.02 0.59 0.11 ' 0.73 0.13
S
a
m
p
l
e

l
o
c
a
t
i
o
n

(
m
m

a
b
o
v
e

m
a
i
n

d
i
s
t
r
i
b
u
t
o
r
)

Channel 6 - mid height (862) 4.11 0.89 0.51 0.23 0.21 0.10 0.39 0.14 0.30 0.06 0.57 0.11 0.54 0.16
S
a
m
p
l
e

l
o
c
a
t
i
o
n

(
m
m

a
b
o
v
e

m
a
i
n

d
i
s
t
r
i
b
u
t
o
r
)

Channel 7 - mid height (862) 1.36 0.19 0.11 0.16 0.00 0.13 0.54 0.12 0.26 0.05 0.67 0.15 0.31 0.08
S
a
m
p
l
e

l
o
c
a
t
i
o
n

(
m
m

a
b
o
v
e

m
a
i
n

d
i
s
t
r
i
b
u
t
o
r
)

Channel 8 - mid height (862) 4.21 0.09 1.86 0.20 0.37 0.20 0.58 0.16 0.24 0.10 2.56 0.59 1.47 0.22
S
a
m
p
l
e

l
o
c
a
t
i
o
n

(
m
m

a
b
o
v
e

m
a
i
n

d
i
s
t
r
i
b
u
t
o
r
)

Channel 4 - top (1494) 3.43 0.12 4.87 0.72 1.45 0.43 0.49 0.16
S
a
m
p
l
e

l
o
c
a
t
i
o
n

(
m
m

a
b
o
v
e

m
a
i
n

d
i
s
t
r
i
b
u
t
o
r
)

Channel 5-top (1494) 3.38 0.16 3.42 2.24 0.92 0.27 0.83 0.36
S
a
m
p
l
e

l
o
c
a
t
i
o
n

(
m
m

a
b
o
v
e

m
a
i
n

d
i
s
t
r
i
b
u
t
o
r
)

Channel 6 - top (1494) 4.34 0.98 1.26 0.29 0.38 0.08
Average of all quadrants - bottom 31.1 20. 2 2.47 3.9 0.81 4.8 1.43 3.7 0.89 4.3 1.90 5.0 1.80 4.2 0.76
Average of all channels at mid-height 4.3 2.23 0.49 0.68 0.32 0.33 0.58 0.36 0.26 0.23 0.70 0.78 0.46 0.41
Estimate of annular gas downflow (SLM) 64 69 50 46 31 39 60
Measured solids circulation (LPM) 14 39 64 71 36 55 51 82
Fraction of helium recycled 57% 10% 1 1 % 7% 5% 9 % 1 0%
3.5.4.2 Helium Addition to Core - Vertically Slotted Panels
An investigation into gas mixing with the reactor core equipped with the vertically slotted panels was
also attempted. For this set of experiments, helium was added to the bottom of channel number 4 for
a period of 10 minutes, and the helium concentration was monitored at locations higher up the core
box. The cold model operating conditions for the tests were:
Main air flow 240 SLM;
Secondary air 20SLM;
No oxidant air flow;
6.0SLM helium flow added to flow channel 4, 130 mm above the bottom of the core box.
The 10-minute helium addition test was repeated four times for four different core sampling points: at
top of channels 4, 5 and 6 and at mid-height of channel 8. See Figure A3.2.7 in Appendix 3.2 for the
plan view of the core box and the locations of the sample points. Results are presented in Figure 3.19.
Figure 3.19: Measured helium concentration (vol%) at different sample points in upper core box after
10 minute continuous injection of helium into bottom of channel 4 (vertically slotted panels)
As all sampling exhibited a system response delay of several minutes due to the long sampling lines
and low sampling flow rates, no conclusions on the dynamic response of the system could be drawn.
The average helium concentrations at the top of channels 4 and 5 were 2.2%and 2.1%respectively,
close to the concentration in the column exit. The average helium concentrations at the top of channel
6 and the middle of channel 8 were significantly lower, 0.8%and 0.7%respectively.
As noted above, the positions of the vertically slotted panels were alternated so as to create a back-
and-forth serpentine-line connection between the channels. The sample point for channels 4 and 5
were thus effectively on opposite sides of the same channel, so the similar helium concentrations are
Time after He injection (mins) Time after He injection (mins)
85
not unexpected. The sample points for channels 6 and 8 were several "U-turns"away from the
channel 4-injection point, clearly reducing gas dispersion. If the helium in channels 6 and 8 were due
solely to the circulation of gas from the annular regions, a concentration of roughly 0.4%would be
expected, so some dispersion of helium from channel 4 likely occurred through the intervening slots.
3. 6 Discussion
The cold model testing clearly showed that solid (i.e. impervious, non-communicating) membrane
panels within the core box led to poor gas-solid distribution among the core channels. Slotted,
communicating membrane panels greatly improve the uniformity within the core, and are thus
preferred in the ICFBMR design.
The pressure impulse lines in the north and south annular quadrants added flow resistance, and thus
these quadrants exhibited significantly lower solids circulation than the other two quadrants. Such
tubing and obstacles should be minimized, especially if external heating of the reactor is used, as this
will lead to non-uniform heat transfer to the annulus solids.
3.6.1 Solids Circulation
Increasing the main feed gas flow to the core draft box increased solids circulation up to a core gas
superficial velocity of approximately 0.5 m/s, at which point circulation tended to level off.
Increasing annular air from 10 SLM to 20 SLM led to a significant increase in the solids circulation
rate. A further increase in the annular air to 30 SLM resulted in only a marginal increase in solids
circulation, or in some cases, no significant change. The cold model testing clearly shows the
importance of independent control of the annular and main gas flows, especially if the reactor is to
operate at variable feed rates.
An annular flow of 10 SLM corresponds to a superficial velocity in the annulus (U
ann
) of 0.0051 m/s,
1.9 times U
m
f of the FCC particles. However, it is very likely that some of the air introduced to the
annulus did not flow up the annulus, but rather was dragged into the core draft box, as noted in earlier
ICFB studies (e.g. Song et al., 1997, Namkung, 2000). An estimate of the amount of annular gas
bypassing to the core is difficult to infer from the cold model data. Annular gas bypassing to the core
would be an important design parameter if the annular gas was to be chemically used in the annulus,
such as air for oxidation. In the ICFBMR design, however, the annulus gas can be compositionally
identical to the main feed (i.e. steam and methane) and transfer of the annulus gas to the core
improves utilization of the reactor feed. Bypassing of feed gas up the annulus would result in lower
utilization of natural gas for reforming and H
2
permeation, but this quantity is judged to be small
86
(<5%of total natural gas feed) and the annular gas would still be available for oxidation in the upper
reactor.
Of the four retained hydrodynamic scaling parameters discussed earlier in this chapter, only the last
term, Gpcore / pp Ucore, contains the solids flux (Gpcore). This scaling parameter suggests that a plot of
circulation flux vs. pp Ucore in the cold model should provide a reasonable estimate of that in the hot
reforming reactor. Figure 3.15 presented above showed the solids circulation rate (mpcore, kg/s) as a
function of the core superficial velocity (Ucore). Given an open area available to flow in the core (Acore
= 0.0188 m
2
), the FCC particle density (1,600 kg/m
3
) and assuming an annular voidage of 0.5, these
data are transformed into solids fluxes (see Figure 3.20 below).
0 200 400 600 800 1,000 1,200
Pro duct o f co re superf icial velo city and particle density (kg/m2 s)
Figure 3.20: Measured cold model solids flux in core draft box (Gpcore) for horizontally slotted and
vertically slotted panels vs. product of superficial gas velocity in core (Ucore) and particle
density (pp), with an annular air flow of 20 SLM
If the geometry of the cold model is maintained, the regression curves in Figure 3.20 are useful
design tools to estimate the solids circulation rate in the hot ICFBMR. Note that the calculated solids
flux is based on the cross-sectional area open to flow in the core (i.e. inner area of core draft box less
area blocked by panels). The catalyst particle density (pp) in the ICFBMR pilot reactor was
approximately 30%higher than that of the FCC particles in the cold model. This implies that in order
to achieve a certain solids flux, the required core velocity in the hot ICFBMR would be less than for
the cold model.
87
The question of what factors control the solids circulation rate remains. Several studies have been
conducted on fluidized beds or spouted beds fitted with draft tubes to generate an internal circulation
of particles similar to the ICFBMR concept. Most of these studies have used a configuration where
the annulus turn into the core draft tube restricts the flow, whether through orifices or by the gap
under the draft tube (i.e. Milne et al., 1992, Song et al., 1997, Shih et al., 2003). In this case, the
annular turn area (orifice or gap) is smaller than the annular area, and the pressure drop over the gap
between the annulus and the draft tube (AP
0
) determines the solids flow rate, G
p
(Song et al., 1997,
adapted from Judd and Dixon, 1978):
C
0
is the particle discharge coefficient, p
an
is the density of the annulus upstream of the gap or orifice
and D
H
is the hydraulic diameter. Equation 3.11 also indicates why, after a certain point, some
researches have found that the rate of solids circulation with additional annular gas levels off, as
bubbles in the annulus reduce the annular density (p
an
n), decreasing the density difference (AP
0
)
between the core and annulus (Song et al, 1997). However in our cold model, the annular gap area
(Agap) is almost twice the annular area (A
ann
) (r = 5.3); hence the pressure drop over the annular gap is
very low and thus equation 3.11 cannot describe the solids circulation. Figure A3.2.16 in Appendix
3.2 presents the measured annular pressure vs. the measured pressure in the bottom of Channel 4
corrected to the same elevation, and shows, as expected, that the annular pressure closely follows the
core pressure.
As shown in Figures 3.11 to 3.13 presented earlier, solids circulation increases significantly when the
annular gas flow increased from 10 to 20 SLM, but did not change significantly when it was
increased beyond 20 SLM. Clearly the flow of particles down the annulus and the annular turn into
the core, restricted solids flow at 10 SLM. Perhaps an increase in bubbles near the bottom of the
annular increased the mobility of solids as they turn into the vessel core. The extra annular air may
have also helped to prevent local defluidization in the annulus.
Figures 3.11 to 3.13 also clearly show a consistent trend of core velocity on solids circulation with all
three core panels tested. For a given annular air gas flow, solids circulation increased nearly linearly
with core gas superficial velocity up to approximately 0.3 m/s, after which solids circulation tended
to level out. In a conventional bubbling fluidized bed, solids are transported vertically within the bed
in the wake of the rising bubbles, as demonstrated in Figure 3.21.
(3.11)
88
Co lo rless
so lid -
Co lo red
so lid ~
7 7
Figure 3.21: Sketches showing solids entrainment in the wake of a rising bubble
(from Kunii and Levenspiel, 1991, after photographs from Rowe and Partridge, 1965).
If solids circulation up the vessel core is primarily due to this mechanism, the solids flux in the vessel
core (Gp
XO
re) could then be described as a function of the wake fraction of the bubbles (fw) and the
volumetric bubble flow up the vessel core (Q
0
).
p,core
= (U
core
- U
mf
)p
p
(!-*) U
corePp
(1 - e)
(3.12)
At core superficial velocities below 0.3 m/s, the fluidization flow regime is likely the bubbling
regime, with the wake fraction relatively constant. For most of the testing in the cold model, U
core

U
m
f, so the circulation rate is therefore approximately proportional to U
com
.
It is further postulated that as the core superficial gas velocity is increased above 0.3 m/s, a gradual
transition to turbulent fluidization occurs, and spherical-cap bubbles are increasingly replaced by
streaking voids (see Figure 3.1), whose carrying capacity levels off to a constant value.
As previously shown in Figure 3.13, the measured solids circulation for the vertically slotted panels
was higher than for the solid panels and the horizontally slotted panels. It is not known what factors
reduced the solids circulation in the horizontally slotted panels, but perhaps it is due to disruption of
the particle-containing wakes in the rising bubbles at the communicating gaps between the channels.
The solid panels demonstrated lower circulation rates than the vertically slotted panels. This is likely
due to periodic blockages of the core flow channels. Why the solid panels show a very slightly higher
circulation rate than the horizontally slotted panels is not known.
3.6.2 Other Geometry Aspects
Some geometric aspects that could be adjusted in the ICFBMR design, but were not tested, are as
follows:
Height of core box: In the ICFBMR design, the height of the core draft box is primarily set by two
parameters: the amount of membrane surface required for permeation and the design superficial gas
89
velocity in the core (U
core
). The height of the core draft box in the cold model, 1.52 m, is the same as
in the ICFBMR pilot reactor. Song et al. (1997) found that doubling the height of the draft tube in the
ICFB system from 0.3 to 0.6 m had a negligible effect on solids circulation. If the circulation rate up
the core depends on bubble wakes as suggested above, it follows that solids circulation would be
relatively insensitive to the height of the core box.
Ratio of annular and core draft box area: If a square core draft box is used in the ICFBMR, the
dimensions of the annulus are set, with the only adjustable parameter being the distance from the
corners of the core box to the column wall. Thus, if square core box is used in the ICFBMR design,
the ratio of the annular area to the core box area will be approximately equal to that of the cold
model. However, other core box geometries, such as a rectangular or circular draft tubes, may be
preferred, as this would allow the annular area to be reduced, thus shrinking the overall volume of the
reactor (see Figure 3.22). The cold model testing indicated that for a given annular gas flow, the
solids circulation rate is a function of the core velocity. However, it is not known how much the
annulus area can be shrunk before it starts to reduce solids circulation. Arrangement of planar
membranes in a non-rectangular draft tube is an additional challenge of the alternate designs, and
testing would be required to establish the solids circulation characteristics of the different geometries.
A. Square core B. Circul ar core C. Chord layout
(col d model )
Membranes \
(annulus)
Figure 3.22: Some alternative ICFBMR layouts
Gap between distributor and draft tube: The gap below the core draft box was 100 mm in the cold
model. As the gap area under the core box is larger that the annular area, there is unlikely to be any
significant improvement on solids circulation by increasing this distance. A very large gap could lead
to increased bypassing of core gas to the annulus and possible start-up issues. The "turn" of solids
from the annulus to the core may well restrict solids circulation, but it is believed that this resistance
could be better addressed with an alternate annular air distributor design.
90
Annular distributor design: The cold model had a relatively complex secondary air distributor. The
cold model design was chosen as it approximated the design of the ICFBMR pilot reactor, where four
small sintered plugs distributed the annulus gas. In many ICFB studies, a conical distributor has been
used (i.e. Milne et al., 1992, Chu et al., 2002, Marschall et al., 1999). Song et al. (1997) tested three
distributors similar to those displayed in Figure 3.23, and reported that the solids circulation for the
flat plate and conical distributor were similar, and higher than for the conical sparger. Intuitively, the
conical distributor appears to be a better design, and indeed Song et al. concluded that the conical
distributor equipped with tuyeres was the preferred arrangement. However, this was because less
bypassing of annular gas to the core was measured with this distributor (Song et al, 1997). In the case
of the ICFBMR, bypassing of annular gas to the core is not critical. If the conical distributor could be
modified with angled jets to accelerate the solids from the annulus to the core, an increase in
circulation might be possible (Xie, 2002), but may not merit the extra fabrication complication. More
study is needed
A. Flat plate B. Conical plate C. Ring sparger
Draft tube
t t t t t t /I I \
Annular
ring
t t
t
o
Annular
windbox
Main windbox
Figure 3.23: Alternate annular distributors, adapted from Song et al. (1997)
3.6.3 Design Implications
Higher design gas velocities in the core reactor reduce the overall reactor volume. The cold modelling
suggests that a design core velocity below approximately 0.3 m/s is appropriate, as this is the highest
gas velocity at which the solids circulation flux varies nearly linearly with velocity. Above 0.3 m/s,
the solids flux levels off, which would correspond to higher temperature gradients in the reactor core.
Of course the core reactor volume also need to be sufficient for the reaction kinetics.
Figure 3.24, generated from HYSYS simulations (see Chapter 6 for description), indicates the
expected temperature gradient from the bottom to the top of the ICFBMR core as a function of solids
circulation rate for one design condition producing 50 Nm
3
/h of permeate hydrogen. If the core
91
velocity in this case is specified to be 0.25 m/s, the flow area in the hot reactor will be nearly identical
to that in the core model (0.026 m
2
). As solids circulation increases, the temperature gradient in the
reactor core is reduced. The predicted normalized membrane area is also plotted on the figure. At
lower solids circulation rates, more membrane area would be required due to three phenomena:
At lower temperatures, the permeance of the palladium foil is reduced.
At lower temperatures, the SMR equilibrium is shifted towards reactants, reducing the hydrogen
partial pressure.
Though not accounted in the data presented in Figure 3.24, reaction kinetics are slower at lower
temperatures.
50 I 1 1.0
0 I , . . I 0.7
0 2 4 6 8
Catalyst sol ids circulation (kg/s)
Figure 3.24: Effect of solids circulation on core reactor temperature drop and normalized membrane
area (conditions: 50 NmVh H
2
, steam-to-carbon molar ratio = 3, methane feed to reactor = 25
NmVh, reactor pressure 1500 kPa, feeds preheated to 650C)
From the core velocity (U
core
= 0.25 m/s) and the reformer particle density (p
p
= 2,100 kg/m
3
), the
predicted solids circulation rate is calculated to be 1.4 kg/s for vertically slotted panels based on the
regression equation in Figure 3.20 presented above. As shown in Figure 3.24, the predicted
temperature gradient in the reactor core is approximately 10C, a very reasonable value given the
large heat input required to support the reforming process. Increasing the circulation rate beyond 1.4
kg/s results in only a marginal reduction in membrane area, indicating that appropriate solids
circulation rates can be achieved in the ICFBMR for the SMR process.
92
Chapter 4. ICFBMR Pilot Plant
This chapter provides the basis on which the ICFBMR pilot reactor was designed,
constructed and tested. Process flowsheets for the pilot plant are provided, both for
external reactor heating (conventional SMR) and with direct air addition (autothermal
reforming). A semi-industrial size reactor (135 mm ID) was constructed and integrated
into an existing pilot plant, which was upgraded with an improved control system. The
nominal design basis of the updated pilot plant was 100 SLM (6Nm
3
/h) of permeate H2,
although the six planar membranes installed into the newpilot reactor were insufficient to
produce this much hydrogen. The ICFBMR pilot reactor proved to be very stable to
operate. However the large scale of the equipment made reactor modifications, such as
internals and catalyst change-outs, challenging. In addition, lowcatalyst activity affected
the reactor performance for several experiments, resulting in the pilot plant test data being
somewhat incomplete and belowinitial expectations. The pilot testing did confirm the key
features of ICFBMR concept and showed the potential for the planar membranes to
withstand the fluidized bed reforming environment. H2 permeate purity was initially very
high (>99.999%, excluding N2) for up to -180 hours of testing, after which the purity
dropped to 99.8%. The hydrogen recovery relative to the feed natural gas was relatively
low(maximum of 1.17 Nm
3
H^/Nm
3
of natural gas), as was the maximum H2 production
(17.6 SLM or 1.06 Nm
3
/h), limited by the installed membrane area.
4.1 Introduction
As described in the previous chapter, cold modelling proved that the ICFBMR concept was viable
from a hydrodynamic perspective. The ICFBMR concept was tested in a large-scale pilot reactor. Six
of the new membranes described in Chapter 2 were integrated into the reformer system to investigate
their performance under actual operating conditions.
Much of the original pilot plant utilized in the work of Adris (1994) and Roy (1998) was re-used in
this work. An externally heated bubbling bed reactor (97 mm ID, 0.66 m tall) had been employed in
93
their tests, with small-diameter tubular membranes for hydrogen withdrawl. This reactor was too
small to house the new internals (core draft box, planar membranes) of the I CF B M R design, so a
larger reactor was designed and built.
4.2 I CF MBR Reactor
Comb i ni ng the process design requirements with mechanical engineering considerations and space
constraints made the design and installation of the new I CF B M R reactor a significant undertaking.
One of the main design challenges was the operating temperature of the reactor shell, as radiant
reactor heaters were to be strapped to the exterior of the reactor, potentially raising the wal l
temperature to values not applicable for stainless steels under the A S M E pressure vessel code. A s a
result, it was decided to house the I CF B M R reactor (V-02 in Figure 4.7, presented later in this
chapter) within a large carbon steel shell (V-01), whic h acted as the pressure vessel. A n automatic
system was designed to pad the carbon steel shell with nitrogen to a pressure approximately 100 kPa
higher than the operating pressure of the inner I CF B M R reactor. The inner I CF B M R reactor only saw
a small differential pressure, and thus could be mechanically designed to pressures much lower than
the external shell design pressure (3,450 kPag). Padding the external shell also ensured that any leaks
in the inner I CF B M R reactor would result in ingress of inert nitrogen, rather than egress of
flammable gases, such as methane and hydrogen, into the confined laboratory work space.
4.2.1 Process Design
Design of the new reactor was an iterative procedure, influenced by the capacity of the existing pilot
plant equipment, the characteristics of the new planar membranes and information gained during cold
modelling experimentation. The I CF B M R reactor was designed and supplied by Noram Engineering
and fabricated by Axton Manufacturing. The final design criteria for the new pilot plant were:
Feed rate: A s the maxi mum natural gas methane feed rate of the existing natural gas compressor
and mass flow controller was 50 S L M (3 NmVh), this became the design gas feed rate. Wi th this
gas feed flow and assuming a steam-to-carbon molar ratio of 3, a design steam rate of 150 S L M
(7.2 kg/h) was established.
Hydrogen production: A n economic reformer design should have product hydrogen recoveries
approaching 214 moles of permeate H
2
per mole of CFL, fed to the reactor. It was decided to
design the pilot system for a permeate hydrogen-to-methane feed ratio of 2, equivalent to 100
S L M (6 NmVh) of H
2
.
94
Heat input: The reactor was equipped with a new preheater, external reactor heaters to supply the
process heat required for conventional SMR operation, and an oxidant delivery system which
could supply air directly to the reactor for autothermal operation.
Mechanical: Although existing components of the pilot plant constrained the operating pressure
to 1,500 kPa, the reactor design was to be sufficient to permit the reformer to operate at
approximately 3,000kPa at 650C.
The above established the design envelope for the new system. Two process flow diagrams (PFDs)
were prepared, one showing operation with external heat input, and the other with direct air addition
(Figures 4.1 and 4.2 respectively). The autothermal PFD has an air addition rate equivalent to 0.4
moles of 0
2
per mole of C H 4 feed, slightly higher than that calculated to operate the reformer
adiabatically in the absence of heat losses. The PFDs indicate that steam was to be the membrane
sweep gas, but in practice nitrogen was used. The mass and energy balances presented in the PFD
stream tables were based on HYSYS simulations.
From the PFDs, the required heat input for the internal preheater and reactor heaters was established
at 3.0 and 6.7 kW respectively (external heating, conventional SMR mode). In order to account for
heat losses and facilitate start-up, these heaters were made significantly larger than the calculated
load.
The required membrane area to produce 100 SLM of hydrogen was calculated based on the
conditions outlined in the externally heated PFD (Figure 4.1) and the membrane flux equation 4.1:
= 0.35 m
2
(4.1)
for z 50E-6 m, Q = 0.0744 mol/s, k
H
= 3.43E-7 mol/m s Pa
05
, and
E
p
= 9,180 J/mol, T= 923K, P
Hh
= 297.7E3 Pa, P
Hl
= 50E3 Pa
In the above calculation, the H
2
partial pressure was assumed to be equal to the reactor exit H
2
partial
pressure (298 kPa). The permeate H
2
partial pressure was set at 50 kPa, assuming a 50%dilution of
the permeate stream with sweep gas. These H
2
partial pressure assumptions are slightly conservative,
as the H
2
partial pressure should be slightly higher in the lower sections of the reactor, and the
permeate H
2
partial pressure lower at the sweep end of the membrane panel. A permeation
temperature of 650C was assumed. Given a nominal permeation area of 0.0258 m
2
for each
membrane, -14 double-sided membrane panels would be needed to provide sufficient area. There
A e f f =- ^ - e x p ( ^ - P H D
ku RT
,0.5 >
95
were locations for 12 double-sided and 8 single-sided panels in the ICFBMR pilot reactor, but only 6
double-sided membranes were installed due to budget and time constraints.
4.2.2 Reac tor L ay out
The ICFBMR reactor is tall and narrow, resulting from two main criteria:
Diameter - set by fluidization velocity: As described in the previous chapter, cold model testing
indicated that the solids circulation was a near-linear function of the superficial gas velocity in
the core up to a value of approximately 0.3 m/s, at which point solids circulation levelled off. The
design core velocity for the ICFBMR pilot reactor was set at 0.3 m/s at the maximum design feed
rate (50 SLMC H 4 , 150 SLM H
2
0) and an operating pressure of 1,300 kPa. The design free core
area in the reactor was thus established at 0.0025 m
2
. The dimensions of the core box was set at
~85 mm square, and the reactor diameter was then fixed at 135 mm to fit the core box
comfortably within the reactor shell, leaving sufficient annular space at the corners of the core
box to permit solids to pass through the gaps.
Height - set by membrane area: The surface area of each ICFBMR membrane panel was 0.0258
m
2
, based on the panel geometry. Twelve panels of this area would give an installed reactor
membrane area of 0.31 m
2
, close to the value of 0.35 m
2
calculated above in equation 4.1.
However, as described in Chapter 2, the effective membrane area of each panel was in
significantly less than the geometrical permeation area.
Figure 4.3 presents the dimensioned layout of the ICFBMR reactor. The main components included:
A - Reactor shell: The reactor vessel was fabricated from stainless steel. Grade 310 was used for
the main 135 mm diameter section, as this component was exposed to the external heaters. All
other vessel components were grade 304 stainless steel.
B - Core draft box: A rectangular, open-ended duct housed the membranes.
C - Membrane panels: As indicated earlier, only six panels were installed in the reactor; the
balance of the membrane places were filled with stainless steel dummy plates. Each installed
membrane panel had separate reactor connections for sweep gas and hydrogen permeate. Sweep
gas entered the top of the membrane panel, counter-current to the up-flowing reactor gases,
whereas permeated hydrogen left the bottom of the panel.
D - Main feed distributor: Preheated reactor feed was introduced into the reactor through a simple
orifice plate distributor in which 49 - 1 mm diameter holes were drilled in a pattern to match the
area of the core draft box (see Figure A4.1.1 in Appendix 4.1).
9 6
FBMR SKID ICFBMR SKID
ELECTRIC
HEATER f l
Stream t 2 i
4 5 6 7 8 9 10 11 12 14 15 16 17 18 2 0 21 22 23 24 30 31 32 33
MOM Ho- 2.04 2.04
7.0a
7.65 5.12 9.I2 9.21 8.21 0.91 6.31 6.06
6.00
8.57 8.57 4.55 3.55 6. 66 4.55 4.86 5\4i
- 0.50
4.61 266 26S 361 361
MoxFlow kq/h
Volumetric Flow mi/h i.3d 6.22 0.007 6.U 0.56 1.39 1.25 2.76 0.14 0.31 6.60 6.6o 2.63 1.47
0.46 0.664
6. 66 6.665 5.96 27.62 4.94 6.665 0.20 6. 26 6.36 6. 36
Molar Flow kmol/h 0.13 0.13 0.39 0.39 0.52 0.52 0.47 0.47 0.05 0.05 0.00 0.00 0.45 0.45 0.23 0.22 D.00 0.27 0.27 0.54 0.28 0.26 11.4 11.4 20.1 20.1
cH4 mol fract 1 0.244 6,244 6.244 6.244
0.244 0.244
0.06b
0.665 0.126
CO 6.043
0.043
O.OBJ
C02 6.176 6. 175 6.341
H20 1 1 0.756 6.756 6. 736 0.756 6.756 6.756 0.486 0.4B6 0.006 1 1 1 0.500 6.056 1 1 1 1
N2 0.790
0.730
1
02 6,210
0.210
H2 0.229 0.229 0.443 0.500. 0.950
Vapour Fraction 1 0 0.124 6.376 1 1 1 1 1 i i 1 1 1 6 1
0
i - 1 1 0 6 6 6 6
Temperature *C 10 15 15 193 147 180 180 650 180 650 15 650 650 250 40 40 15 15 133 650 40 40 15 30 15 30
Pressure kPa (abs) 150 1350 1350 1350 1350 1350 1350 1300 1350 1300 1350 1300 1300 1300 1300 1300 2000 150 150 150 150 150 150 150 150 150
MW kq/kmol 16.0 16.0 1B.0 18.0 17.3 17.5 17.5 17.5 17.5 17.5 28.9 28.9 19.2 19.2 20.4 18.0 28.0 18,0 18.0 10.0 2.8 18.0 18,0 18.0 18.0 18.0
Density kq/m3 1.03 9.3 999 51.4 18.4 6.57 6.57 2.98 6.57 3.0 16.39 4.87 3.26 5.83 10.29 992 23.7 999 0.82 0.20 0.16 992 999 995 999 995
Viscosity CP 0.011 0.011 1.14
- -
0.013 0.0)3 0.028 0.013 0.028 0.019 0.045 0.030 0.018 0.015 0.65 0.017 1.1 0.013 0.024 0.0087 6.65 1.1 o.ao 1.1 0.80
THermol Cona. W/m K 0.032 0.033 0.60
- -
0.039 0.039 0.097 0.039 0.097 0.026 0.063 0.116 0.D67 6. 661 0.63 0.025 6. 60 0.027 0.18 0.1? 0.63 0.60 0.62 0.60 0.62
Heat Copacity kJ/kqX 2. 22 2.31 4.05 4.29 3.62 2.20 2.20 2. 72 2.20 2.72 1.04 1.13 2.18 1.93 1.66 4.04 1.04 4.05 1.95 3.51 10.2 4.04 4.05 4.04 4.05 4.04
Enthalpy kW -2.66 -2.66 -3i.ia -29.22 -31.8S -28.23 -25.41 -22.73 -2.B2 - 2 . 5 3 0.00 0.00 -21.41 -23.36 -9.66 -16.97 0.00 -21.41 -17.81 -14.98 -0.93 -20.15 -905.6 -902.2 -1591.2 -1585.1
NOTE I: OXYGEN / AIRDISTRIBUTORREQUIRED
NOTE 2:MULTIPOINTTHERMOCOUPLES REQUIRED
NOTE 3: PRESSURE TAPS REQUIRED
NOTE 4: MAIN. CORE riUlDIZATION CAS
NOTE 5: ANNULUS GAS
NOTE 6: HEATER DUTIES DONOTINCLUDEHEATLOSSES
INTERNALCIRCULATING
FLUIDIZEDBEDMEMBRANE REFORMER
PROCESS FLOWDI AGRAM
50 SLM CH4 FEED, 100SLM H2. NO OXIDANT ADDITION
50% SWEEP STEAM DILUTION
B-Z0B45-13B5
Figure4.1: Process flow diagram (external heating)
FBMR SKID ICFBMR SKID
NOTE * /?> /tf> NOTE 5
Stream 1 i 1 2 i 4 5 6 7 8 9 10 11 12 14 IS 16 17 18 20 21 22 2i 24 30 31 32 33
2.04 2.04 7.6fl 7.06 9.12 9.12 B.21 B.21 6.91 6.91 S.fiS S.65 17.23 17.23 12.69 5.14 5.66 4.86 4.Bb b.41 o.ao 4,61 286 361 361
7 S
Volumetric Flo*

l.9fl 0.218 6.007 6.41 673 1.3S 1.25 176 0.14 6.31 6.S3 1.76 4.34 2.43 0.89 6.665 0.00 0.005 5.96 27.62 4.94 0.005 0.29 0.29 0.36 0.36
Motor How kmol/h 0.13 0.13 0.39 0.39 O.S2 0.52 0.47 0.47 0.05 0.05 0.30 0.30 0.73 0.73 0.45 0.29 O.OO 0.27 0,27 0.54 0.28 0.26 15.9 15.9 20.1 20.1
CM*
1
mol Iroct 1 1 0.244 6.244 6.244 6.244 6.244 6.244 6.06S 6.665 6.065
6 0.022 6.622 6,635
Cb2 6.147 6.147 0.246
H20 1 1 0.756 6.756 6.756 6.756 0.756 6.756 6.3S3 6.393 6.667 1 1 1 0.500 0.050 1 1 1 1
N2 6.796 0,790 6.323 6.323 0.52S 1
02 6.216 6.216
H2 0.112 0.112 0.1B2 0.500 0.950
Vopour rraction 1 0 6.387 6.531 1 1 1 1 1 t 1 0 1 0 1 1 1 0 0 U 0 0
Temperature "C 16 i i 15 193 166 186 160 650 180 650 15 650 650 250 40 40 15 15 133 650 40 40 15 30 15 30
Pressure kPo (obs) i5o 1350 1350 1350 1350 1350 1350 1300 1350 1300 1350 1300 1300 1300 1300 1300 2000 150 150 150 150 150 150 150 150 150
MW ko/krrtol 16.0 16.0 18.0 1B.0 17.5 17.5 17.5 17.5 17.5 17.5 28.9 28.9 23.3 23.5 26.9 18.0 28.0 18.0 18.0 10,0 2,8 18.0 18.0 18.0 18.0 16.0
Density 1.03 9.3 999 17.1 12.5 6.57 6.57 2.98 6.57 3.0 16.39 4.87 3.97 7.09 13.60 992 23.7 999 0.B2 0.20 0.16 992 999 995 999 995
CP 0.011 0.011 1.14 _
-
0.013 0.013 0.028 0.013 0.028 0.019 0.045 0.033 0.021 0.018 0.65 0.017 1.1 0.013 0.024 0.0087 0.65 1.1 0.80 1.1 0.80
Thermal Cond. W/m K 6.032 0.033 0.60
-
0.039 0.039 . 0.097 0.639 6.69? 0.026 0.063 6.687 0.051 0.037 6.63 0.025 0.60 0.027 0,18 0.17 0.6J 0.60 0.62 0.60 0.62
Heat Capacity kJ/kg'C
i.ii
2.31 4.05 3.65 3.31 2.26 2.20 2.72 2.20 2.72 1.64 i.ii 1.64 1.49 1.20 4.64 1.04 4.05 1.95 3.51 10.2 4.04 4.05 4,04 4.05 4.04
Enthalpy -2.66 -2.66 -31.la -28.18 -30.85 -28.23 -25.41 -22.78 -2.82 -2.53 -0.03 1.60 -27.14 -30.13 -12.4a -22.48 0.00 -21.41 -17.81 -14.98 -0.93 -20.15 -1259.1 -1254.3 -1591.2 -1585.1
NOTf 1: OXYGEN / AIR DISTRIBUTORREQUIRED
NOTE 7: MULTIPOINT THERMOCOUPLES REQUIRED
NOTE 3: PRESSURE TAPS REQUIRED
NOTE 4: MAIN CORE ELUIDIZATION CAS
NOTE 5: ANNULUS GAS
NOTE 6: HEATEP. DUTIES DONOTINCLUDE HEAT LOSSES
NORAM INTERNALCIRCULATING
FLUIDIZED BEDMEMBRANEREFORMER
PROCESS FLOW
SO SLM CH4 FEED. 100SLM H2. AIRADOmON
SOX SWEEP STEAM DILUTION
B - Z 0B 4 5 - 13 9 6
Figure 4.2: Process flow diagram (direct air addition)
N2 sweep^>
(multiple)
H2 permeate)>
(multiple)
Reactor Exit
G: exit gas filter
A: vessel shell
settled catalyst bed height
E: oxidant distributor
C: membrane panels with sweep
inlet and permeate outlet
B: open ended core draft box
H: external reactor heaters
E: annular distributor
D: main distributor
Figure 4. 3: ICFBMR pilot reactor (dimensions in mm, not to scale
99
E - Secondary feed distributor: Preheated annular gas was distributed to the annular quadrants via
four Vi" (6 mm) OD stainless steel sintered metal plugs (20 um nominal pore rating, Mort
Corporation model 6500-
1
/4-V
/
8-20). A photograph of the assembled main and secondary
distributors is presented in Figure A4.1.3 in Appendix 4.1.
F - Oxidant feed distributor: Preheated air was added to the fluidized zone above the core box
through a VS" (13 mm) OD sintered Hastelloy C276 tube (50 mm long, 2 um nominal pore
rating, Mott Corporation). The oxidant distributor was installed horizontally in the reactor,
perpendicular to the membrane panels. Pressure drop data for the three feed distributors are
presented in Figure A4.1.2 in Appendix 4.1.
G - Exit fdters: Non-permeate reactor gases left the reactor via two tubular metal fdters made
from sintered stainless steel (300 mm long, 38 mm OD, 5 urn nominal pore rating, Mott
Corporation). These fdters ensured that only traces of catalyst solids left the reactor. The filter
pressure drop for a flow of ambient temperature nitrogen is presented in Figure A4.1.27,
Appendix 4.1.
H - Heaters: External heaters were clamped onto the reactor. Initially ceramic fibre heaters were
used. However, these failed during the initial pilot plant run, likely due to oil binders in the
insulation short-circuiting the heating wires. The original ceramic heaters were then replaced by
tubular heaters.
The total internal volume of the reactor shell is 0.045 m
3
. The volume of catalyst required to fill the
reactor to the top of the core draft box is approximately 0.021 m
3
. Detailed mechanical drawings for
the external pressure vessel (Figures A4.1.4 to A4.1.6), internal reactor (Figures A4.1.7 to A4.1.9),
internal preheater (Figure A4.1.10) and core draft box (Figure A4.1.11) are provided in Appendix 4.1.
ICFBMR reactor assembly instructions and installation photographs appear in Appendix 4.2.
A formal hazard and operability study (HAZOP) was conducted on the reactor design and pilot plant
modifications. The reactor and pilot plant were inspected by the MRT and CHBE safety committees
prior to operations.
4.2.3 Memb rane Assemb l y L ay out
Rather than risk damaging the palladium membranes in the initial commissioning runs, dummy
internals were initially installed in the reactor. These internals were made from carbon steel and were
dimensionally similar to the membrane assembly presented in Figures 4.5 and 4.6. However, the
dummy membrane panels were thicker (9.5 mm) than the actual membrane panels (6.3 mm) and had
100
no inter-channel communication slots. A drawing for the dummy internals is presented in Figure
A4.1.26, Appendix 4.1.
After commissioning, the carbon steel internals were removed and replaced with the membrane
assembly. Of the twelve membrane positions in the ICFBMR pilot reactor, membrane panels
occupied six spaces for a total of 0.15 m
2
membrane area, based on panel geometry. The balance of
the membrane spaces were filled with '/i " (6 mm) thick stainless steel dummy plates. It would have
also been possible to install six additional single-sided membranes on two of the reactor walls,
bringing the total possible installed membrane area to 0.41 m
2
, in excess of the 0.35 m
2
initially
estimated to produce the design pure H
2
flow of 100SLM.
Core box
:
4
3
A. Possible membrane positions B. Installed ICFBMR panels
Figure 4.4: Location of membranes in ICFBMR reactor (numbered items are installed membranes as
described in Chapter 2, "X" and "Y" are solid V*" thick stainless steel plates. Possible single-
sided membranes on two core box outside walls are not shown.)
Cold modelling (Chapter 3) experiments clearly showed that communication slots between the
membrane channels are preferred to solid (non-communicating) membrane plates. The membrane
panels in the ICFBMR were assembled with horizontal communication slots between panels, as this
maximized the width of the membrane panels. There were three vertical panel rows in the pilot
reactor, with the six membranes installed in the first and third row. The middle (second) panel row
was filled by a plate of stainless steel with no communication slots. Therefore, channels 1 and 2
101
communicated, and channels 3 and 4 communicated, but the middle plate prevented gas and solid
exchange between channels 2 and 3. In retrospect, it would have been preferable to have also had
communication gaps in the middle panel. Figure 4.4 presents a schematic of the membrane
installation showing the location of the six membrane panels described in Chapter 2.
The three membranes and one dummy panel were connected into a row (Figure A4.1.12) by three
"H" shaped pieces (Figure A4.1.15 in Appendix 4). This formed six communication gaps in the
assembly row, each with dimensions of 57 x 22 mm. The communication gaps accounted for 6.5%of
the total row area, slightly less than the 9%fraction in the cold model tests.
Figure 4.5 presents a plan view of the reactor internals. The flow channels within the core box were
identical (16 mm wide). The minimum gap for solids flow between the core box corner and the vessel
wall was approximately 8 mm, more than 60 times greater than the maximum catalyst particle size
used in the reactor (125 pm), large enough to prevent catalyst bridging (Grace, 1982). The three rows
of vertical membranes were held in place by a series of threaded rods. In order to prevent stainless
steel parts from contacting the palladium membrane surfaces, a thin graphite gasket was inserted
between the membrane and the stainless steel backing strip required to secure the panels. Detailed
drawings of the membrane assembly components are provided in Appendix 4.1 (Figures A4.1.12 to
A4.1.15). An end view photograph of the final membrane assembly prior to installation in the reactor
is presented in Figure 4.6.
Figure 4.5: Plan view of ICFBMR reactor internals
102
Figure 4.6: End view photograph of final membrane assembly
4.2.4 Reac tor I nstrumentation
The reactor instrumentation is summarized in the ICFBMR reactor piping and instrument drawing
(Figure A4.1.19 in Appendix 4.1). The two types of instruments used to monitor the ICFBMR
reactor were:
Thermocouples: Long, type K, multipoint thermocouples were inserted vertically downward into
the reactor from the upper reactor flange in order to measure temperature profiles in the annular
region, reactor core and reactor gas space. See Table A4.1.1 in Appendix 4.1 for full
thermocouple descriptions.
Pressure transducers: The reactor pressure (gauge) was measured in the vent space of the internal
vessel. Differential pressure taps were installed at several points in the reactor. See Table A4.1.2
in Appendix 4.1 for full transducer descriptions. Five sampling points were also placed in the
reactor. Three differential pressure transducers were used (Omega PX-750, 0-2.54m WC). The
sampling line tips were covered with a sintered stainless steel plug (nominal 20 pm, Mott 6500-
1/4-1/8-20) to prevent catalyst entry (see Table A4.1.3 in Appendix 4.1 for locations).
103
Instrument locations within the ICFBMR reactor are summarized in Figure A4.1.20 (Appendix A4.1).
Pressures and temperatures of the external pressure vessel were monitored to ensure that the reactor
operated within its mechanical design limits. Instrument measurements were logged in the control
computer twice per minute.
4.3 Pilot Plant Description
Figure 4.7 presents a process schematic of the pilot plant. The main feeds to the system are
compressed natural gas, deionized water and, if running ATR, compressed air. Table A4.2.4 in
Appendix 4.1 provides a description of the main equipment components. The main process blocks of
the pilot plant included:
Natural gas feed: Natural gas was first compressed to approximately 2,000kPa, then desulfurized
at ambient temperature in an adsorbent bed filled with CuO (8 wt%) impregnated into granulated
activated carbon (Calgon Sulfasorb-8, 4x10 mesh). A typical analysis of the natural gas supply
for the Vancouver area is shown in Table A4.1.5, Appendix 4.1. As the methane content is high
( > 95% ), the natural gas was assumed to be 100%methane for all process calculations.
| Sweep N2^-
from cylinders
jOxidation Air/-
f ro m cylinders
Natural gas^ ( V
frnm mai ns ^
Gas compressor
(C-1)
City water
Desulfurizer
(DSU)
Deionizer
Water
"pump"
(V302A/B)
(DIU)
Water
"pump"
(V302A/B)
Condenser (E-2)
Hydro gen^
to vent / GC
Figure 4.7: Pilot plant schematic
Off-gas ^>
to vent / GC
j Condensate^
to drain
104
Water feed: City water was deionized in a mixed-bed ion exchange system (US Filter, activated
carbon bed followed by two mixed resin beds). The water was then pressurized to approximately
2,000 kPa in V302A/B and metered to a preheat interchanger (E-l).
Reactor feed: Natural gas and steam were mixed, and then preheated in the external electrical
preheater (E-3) and then in an internal electrical preheater (H-l).
Reformer: The natural gas and steam reacted on the fluidized catalyst to produce a reformate
mixture (H
2
, CO, C0
2
, CH 4, H
2
0). The endothermic reaction heat was supplied by external
heaters or by direct air addition to partially oxidize the reactor gases.
Membranes: H
2
permeable membranes removed produced hydrogen directly from the fluidized
bed reformer. An inert sweep gas (N
2]
Praxair industrial grade, >99.995%) could be used to
enhance hydrogen permeation. The combined permeate H
2
flow from the active membranes was
measured with a dry gas meter (American Meter, model AM-250) before being vented to
atmosphere. The permeate H
2
was analyzed in a gas chromatograph ("GC #2" in Table A2.2 in
Appendix 2) by injecting from filled sample bags.
Off-gas treatment: The hot non-permeate reactor gases leaving the reformer were cooled to
ambient temperature and condensate was separated before the off-gas was vented. The off-gas
could also be sent directly to a gas chromatograph for analysis ("GC #1" in Table A2.2 in
Appendix 2).
Piping and instrumentation drawings (PIDs) for the pilot plant are presented in Figures A4.1.16 to
A4.1.18 in Appendix 4.1. The pilot plant was controlled by a programmable logic controller (PLC,
GE Fanuc, series 90-30), which ran both the control loops and the safety shutdown logic. The pilot
plant operator had access to the PLC program through a control computer, which ran a custom-built
program created using commercial HMI (human machine interface) software (Cimplicity). The five
operating screens from the HMI program used to operate the pilot plant are presented in Figures
A4.1.21 through A4.1.25 in Appendix 4.1. The main control variables in the pilot plant were:
Natural gas flow (mass flow controller).
Water flow (measured by a turbine flow meter, flow manually adjusted).
Oxidant air flow (mass flow controller).
Preheat temperature (adjusted by heater input).
Reactor temperature (adjusted by heater input or by air addition).
Reactor pressure (automatic control valve).
105
4.4 Pilot Plant Operation
Detailed operating instructions for the pilot plant are located in Appendix 4.3. The general procedures
to start-up the system are listed below. The shutdown procedure was a reverse of the start-up
procedure.
Start the control computer and PLC.
Open H
2
and N
2
gas cylinder supplies.
Pressurize external shells of preheater and ICFBMR reactor with N
2
.
Fluidize the ICFBMR with N
2
at low pressure (< 300kPa). .
Turn on the process heaters and slowly raise the reactor temperature at a rate of <2C/minute
until the bed reaches 250C.
Introduce H
2
, then raise slowly raise the reactor temperature to 500C at a rate of <3C/minute in
a N
2
/H
2
atmosphere.
If required, hold the reactor at conditions suitable for catalyst reduction.
Set a small flow of water, converted to steam in the feed preheaters, followed by natural gas.
Sample the non-permeate reactor off-gas (ROG) until CO present, indicating CFL reformation.
Shut off H
2
, then stabilize operations at the desired temperature, pressure and feed rate.
Measure permeate flow using a stopwatch and dry gas meter.
Measure permeate purity (GC #2).
4.5 Catalyst
The total catalyst charge in the ICFBMR pilot reactor was 0.021 m
3
, which brought the settled bed
depth just over the top of core box. The free volume in the core box (the volume not occupied by
membranes and dummy panels) was 0.0085 m
3
. It is in this volume that the bulk of the reforming
reaction occurs. The SMR reaction volume (V) increases to 0.0090 m
3
if we include the reactor
volume immediately above the bottom distributor, but below the core box. Under the flowsheet
conditions presented in Figure 4.2, the methane/steam feed has a volumetric flow of 2.8 m
3
/h. If we
assume that a bubble void volume of -20%of the core box volume not available for reaction, an
estimate of the SMR space velocity (s) at the ICFBMR flowsheet operating conditions (1,300 kPa,
650C) can be made:
b
>f
\

m f J
2
-
S m l h 1
=39 0/. " ' (4.2)
0. 0090w
3
0.8
106
The relatively low space velocity in the ICFBMR pilot reactor is a result of the need to accommodate
the hydrogen membranes in a practical layout for fluidization. Commercial NiO catalysts can be
operated at space velocities above 200,000 h"', but conventional fixed-bed SMR reformers operate
with significantly lower space velocities due to heat transfer and mass transfer constraints. Given the
relatively large volume available for reaction in the ICFBMR pilot reactor, it was decided that it
would be acceptable to dilute the active catalyst with alumina to conserve catalyst stock. It should be
noted that ICFBMR operates ~300C colder than the conventional SMR process, and therefore
reaction kinetics will be slower. Two types of catalyst were employed separately in the ICFBMR
pilot plant:
SMR catalyst: A conventional SMR catalyst, Sud Chemie G-91 5/8"x 1/4"EW, was used initially.
The SMR catalyst (18%NiO, 1.6%K
2
0, supported on alumina) was designed for a conventional
fixed bed reformer, and was in the form of spoked cylindrical rings. The catalyst rings were crushed
in a grinder, then lightly fluidized for several days in atmospheric air. The resulting material was then,
sieved to obtain a powder in the particle range of 50 to 125 urn. The crushed SMR catalyst was then
diluted with an equal volume of alumina powder before being introduced into the pilot reactor.
Autothermal reforming (ATR) catalyst: A novel ATR catalyst was prepared by a commercial catalyst
supplier on MRT-suppIied alumina substrate. The catalyst supplier indicated that this ATR catalyst
formulation had been successfully tested for ATR in the form of a fixed-bed monolith, but had not
been previously used in a fluidized bed. By agreement with the catalyst supplier, no chemical
analysis could be undertaken on this ATR material. It is likely that the formulation was based on a
noble metal, such as rhodium, palladium or platinum. See Ayabe et al. (2003) for a discussion of
various noble metal ATR formulations.
In order to produce a fluidizable ATR catalyst, a high-quality y-alumina powder (Alcoa HiQ
7S19CC) was supplied to the catalyst manufacturer for impregnation. Its average particle diameter
was 87 urn (see Figure 3.2 in Chapter 2 for particle size distribution). Before impregnation, the
alumina powder was preconditioned at UBC by lightly fluidizing with air for several days in a
Plexiglas column. The alumina was then screened (+38 urn, -250 um). This preconditioning was an
attempt to remove any fines that might be initially produced by fluidization, but in fact very few fines
were found in the final screening. For the ICFBMR experiments, the ATR catalyst was diluted 9:1 by
the same alumina as had been utilized as the catalyst substrate.
107
Particle size distributions and hydrodynamic characteristics for the two catalysts are summarized in
Chapter 3. Both catalysts can be considered Geldart type A powders. The activity of the catalyst was
tested in a microreactor prior to loading the pilot reactor and after pilot test runs. Appendix A4.4
describes the microreactor system set-up. The microreactor tests did not attempt to obtain intrinsic
kinetic data as their purpose was to check catalyst and compare activity of fresh and used catalyst at
space velocities significantly higher in of the ICFBMR pilot reactor.
4.6 Pilot Plant Experiments without Membranes
A number of experimental reforming runs were conducted in the ICFBMR pilot plant, initially with
dummy steel internals installed, then with palladium membranes. The overall objectives of the
ICFBMR pilot testing were:
Qualitative evaluation of the ICFBMR reactor concept, including reactor stability, reactor
isothermality, catalyst circulation and segregation of nitrogen in the oxidation air from the reactor
core.
Quantification of the reactor performance, including hydrogen recovery and demonstration of an
equilibrium shift.
Evaluation of the planar palladium membranes in a fluidized bed reformer.
The process variables explored in the pilot plant work included:
Reactor pressure and temperature.
Natural gas feed rate.
Steam-to-methane molar feed ratio.
Operation with and without sweep nitrogen.
External heating (SMR) and autothermal operation (ATR) with varying air feed rate.
Table 4.1 summarizes the pilot plant experimental program. No membranes were installed in the first
run, as its purpose was to commission and prove the pilot system. A carbon steel dummy internal was
inserted in the ICFBMR to simulate the membranes, similar to the cold model testing. After the first
run, the carbon steel dummy assembly was replaced by membrane assembly, which remained
installed for the duration of the experimental program. Not all of the data from the pilot runs are
described in this chapter; only results that are believed to give insight into the ICFBMR performance
are presented.
108
Table 4.1: Summary of ICFBMR experimental runs
Run Dates Catalyst Comments Run time (h)
1
July - Sept, 2003 Diluted NiO
Commissioning runs, dummy
internals installed (no membranes)
2
Aug 9-12, 2004 As above
Reactor heaters replaced
Membranes installed
90
3
Sep 20-22, 2004 As above
Heluim tracer study
SMR &ATR testing
65
4
Oct 26-28, 2004 As above Low catalyst activity experienced 65
5
Dec 13-14, 2004
Used ATR (11%)
diluted with alumina
Low catalyst activity experienced 24
6
Aug 18-21,2005
Virgin ATR (10%)
diluted with previous
ATR material
SMR &ATR testing
Up to 650C operation
Low catalyst activity experienced
after -40 hours
90
334
A series of experimental runs was conducted on the ICFBMR pilot plant with dummy internals
installed in the reactor. The specific objectives of these runs were:
To prove operation of the pilot plant, including the PLC control system and ICFBMR heaters at
reforming temperatures and pressures.
To investigate hydrodynamic characteristics, such as bed and distributor pressure drops.
To perform reforming runs on the reactor to confirm catalyst activity and gas chromatography
procedures.
The core draft box of the steel dummy matched the dimensions'of draft box used to house the
membrane internals in subsequent ICFBMR experiments. However, the dummy internals had three
solid (i.e. non-communicating) plates to simulate the membrane surfaces, while the membrane
assembly had horizontal communications slots (Figure 4.4). As discussed in Chapter 3, results from
cold model experimentation indicated that the non-communicating panel design is prone to
maldistribution of solids and gas among core flow channels, leading to flow instability.
The reactor was filled with 21 liters of the diluted NiO catalyst powder mixture (50 wt%SMR
catalyst, balance alumina). The physical properties and fluidization characteristics of the NiO catalyst
mixture are summarized in Table 3.1 in Chapter 3. This batch of catalyst had been previously used in
reforming experiments conducted by MRT. As indicated in Table 4.1, this catalyst mixture was used
for ICFBMR pilot plant runs #1 through #4. The settled catalyst bed depth was confirmed to be 25
109
mm above the top of the core draft box. The catalyst was reduced by fluidizing for four hours in a
30%H
2
, 70%N
2
mixture at 500C and 300kPa. Notable results of the commissioning runs include:
Although the chemical duty of the reforming reaction was modest, the temperature profile within
the reactor core was very uniform (less than ~10C variation).
Overall heat losses from the reactor were found to be -2 kW.
The freeboard of the reactor was about 30-50C colder than the main bed, resulting in reaction
reversal in the freeboard. The gas analysis of the outlet gases therefore tended to show
significantly lower methane conversions than expected based on the main reactor operating
temperature. This phenomenon was present in all of the experimental runs to some degree.
The pressure drop over the two sintered metal outlet filters was stable and acceptable. As a result,
the back-pulsed nitrogen cleaning system was not required.
Several components in the ICFBMR system did not perform as well as expected and had to be
replaced after the commissioning runs:
ICFBMR heaters: After approximately 36 hours of service, the resistance of the four ceramic reactor
heaters (Watlow VS108A30S) dropped by -25%. Their resistance continued to decrease to about
-50%of their original value. At the end of the commissioning runs, the internal ICFBMR was
removed from the pressure shell, and the ceramic heaters were replaced with four new 0.5 kW tubular
heaters (Watlow Incoloy RDN134J10S). It is believed that organic binders present in the insulation
blanket permeated the ceramic heaters, leading to short-circuiting of the heater wires. The ceramic
heaters clamped onto the internal preheater were of design similar to the failed units, but surprisingly
suffered no performance deterioration during the ICFBMR pilot program.
Plugged distributors: The secondary feed distributor initially installed in the ICFBMR incorporated a
ring header with an angled distribution point in each annular quadrant (Figure A4.5.1, Appendix 4.5).
The 0.6-mm diameter holes in the distributor partially plugged with catalyst solids, and the assembly
was then replaced by the sintered metal distributor presented in Figure A4.1.3 in Appendix 4.1.
Similarly, the original orifice air distributor (Figure A4.5.2, Appendix 4.5) also partially plugged with
catalyst solids during commissioning runs, and was replaced by the sintered metal distributor
described in Section 4.2.2. Although orifice distributors are generally preferred for fluidized beds, the
many start-ups and varied gas flows presented opportunities for backsifting, which was prevented by
the sintered metal distributors.
110
Thermocouples: Several of the multipoint thermocouples failed in service, likely a result of the
bending required by the rather complication installation procedure. Disassembly and re-assembly of
the pilot plant reactor was challenging and very time-consuming. As a result, the failed multipoint
thermocouples were not replaced, and temperature profile information from the pilot plant tests was
incomplete.
4.7 Pilot Plant Experiments with Membranes
Although the installation of membranes did not complicate reactor control, the extra flow and gas
analyses added extra operational tasks. Additional upgrades to the pilot control system, such as a
permeate H
2
mass flow meter and an automatic gas chromatograph sampling system, would have
facilitated generation of reliable experimental data.
A mass balance closure around the pilot plant was attempted for several atomic species (carbon and
nitrogen) during a number of the experimental runs, but was not possible for hydrogen and oxygen, as
the condensed water in the reactor off-gas was not measured. The error in the atomic carbon balance
(carbon in - carbon out) was generally within 15%. Although the reactor feed gas flow was known
accurately, the reactor off-gas flow was measured manually with a dry gas meter and stopwatch, and
there was a potential for leaks from the pressurized system.
4.7.1 Membrane Performance
The performance of the H
2
membranes is the key to the ICFBMR system. The three most important
membrane performance parameters are:
Purity - Ultrahigh purity is desirable in order to meet fuel cell specifications.
Flux - Sets the H
2
production rate of the system.
Effectiveness - Defined here as the fraction of measured H
2
flux relative to the predicted
flux, thus a measure of the excess membrane required above theoretical predictions.
4.7.1.1 Membrane Performance
The total cumulative time that the membranes were exposed to hot, fluidized operating conditions in
the pilot reactor was approximately 14 days. The membranes cycled from ambient conditions to hot
temperatures (>500C) six times. As presented in Figure 4.8, the combined hydrogen permeate was
initially found to be "pure"H
2
(>99.999%, excluding N
2
present from sampling or sweeping) until the
cumulative run time was approximately 180 hours, from which point the averaged measured purity of
the combined permeate was 99.8%(dry basis). Given the presence of methane, it is likely that there
were also traces of steam in the permeate H
2
at concentrations of -0. 2% . The times of the six start-
111
ups / shutdowns of the pilot reactor are also shown on Figure 4.8, as are the reactor core operating
temperature (right hand axis). Membrane impurities were detected midway through the third test run,
just after the reactor core was operated at 575C. However, a link between operating temperature and
H
2
purity cannot be concluded. The maximum core operating temperature was 650C, near the end of
the last run.
Table 4.2 summarize permeate testing results for each of the six membranes panels installed in the
reactor. No leaks were detected in four membranes during the pilot testing, and the two leaking
membranes produced relatively high purity hydrogen throughout the entire pilot test.
Table 4.2: Permeate purity (dry basis) from membranes operating in ICFBMR pilot reactor
(excluding N
2
, see Figure 4.4 for location of membranes in the reactor)
Membrane Location Run time to 1
st
detected leak (hours)
Lowest detected
H
2
purity
1 3
rd
from top (right) No impurities detected >99.999%
3 2
nd
from top (right) 253 99.72%
4 Top (right)
No impurities detected >99.999%
5 3
rd
from top (left) 173 99.67%
6 2
nd
from top (left) No impurities detected >99.999%
8 Top (left) No impurities detected >99.999%
4.7.1.2 Membrane Flux Testing
In Table 2.4 (Chapter 2), the effective area of each of the membranes was calculated from permeate
test data. From this, the total permeation area of the six membranes installed in the pilot reactor was
calculated to be 0.060 m
2
. Individual flux testing of the membranes installed in the pilot reactor was
periodically performed at elevated temperature (>500C) under a pure H
2
atmosphere with no N
2
sweep to the membranes, to ensure that the partial pressure of hydrogen in the system was equal to
the absolute pressure. H
2
was fed to the pilot reactor in excess of the membrane flux and above the
minimum fluidization velocity. The effective permeation area of each membrane was calculated
based on the measured flux and Sievert's law permeation equation (equation 4.1). Table 4.3
summarizes the calculated effective area of each of the six membranes during two such tests, as well
as the pre-pilot data from Chapter 2. As previously noted, the expected permeation area of each
membrane based on the panel geometry was calculated to be 0.0258 m
2
(six panel total =0.155 m
2
).
112
100.0
99.8
b 99.6

a
CM 99.4
I
99.2
Combined H2 permeate (left axis)
Startup / Shutdown
A Core temperature (right axis)
A
A \
A A A A A
.->

AAA

/f t
2A
A
650
600 ~
o
3
+>
re
550
E
o
L.
o
500
99.0
50 100 150 200
Run time (hours)
250 300
450
350
Figure 4.8: Purity (dry basis ) of combined hydrogen permeate (excluding N
2
) and core reactor temperature over
the duration of the I CF BMR pilot reactor testing
The data from the reactor flux testing generally gave calculated membrane areas slightly higher than
the pre-reactor permeation testing. The flux data are somewhat inconsistent, especially for panel #8,
but for the most part the relative areas of the membranes are approximately the same within each data
set. It is likely that some of the measured variation is real (i.e. adsorbed surface impurities during the
pre-pilot permeation tests), but experimental error such as temperature variation and gas leaks in
permeation testing equipment probably also contributed to the inconsistency.
Table 4.3: Calculated effective permeation area of the membranes installed in the pilot reactor (see
Tables A4.6.2-3, Appendix 4.6 for data, 0.0258 m
2
is expected permeation area of 1 panel
based on membrane geometry)
Membrane
Average of calculated effective permeation area (m
2
)
Membrane
Pre-pilot testing
(Table 2.4)
After run #5 During run #6
1 0.0121 0.0154 0.0142
3 0.0101 0.0124 0.0118
4 0.0075 0.0102 0.0099
5 0.0142 0.0184 0.0165
6 0.0059 0.0075 0.0064
8 0.0101 0.0113 0.0080
Total 0.0599 0.0752 0.0668
Fraction of
1 0.0258 m
2
38.7% 48.6%
43.2%
4.7.1.3 Flux Under SMR Conditions
The effective membrane area for a number of ICFBMR operating runs is presented in Table A4.6.4,
Sheet3 (Appendix 4.6). The effective membrane area was calculated based on equation 4.1 and the
reactor operating variables for each operating point. The variables needed to calculate the effective
membrane area were:
Temperature - The average reactor core temperature was used.
H2 partial pressure in the permeate:
o Assumed to be 101 kPa for all non-sweep operating points.
o For the N
2
-sweep cases, the H
2
partial pressure was assumed to be 101 kPa multiplied by
the measured H
2
mole fraction of the combined permeate stream, which was typically in
the range of 35 to 50%.
H
2
partial pressure in the reactor:
o For SMR operation (no air addition), the H
2
partial pressure was estimated by calculating
the equilibrium reactor gas composition from the reactor feeds, temperature and pressure
114
at two points within the reactor (inlet and exit, after H
2
permeation). The permeate H
2
partial pressure used for permeation was the average of the two values,
o For ATR operation (air addition to top of reactor), the reactor equilibrium was calculated
as in the SMR case, except that 0
2
was excluded (as it is consumed in the upper reactor,
away from the membranes) and only 10%of the N
2
in the oxidation air was assumed to
reach the core permeation zone, based on results from the cold model work. The balance
of the N
2
in the oxidation air was assumed to not circulate to the reactor core, but rather
to leave the reactor directly.
The average permeation area calculated from the data listed in Table A4.6.4, sheet 3 (Appendix 4.6)
for the case of no sweep gas is 0.075 m
2
, similar to the areas calculated in Table 4.3 based on the pilot
flux tests. This implies that the membrane "efficiency"was close to 100%in the pilot reactor for the
no-sweep operating points.
The average calculated permeation area calculated for cases with sweep nitrogen was lower (0.059
m
2
). This is likely due to the assumed H
2
permeate partial pressure being less than under actual
operating conditions. As the H
2
flux on each panel varied somewhat, the H
2
permeate partial pressure
on any individual membrane would not necessarily be equal to the measured combined H
2
permeate
concentration. In addition, the gas mass transfer resistance on the permeate side of the membrane
means that the H
2
partial pressure will be higher than the permeate gas leaving the membrane panel.
Clearly the N
2
membrane sweep was less than fully effective.
4.7.2 SMR Operation (External Heating Only)
The highest membrane flux was expected for SMR operation at the highest reactor operating
temperature and pressure, with sweep gas fed to the membranes. However, this turned out not to be
the case, as the catalyst activity at the highest core operating temperature (650C) was low. The
maximum recorded H
2
production rate was 17.6 SLM (1.06 Nm
3
/h) at 589C and 1,209 kPa using
nitrogen sweep to the membranes. Table A4.6.4, Appendix 4.6, summarizes the measured hydrogen
flux different operating points.
As discussed above, the measured exit gas composition of the reactor is not a true measure of the gas
composition in the reactor core as the temperature drop in the freeboard reverses the SMR reaction.
The only practical way of estimating the theoretical membrane flux is to assume that the non-
permeate reactor gases are at equilibrium at the reactor temperature and pressure. However, in a
significant number of the data points in Table A4.6.4, the measured methane conversion in the reactor
115
off-gas exceeded the equilibrium methane conversion with no H
2
removal. This is evidence of an
equilibrium shift caused by in-situ H
2
removal.
Experimental data showing the effect of the main process operating variables is now presented. In
some cases the pilot plant results are somewhat sparse, as it proved difficult to operate the pilot
single-handedly. However, in general the reactor performance followed trends suggested by
equilibrium reactor modelling.
4.7.2.1 Effect of Temperature
Increasing temperature increases the H
2
flux by shifting the SMR equilibrium towards products and
by increasing the permeance of the palladium foil. Figure 4.9 presents selected H
2
recovery data as a
function of reactor temperature from run #3, with and without sweep N
2
to the membranes. The
enhancement of H
2
recovery by sweep N
2
is evident. In addition to experimental error, some of the
data scatter is due to the fact that other operating variables (such as reactor pressure, steam-to-carbon
ratio and permeate H
2
partial pressure) could not be controlled to be identical for each operating
point. Nevertheless, both sets of experimental data reasonably follow the predicted trend lines.
1.2
0.4 -I 1 , , , , 1
550 560 570 580 590 600 610
Temperature (C)
Figure 4.9: Permeate hydrogen recovery relative to gas feed rate as function of reactor temperature
and N
2
sweep (run #3, 15 SLM natural gas, reactor pressure ranges from 1,090 to 1,275 kPa,
S:C = 2.1 to 4.0, predicted lines are 15SLM CR,, 2.4 SLM N
2
, S:C = 3.0, 1,200 kPa, permeate
pressure = 101 and 50 kPa for sweep / no-sweep respectively, area = 0.060 m
2
)
Figure 4.10 presents another set of H
2
recovery data as a function of temperature at slightly higher
temperatures. Again, hydrogen recovery increased with temperature, though it should be cautioned
that the catalyst activity for these operating conditions was low. The enhancement of the H
2
recovery
with sweep N
2
is again shown. Figure A4.6.1 (Appendix 4.6) presents the measured and predicted
methane conversion for these operating conditions.
116
1.0
>
o
u
<D
I
o
C N
X
0. 8
0. 6
0. 4
0. 2
0. 0
Imodel for A = 0.06 m2, 50 kPa permeate
X model for A = 0.06 m2, no sweep
A no sweep - measured
sweep - measured


Q

g
A
n
A
A
560 580 640 660 600 620
Temperature (C)
Figure 4. 10: Permeate hydrogen recovery relative to natural gas feed rate as function of reactor
temperature and sweep gas (1, 060 kPa, steam-to-carbon = 3. 0, run #6)
4.7.2.2 Effect of Steam-to-Carbon Ratio
The steam-to-carbon feed ratio was varied in some experimental runs. As shown in Figure 4. 11, the
predicted and measured effect of this variable on H
2
production is modest. It should be noted that the
catalyst activity was again low during these test runs. Although the effect on the H
2
flux is modest,
lower steam-to-carbon ratios tend to improve the thermal efficiency of a SMR system. Figure A4.6.2
(Appendix 4.6) presents the corresponding measured and predicted methane conversions.
0. 7
0.6
0. 5
0. 4
0. 3
0.2
0.1
0. 0
>
o
o
k.
X
O
cvi
I
model for A = 0.06 m2, 50 kPa permeate
model for A = 0.06 m2, no sweep
sweep
A no sweep
2.0 2.5 3.0 3.5 4. 0
Steam-to-carbon molar ratio
Figure 4. 11: Permeate hydrogen recovery relative to natural gas feed rate as function of steam-to-
carbon molar ratio and sweep gas (1, 060 kPa, 570C, run #6)
117
4.7.2.3 Effect of Feed Rate
At very high hydrogen recoveries (> 2V
2
moles H
2
per mole of natural gas feed) the H
2
partial
pressure in a plug flow membrane reactor drops significantly at the reactor exit, decreasing the flux
through the membranes located near the reactor exit (see modelling output in Chapter 6) . However,
at low hydrogen recoveries (less than ~IV
2
moles H
2
per mole of natural gas feed), the H
2
partial
pressure does not decrease significantly with in-situ H
2
removal. This is the situation in the pilot
plant, as the hydrogen flux was found to only decrease marginally at lower feed rates. Figure 4.12
presents all of the Table A4.6.4 hydrogen recovery data as a function of the natural gas feed rate.
There is variation in the data, as there was no attempt to match the operating conditions (e.g.
temperature, pressure, sweep gas), but the trend is clearly to higher H
2
recovery at lower natural gas
feed rates. This figure also highlights that the pilot reactor performance was flux limited. The
installed membrane area governs the H
2
production rate; varying operating conditions only modestly
affects the membrane flux. Figure A4.6.3 (Appendix 4.6) presents the same data, but expressed as the
absolute permeate H
2
flux, showing that this was almost independent of the natural gas feed rate.
1.4 T .
1.2 H
0.0 "I 1 1 1 , , r ~\
10 15 20 25 . 30 35 40 45
Natural gas feed rate (SLM)
Figure 4.12: Hydrogen recovery as a function of natural gas feed rate for all data in Table A4.6.4
The highest measured hydrogen recovery was 1.17 Nm
3
/Nm
3
of feed natural gas (data set #20, Table
A4.6.3, Appendix 4.6). The feed flow of natural gas was 15 SLM for this operating point. Higher
recoveries were anticipated for the high temperature operating points in run #6, but poor catalyst
activity hindered reactor performance.
118
4 . 7. 3 ATR Operation (Air Addition)
A series of ATR experiments were performed to determine the effect of the rate of air addition on
hydrogen production. The reactor was first stabilized under SMR conditions at 1,100 kPa and a core
temperature at ~560C. The natural gas feed was set at 20 SLM and the steam-to-carbon ratio at 3.0
for all test points. Air was then introduced in increments up to a maximum feed oxygen-to-methane
molar ratio (0
2
:CH}) of 0.6. A constant flow of sweep nitrogen was maintained to the membrane
panels. No methane or carbon monoxide impurities were detected in the permeate testing. A summary
of the operating conditions and experimental results are presented in Table A4.6.6, Appendix 4.6.
Figure 4.13 presents the H
2
partial pressure in the reactor predicted by the Gibbs reactor equilibrium
model if the system were well mixed for operating conditions #1-8 in Table A4.6.6, and account for
the measured permeate H
2
removal. As the air addition rate increased, the H
2
partial pressure in the
reactor decreased, reducing the membrane permeation driving force.
250 j
<D
3
225 n
(A
tn
0)
l _ 200 -
Q.
re
0.
175 -
ro o
o . -o
o 150 -
c
t
o

E
150 -
re
o 125 -
i _
CN
X
100 --
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7
02 : CH4 Mo l ar Rati o
Figure 4.13: H
2
partial pressure in a well-mixed reactor for ATR experimental conditions predicted
by equilibrium model (560C, 1100 kPa, NG feed 20.1 SLM, S:C = 3.0, sweep N
2
to membranes)
Figure 4.14 presents the measured hydrogen flow as a function of the air addition rate. The measured
flow of permeate H
2
was not significantly affected by air addition. This insensitivity of H
2
flux to air
addition is a key advantage of the ICFBMR configuration. Also plotted on Figure 4.14 is the
predicted H
2
flux for a well-mixed system, based on the H
2
partial pressures from Figure 4.13,
normalized to the measured H
2
flux with no air addition. If the entire system were well mixed, the
lower H
2
concentration in the reactor would reduce the membrane flux by almost 40%. However, the
H
2
permeate flow did not change significantly in the ICFBMR pilot testing, confirming that only a
small portion of the nitrogen in the oxidation air circulated to the reactor core.
119
w
ra
E
CD
Q.
5
o
H
CM
X
12
10
8
6
4
2
0
A H2 flux (measured)
A Predicted H2 flux (no rmalized)
0.0 0.1 0.2 0.5 0.6 0.7 0.3 0.4
02.CH4 Molar Ratio
Figure 4.14: Effect of air addition on Ff
2
flux (measured and predicted for well-mixed reactor,
560C, 1100 kPa, NG feed 20.1 SLM, steam-to-carbon = 3.0, sweep N
2
to membranes)
As the oxidant air flow increased, the reactor heaters were reduced from an initial power of 4.2 kW
(SMR, 0
2
:CH4 = 0) to 0 kW at the highest air addition rate (0
2
:CH
4
= 0.6). Simulations presented in
Chapter 7 show that an 0
2
:CH4 molar ratio in the range of 0.35 to 0.4 should be sufficient for the
reactor to run adiabatically. However, the pilot reactor has significant heat losses, so that adiabatic
0
2
:CH4 ratio would be even higher than 0.6 if commercially viable H
2
recovery ratios could be
achieved in the pilot plant. In any event, the testing did show that the reactor duty, although modest,
could be fully sustained by air addition. Under SMR conditions, the temperature profile within the
reactor core was flat, with a temperature variation of approximately 10C. This increased to ~20C at
the highest air addition rate (see Table A4.6.7, Appendix 4.6 for temperature profiles at different air
addition rates).
Figure 4.15 presents additional test data that again indicate that the hydrogen flux is relatively
insensitive to the air addition rate. It should be noted that it likely that the catalyst activity was
somewhat low during these tests. Nevertheless, the H
2
flux was not reduced significantly with air
addition. Also shown is the significant increase in hydrogen flux when sweep N
2
is used.
120
14
12

1 0
s
W 8
X
6
CN
1
4
sweep
no sweep
0 0.1
0.4 0.5
0.2 0.3
02.CH4 Molar ratio
Figure 4.15: Permeate hydrogen flow (with and without sweep gas) with varying air addition rate
(645C, 1060 kPa, N G feed = 20 S L M , steam-to-carbon = 3, A T R catalyst)
4.7.4 Solids Ci rc ul ati on Tests
Similar to the cold model work presented in Chapter 3, a series of helium tracer experiments was
conducted to investigate internal movement of gas and solids within the reactor. Helium was metered
to the reactor through the main oxidant distributor with a rotameter (Figure A4. 5. 3, Appendix A4.5).
Gas samples were taken from various points in the reactor, then analyzed for their helium
concentration in a gas chromatograph.
Figure 4.16 presents the reactor schematic and sample point locations for the tracer tests. Reactor gas
was directly sampled from the annulus, core and freeboard (Points D, E, H , I in Figure 4.16) and the
reactor outlet. During these tests, the reformer was operated under S MR conditions (no air addition)
at ~595C (core), 1,100 kPa with a natural gas feed rate of 42 S L M and a steam-to-carbon molar ratio
of 3.0. The permeate hydrogen flow (with sweep nitrogen) was measured to be between 16 and 17
S L M (as 100% H
2
) during the helium trials.
Figure 4.17 presents the measured helium concentration and methane conversion at various points
within the reactor (see Table A4.6.1 for data). The measured helium concentrations provide strong
evidence of positive solids circulation. Several points are notable:
The helium concentration in the annulus at mid-height was approximately half the reactor exit
concentration. At the top of annulus, the gas composition would be expected to be similar to the
reactor exit. The fact that the annular helium concentration was lower may result from uneven
mixing of the helium in the upper reactor, or modest stripping due to the secondary feed gas.
121
Oxidant f eed
1,380 kPag
He
Sampl e " D"
in slot 2
Sampl e "I" \
in annulus
Sampl e "E" -
in slot 2
Reactor off-gas
(to G C / vent)
Secondary
feed (4)
Oxidant distributor
Sol id divider
Sol id dummy plate (1 of 2)
Sampl e " H" in slot 3
" Membrane (1 of 6)
Core draft box
-t X h To G C
Permeate H2
Main
f eed
Figure 4.16: ICFBMR helium tracer test schematic
The helium concentration in all of the core samples was 5 to 7% of the helium content at the
reactor exit. The fact that the helium concentration was similar in the top and bottom of the core
strongly suggests that the great majority of helium enters the core from the solids circulated from
the bottom of the annulus, rather than due to axial dispersion from the top of the reactor. The
helium tracer testing in the cold model (Section 3.5.4) did find slightly higher helium
concentrations in the top of the core box, likely due to the cold model sample points being located
122
very close to the top of the core box (90%of core height), whereas the pilot reactor sample points
were located somewhat lower (75%of core height).
Non-permeate off- Annulus (I) Slot 2 bottom (E) Slot 2 top (D) Slot 3 top (H)
gas
Figure 4.17: Measured helium concentration (black bars) and methane conversion (open bars)
from ICFBMR He tracer tests (see Table A4.6.1, Appendix 4.6 for data)
The helium concentrations provide strong evidence of the intended up-the-core, down-the-
annulus solids circulation pattern. If the reactor were running under ATR conditions, the helium
concentration profile suggests that only 5 to 7%of the nitrogen in the oxidation air would be
circulated to the reactor core. This corresponds to findings in the cold model helium tracer tests,
where approximately 10%of the helium fed through the oxidant distributor was found to
circulate to the reactor core (see Section 3.5.4).
The core helium concentration was an average of 12%of the measured mid-height annular
concentration. From this, an estimate of the solids circulation rate can be made using the same
equations as in the cold modelling chapter (Section 3.5.4.1). Assuming that the entire reactor feed
flows up the reactor core (42 SLM natural gas, 126 SLM steam), the following estimates of
various reactor hydrodynamic parameters were obtained (see Table A4.6.5, Appendix 4.6 for
calculation details):
Core superficial velocity (U
core
) = 0.18 m/s
Solids circulation rate (m
p core
)= 0.22 kg/s
Solids flux up core (G
pcore
) = 45 kg/m
2
s
Downward velocity of solids in annulus = 0.027 m/s
123
Predictive scaling correlations were developed for the solids flux (positive when flux upwards)
for both horizontally and vertically slotted panels in the cold model testing presented in Chapter 3
(Figure 3.20):
Vertically slotted panels G
pcore
= -1.03E-4(t/
core
p
p
f + 0.180(/
c ore
p
p
) -11.3 (5.1)
Horizontally slotted panels G
pcore
= -4.14E-5(<7
core
p
p
f + 0.083(<7
core
p
p
) +0.65 (5.2)
From the calculated value of U
cart
, (0.18 m/s) and the catalyst particle density (2,150 kg/m
3
), the
predicted solids fluxes (G
pcore
) are 42 and 28 kg/m
2
s for vertically and horizontally slotted panels
respectively, close to the estimate obtained from the experimental data (45 kg/m
2
s). The pilot
plant membrane assembly most closely matches the horizontally slotted panels in the cold model.
Although this is but one data point, the result suggests that the cold modelling results can be used
for hydrodynamic evaluations of the hot, pressurized system.
The measured methane conversion from the in-bed samples was significantly higher than
measured in the reactor off-gas. As discussed above, the reactor freeboard operates cooler than
the main reactor due to heat losses, causing a reverse shift in the equilibrium. Gas analyses are
presented in Table A4.6.1 (Appendix 4.6). The highest measured conversion was in the annulus,
adjacent to the heated reactor wall, as this was the hottest part of the reactor. Table 4.4 presents
the calculated equilibrium temperature needed to match the measured methane conversion at each
point, given the species composition measured by the gas chromatograph. Except for the non-
permeate reactor off-gas sample, the predicted equilibrium temperatures are reasonably close to
what was measured in the reactor.
Table 4.4: Local measured and corresponding equilibrium temperatures
Sample location Temperature (C) Sample location
Measured Equilibrium predicted
from gas analysis
Reactor off-gas (freeboard 579 597
Point I (annulus) 628 621
Point E (bottom slot 2) 593 589
Point D (top slot 2) 595 597
Point H (top slot 3) 590 583
4.8 Catalyst Testing
The catalyst used in the reformer was also tested in a microreactor to its confirm activity. The test
conditions were not in the kinetically controlled region; rather the test conditions were chosen to
124
permit comparison to previous catalyst testing performed by MRT. The tests allowed the relative
activity of the catalyst materials before and after use in the pilot reformer to be ascertained.
4.8.1 S M R Cataly st Testi ng
As indicated earlier, the NiO on alumina catalyst is designed for SMR conditions (no oxidant
addition), and it was not unexpected that the catalyst deactivated after prolonged exposure to ATR
conditions. Figure 4.18 summarizes catalyst microreactor testing under SMR conditions of fresh
catalyst before ICFBMR service, and the SMR catalyst removed from the ICFBMR reactor after the
first and third runs (see Table A4.7.1, Appendix 4.7 for data). The fresh and first-run catalysts show
near-equilibrium conversion. The reason for the initial conversion being slightly above equilibrium
and the slow decline in conversion of the fresh catalyst is not known, but is likely attributable to
small variations in the microreactor temperature.
The catalyst performance after the last SMR catalyst run (run #4 in Table 4.1) clearly shows
declining activity, confirming pilot plant observations. Some residual activity exists, but clearly the
catalyst is no longer useable.
100 -, 1
0 4- , , r ; 1 1
0 25 50 75 100 125 150
Time on stream (h)
Figure 4.18: CFLt conversion in microreactor with NiO catalyst (0.3 g of 50%NiO catalyst and 50%
alumina, 550C and 201 kPa, CFL, feed = 30 Nml/min, H
2
feed = 30 Nml/min, steam-to-carbon
ratio = 3.5, space velocity at inlet conditions = 99,400 h"
1
)
4.8.1.1SMR Catalyst Characterization with TGA and XRD Analysis
When operating the ICFBMR in ATR mode, the catalyst is cycled through oxidizing and reducing
zones. Although the fluidized bed dissipates heat much more quickly than fixed beds, the oxidation
125
zone still exposes the catalyst to elevated temperatures near the air distributor for brief periods of
time. The causes for deactivation of NiO in ATR service have been attributed to nickel oxidation,
carbon formation, sintering and spinel formation (Tomishige et al., 2004). In an attempt to determine
the mode of deactivation for the SMR catalyst, thermo-gravimetric analysis (TGA) and X-ray
diffraction (XRD) analyses of the spent catalyst were undertaken.
TGA analyses of the SMR catalyst are presented in Appendix 4.8. Catalyst samples (~18 mg) were
heated in an air/nitrogen mixture from ambient temperature to 800C, with the sample mass
continually measured. This technique detects sample loss or gain due to oxidation or volatilization.
The fresh catalyst lost almost 4%of its weight, perhaps due to moisture and residual volatiles. The
spent catalyst samples showed no significant weight change, indicating that there were no large
deposits of carbon. However, it should be noted that the spent catalyst had a grey-black appearance,
and small traces of carbon may have been present, below the detection limit of the TGA system used
(< -0.25%).
XRD analyses of several SMR catalyst samples are presented in Appendix 4.9. There were no
significant differences in the spectra from fresh and spent catalyst, suggesting that spinel formation
was not significant.
4.8.2 A T R Cataly st Testing
Two ICFBMR runs were carried out with the novel ATR catalyst from a large commercial supplier.
The first run used a mix of previously-used ATR diluted with alumina. The second ATR run used a
mix of virgin ATR blended with bed material from a previous run. Low catalytic activity was
experienced in both runs, resulting in disappointing reactor performance.
The activity of the virgin ATR catalyst (diluted 50%with alumina) was tested in a microreactor under
ATR and SMR conditions (Figure 4.19, data in Table A4.7.2 in Appendix 4.7). The space velocity of
the catalyst was 12,000 h"
1
under SMR conditions. The methane and steam flow to the reactor were
kept constant during the various operating modes. Air was used in the ATR mode. Alternating SMR
and ATR operating conditions were also tested by cycling the air on for one minute, then off for one
minute over a 45-minute period (see "0
2
cycling" in Figure 4.19).
The catalyst activity was relatively stable over the 100-hour test run. There is some variation in the
data, especially the initial "ATR" run, likely attributable to deviations of the microreactor
temperature from 550C. As the space velocities in these tests were relatively low, the measured
126
methane conversions were close to equilibrium values (see Table 4.5), except for the last "ATR" run,
where the measured methane conversion was slightly lower.
80 -, - I
I - B- 2. S MR With H2
O ! A 3.SMR Without H2
j X 4.02 Cycling
I A 5.ATR
20 -I , : , : ; , 1
0 30 60 90 120
Run time (hours)
Figure 4.19: CFL, conversion in microreactor with virgin ATR catalyst (mix of 0.3 g ATR catalyst and
0.3 g alumina at 550C and 200 kPa, space velocity = 12,000 h"
1
under "SMR" conditions,
steam-to-carbon = 3.5 and CH
4
feed = 60 Nml/min for all tests, "ATR" used air addition with
0
2
:CFL, molar feed ratio = 0.36, all tests except "SMR without H
2
" used H
2
:CH
4
molar feed
ratio =1.0)
Table 4.5: Equilibrium methane conversions for Figure 4.19
(equilibrium conversions are calculated at average measured bed temperature)
Test Description Equilibrium
CH
4
conversion
Measured C T
4
conversion
Test Description Equilibrium
CH
4
conversion Average Std.
Deviation
ATR 57.6% 58.6% 3.8
SMR with H
2
41.1% 42.2% 0.96
SMR without H
2
53.1% 53.9% 0.11
0
2
cycling (same as data #2) 41.1% 39.8% 0.75
ATR (similar conditions as data #1) 55.1% 48.7% 0.29
As discussed above, the catalytic properties of the ATR bed materials in the ICFBMR pilot plant
were poor. This was confirmed in post-run microreactor testing of the bed materials. Both the used
and virgin ATR catalyst mixtures (1
st
and 2
nd
samples respectively in Figure 4.20) showed extremely
low reforming activity. The methane conversion measured during ATR operation is due to reaction of
methane with oxygen. The cause of the loss in catalytic activity is not known, and as the material was
subject to a non-analysis agreement, further testing of the used ATR catalyst was not performed. The
127
catalyst supplier has indicated that this catalyst formulation has been proven to be stable in the form
of an impregnated monolith under both SMR and ATR conditions.
50
40
' 30
>
C
o
o
T t
X
o
20 H
10
1st sample - ATR
- A - 1st sample - SMR
- - 2 nd sample - ATR
-B-2 nd sample - SMR
10 20
Run time (hours)
30
Figure 4.20: Microreactor testing of diluted ATR catalyst after use in ICFBMR pilot plant ("1
st
sample"is used ATR mixture, "2
nd
sample"is virgin ATR mixture, 1.65 g of catalyst mixture at
550C and 200 kPa, space velocity = 12,000 h'
1
under "SMR" conditions, steamxarbon = 3.5,
CFLt feed = 30 Nml/min, H
2
:CH
4
molar feed ratio = 1.0 for all tests, "ATR" used air addition
with 02:CH4 molar feed ratio = 0.5)
The composition of the ATR is not known, but it is possible that it contained rhodium (Rh), as this is
the most common precious metal reforming catalyst described in the literature. Instability of Rh-
catalysts in membrane (Kurungot and Yamaguchi, 2004) and non-membrane reformers (Watson and
Daly) have been described. Sintering of the dispersed Rh particles due to thermal instability of the
catalyst substrate (alumina, ceria and others) is main cause attributed to the Rh deactivation. Perhaps
the y-alumina provided to the ATR catalyst supplier for impregnation was not stable at the elevated
temperatures present in the oxidation zone, but we are unable to draw definitive conclusions without
analysis of the material. In addition to this instability, Beurden et al. also identify the high cost of Rh-
based catalysts as a barrier to commercialization of membrane reformers. Perhaps a more economic
alternative to Rh can be developed, such as bimetallic catalysts based on Ni modified with small
amounts of Pd, Pt or Rh (Mukainakano, 2007).
4.9 Discussion
The membrane area installed in the reactor limited reactor performance, and only a fraction of the
nominal H
2
design capacity was achieved. However, the H
2
production could be reasonably predicted
using a simple equilibrium model coupled with the membrane permeation equation, so it is likely that
128
the design production rate could be achieved if sufficient membrane area were to be installed. The
effect of the main process variables (temperature, pressure, steam-to-carbon ratio, N
2
sweep)
generally followed model predictions.
The permeate H
2
production was relatively insensitive to the natural gas feed rate, as the flux was set
by the limited membrane area in the reactor. As a direct result, the highest hydrogen recovery was
achieved at the lowest natural gas feed rates. This is characteristic of membrane reactors, and
highlights how the reactor performance is overwhelmingly governed by permeation. Only through
increasing the permeation capacity, either by increasing area or decreasing foil thickness, can H
2
production be significantly increased.
The H
2
flux increased significantly when a N
2
membrane sweep was used as it decreased the H
2
partial pressure on the backside of the membrane. Use of an inert gas such as nitrogen for membrane
sweep is not practical for a commercial unit, as an impure hydrogen product would be produced. Use
of sweep steam, as was originally intended for the pilot tests, would be possible as it can be
condensed from the permeate stream. Residual moisture in the H
2
product is acceptable for some
applications such as fuel cells. However, there is a significant energy penalty with use of sweep
steam, and the overall thermal efficiency of the system would suffer. In addition, the water from
which the sweep steam is generated would have to be of extremely high quality, as trace impurities
would end up in the product hydrogen.
Another method of decreasing the H
2
partial pressure in the permeate stream is to lower the absolute
pressure with a vacuum pump. This has been used successfully in pilot tests at both MRT and Tokyo
Gas (Klassen, 2005). It theoretically introduces no impurities into the permeate hydrogen. There are
obvious safety issues with vacuum operation, as there is an inherent risk of air ingress into the
permeate line, posing an explosion risk. This was of special concern here, as the permeate stream
would have to pass through a vacuum pump, a potential source of ignition. Air ingress would also
affect product quality.
The permeability of the membranes did not decrease during the pilot testing. Another important
finding is that the measured permeation fluxes during the pilot reforming tests were reasonably close
to the predicted value, indicating that "effectiveness"of the membrane was close to 100%and
suggesting that the mass transfer resistance within the fluidized bed was low. Value of less than.
100%may be due to:
Mass transfer resistance of hydrogen on the reactor side of the membrane.
129
If using an inert sweep gas, mass transfer resistance on the permeate side.
Pressure drop in the permeate system, so that the absolute pressure on the backside of the
membrane is higher than the measured pressure at the outlet.
Fouling, sintering or other degradation of the palladium foil.
Low catalyst activity.
The calculated membrane effectiveness was close to 100%in the pilot tests, higher than compared to
the work of Adris (1994). Perhaps the flow channels in the membrane assemble contributes to near
plug-flow conditions, reducing axial dispersion and enhancing bed-to-membrane mass transfer. It is
difficult to project whether the membrane effectiveness would decrease if the membrane flux and FL.
recovery were increased to economically practical values. Further experimentation is needed.
Theoretically, dense Pd membranes produce ultra-high purity H2. Given the tight feed specifications
of fuel cell manufacturers, this is a very attractive feature of membrane reactors. Although the H
2
quality decreased to -99.8%midway through the pilot tests, high-purity product was initially
produced, and there were no catastrophic membrane failures, even when the temperature was
increased to 650C. This shows the potential of the uncovered planar membrane to withstand the
fluidized bed environment, but more work is needed to show longevity over months of operation and
to establish a practical upper operating temperature.
Low catalyst activity resulted in poor results for some experimental runs. The deactivation of the
SMR (NiO on alumina) catalyst was not unexpected, as this catalyst is not designed for autothermal
reforming. However, the poor performance of the ATR catalyst was a surprise, and limited the extent
of autothermal reactor testing. No conclusive reasons for catalyst deactivation were found. More
discussions with the ATR catalyst supplier and further testing are needed to better understand the
catalyst performance. One advantage of fluidized beds is that catalyst can be replaced on-line, but this
was not practical with our pilot reactor configuration.
Finally, note that the while the mechanical design of pilot reactor allowed economical carbon steel to
be used for the pressure shell, the complicated geometry was impractical for research purposes. A
simpler, smaller reactor using higher-quality materials may have been more expensive, but would
have greatly helped experimentation. Other areas of the reactor design that could be improved
include:
Reactor connections - There were a very large number of connections to the reactor, especially
on the top flange, primarily for membranes and instrumentation. A change in the membrane
130
design, for example increasing the membrane panel height or eliminating membrane sweep,
would reduce the number of connections and simplify reactor assembly.
Membrane access - The core assembly was housed in a rectangular core box, which hung from
the top reactor flange. Assembly of the core internals was very time consuming. A mechanical
design that would allow improved access to the membranes would be desirable. An alternative
reactor geometry is proposed in Figure 4.21. It uses the chord layout proposed in Figure 3.22
(Chapter 3), in which the catalyst solids return to the bottom of the reactor via two chord
segments, rather than via an annulus. Membranes could then be access through flanges on the
side of the cylindrical reactor. Another benefit is that the membranes would then occupy a greater
fraction of the reactor volume, reducing the overall size of the reformer vessel.
Oxidation air Reactor off-gas
Top of core divider
Membranes
NG / steam feed
Catalyst returns (2)
Membrane flanges
Bottom of core divider
Figure 4.21: Alternate ICFBMR reactor layout (elevation and plan view)
131
4.10 Conclusions
Although operation of the pilot plant proved to be challenging due the scale of the equipment, and
lack of automation, sufficient results were obtained to validate the main features of the ICFBMR
configuration. Conclusions from the pilot testing include:
The uncovered membrane panels withstood ~14 days of hot operation and six temperature cycles
with no catastrophic failures. The permeate hydrogen was initially very pure (>99.999%,
excluding N
2
), but dropped to 99.8%(dry basis) after approximately 180 hours of testing. Four of
six membrane panels did not exhibit any measurable leakage during the pilot tests. Membrane
longevity in hot fluidized bed environments requires further study.
The permeability of the membranes was not significantly affected by pilot testing.
The membrane "effectiveness" was close to 100%in the reforming experiments when no
nitrogen sweep was used. The effectiveness of the N
2
sweep was slightly lower than predicted by
modelling.
Solids were shown to circulate within the reactor at a rate close to that predicted by cold model
scaling correlations.
Air addition had only a modest impact on membrane flux, confirming cold model testing that
showed that only a portion of the N
2
in the oxidation air circulated to the reactor core.
A positive shift in the equilibrium due to in-situ H
2
removal was demonstrated.
132
Chapter 5. Post-Run Membrane Testing
The ICFBMR pilot reactor was disassembled after the experimental runs described in the
previous chapter. The six membranes were removed from the internal reactor assembly,
inspected for damage and tested for leaks. Two of the membrane panels were placed in a
permeation vessel and flux tested. The results showed that the membrane flux was slightly
higher than measured before those membranes were installed in the pilot reactor.
Permeate purity testing on these membranes indicated small leaks, though measured
hydrogen separation factors were still very high. The membrane foil of one membrane was
removed from its stainless steel substrate. SEM-EDX analyses indicated significant scaling
on the backside of the membrane foil, likely the cause of the lower-than-expected
permeation flux of the ICFBMR panels.
5.1 Membrane Removal and Observations
After the pilot tests, the core draft box containing the membrane assembly was removed from the
pilot reactor together with the top reactor flange. Figure 5.1presents a photograph of the I CF BMR
internals being removed from the reactor. Note the grey catalyst scale on all surfaces. A large lump of
catalyst was found adhering to the reactor outlet filters, but this did not totally block the filter
surfaces, and was easy to remove. The outlet filter pressure drop was acceptable during all pilot plant
runs (<100 kPa). No other significant lumps of catalyst were observed on any other internal surfaces.
A l l installed parts were still firmly attached, and no degradation of any components could be seen.
Threaded nuts could be unbolted normally.
The pass-through connections on the top flange (i.e. thermocouples, pressure taps, sweep gas lines,
hydrogen permeate) were removed or cut, and the core box was disconnected from the top flange.
Next the membrane assembly was removed from the core box by first disconnecting the rods securing
the assembly to the box, then by pushing the assembly out of the top of the core box. The assembly
was firmly stuck in the core box, and was removed by knocking the bottom of the assembly with a
heavy hammer.
133
Figure 5.1: ICFBMR internals being removed from horizontal pilot plant reactor
The internal membrane assembly held up well, with all clips, wires, gaskets and nuts still firmly in
place. All metal surfaces were covered with a uniform grey scale, with the exception of half of one
side of membrane panel #8, which was relatively clear. Figure 5.2 shows a photograph of the internal
assembly prior to it being dismantled.
The six membrane panels were removed from the membrane assembly, and then individually leak
tested using the refrigerant detection procedure described in Chapter 2. Significant leaks were
detected on membranes #1, 3, 4 and 5, but not always on both faces of the panel. A possible leak was
found on panel #8. No leaks were found on the membrane surfaces of panel #6. In addition, a small
leak was found on the permeate tube weld on panels #1 and 8. Figure A5.1 in Appendix 5
summarizes the membrane observations and refrigerant leak detection results.
134
Figure 5.2: ICFBMR membrane assembly after service in pilot plant reactor
5.2 Membrane Flux Testing
Panels #6 and 8, thought to be leak-free from the refrigerant check, were flux-tested in the membrane
permeation rig shown in Figure 2.12. Panel #8 was installed at the top of the core draft box, while
panel #6 was located immediately below (see Figure 5.2 above). The permeation vessel contained
pure hydrogen and was heated to 560C. The vessel pressure was varied between 170 and 585 kPa,
and the flux on the two panels measured. The permeate pressure was 101kPa, and no sweep gas was
used. Figure 5.3 presents the resulting flux data as a function of the difference of the square root
hydrogen partial pressures (see Table A5.1 in Appendix 5 for data). The data in Figure 5.3 are very
linear, and the trend line passes near the origin, as would be expected if the hydrogen permeation
followed Sievert's equation.
The membrane panel permeation area was previously calculated to be 0.0258 m
2
from geometry.
Based on membrane permeation equation 2.10, the effective permeation area of the two panels, were
found to be 0.0081 and 0.0167 m
2
for membrane #6 and 8 respectively. These values are significantly
135
higher than previously determined in flux testing prior to the membranes being installed in the pilot
reactor and pilot reactor flux testing (see Table 5.1). The data for panel #8 is especially inconsistent.
0. 004
(A
15 0. 003
0. 002
5
o
0J
-4-
CO
I 0. 001
0 .
R
2
= 0. 9987 ...
x Panel #8
- Panel #6
_
" " '
R
2
= 0. 9995
0 100 200 300 400 500
Partial H2 pressure, hi gh
A
0.5 - Partial H2 pressure, l ow
A
0.5 ( Pa
A
0.5)
Figure 5.3: Post-pilot run flux test data for membrane panels #6 and #8 at 560C
Table 5.1: Calculated effective membrane permeation area, before, during and after pilot runs
Panel Pre-pilot testing Average of pilot flux Post-pilot testing
testing in run 5 and 6
Effective Fraction of Effective Fraction of Effective Fraction of
area (m
2
) expected area (m
2
) expected area (m
2
) expected
#6 0.0059 23% 0.0069 27% 0.0081 31%
#8 0.0101 39% 0.0096 37% 0.0167 65%
The increases in the calculated effective permeation area are not due to membrane leaks, which were
found to be small (see next section). The low initial membrane permeation rate may have been due to
organic impurities initially adsorbed onto the membrane surface, later removed during the ICFBMR
pilot tests. It is not likely that wear of the palladium foil by particle fluidization thinned the
membrane, as a heavy catalyst scale was present on the membrane surface. Subsequent to the pilot
testing, it was found that exposure of the membrane to air at high temperatures (>500C) can oxidize
organic contaminants, restoring the membrane flux (Li, 2005). Another possible explanation for the
higher flux in the post-pilot tests is that surface catalyst scale may have been dislodged during
removal of the membrane assembly from the reactor.
5.3 Permeate Purity
The purity of the permeate gas from panel #6 and 8 was also tested. An equimolar mixture of
hydrogen and helium was fed to the permeation rig (Figure 2.12 in Chapter 2). The rig was then held
136
at the same temperature (560C) as in the flux test described in the previous section. The purity of the
permeate hydrogen was measured with a gas chromatograph, which detected small amounts of
helium in the permeate stream from both panels, indicating pinhole leaks. Table 5.2 summarizes the
permeate purity data, in which the hydrogen-to-helium separation factors are calculated from:
H
2
: He separation factor = {^"/[p _ p jj^
PHeh
~ ^J/j j (5-1)
Equation 5.1 is simply a ratio of the flux to partial pressure driving force for the two species. The
partial pressure difference, rather than the difference in the square root partial pressures, is used as
this permits comparison with microporous membranes. It should be noted that helium has a very
small atomic radius, and thus leaks of heavier compounds such as methane and carbon monoxide
should be lower than for helium. The concentrations of helium in the permeate stream are still low,
and thus did not significantly affect the analysis of hydrogen flux data presented in the previous
section.
Table 5.2: Permeate purity in post-pilot runs
(560C, 50:50 mixture of H
2
and He in permeation vessel, 101kPa permeate pressure)
Panel Vessel pressure (kPa) [He] in permeate H
2
:He separation factor
#6 439 0.031% 6071
#6 439 0.029% 6360
#6 439 0.028% 6525
#8 494 0.25% 671
#8 494 0.26% 660
Gas chromatograph analyses from membrane panels #6 and #8 during the last pilot test did not
indicate any non-hydrogen species. It is not known whether the leaks found during the above post-run
testing were present during the pilot work. They could have been a result of the heavy handling
required to remove the membrane assembly from the ICFBMR core box. >
5.4 Foil analysis with S EM / EDX
The palladium alloy foil from membrane panel #1 (side A) was removed from the stainless steel
substrate by peeling off one corner using a knife. The foil was bonded firmly to the sealing edges, but
could be removed with a firm tug. The permeation area, which was covered by alumina, also
appeared to be bonded to the foil, though more loosely than the seal edges. Figure 5.4 shows a corner
of the membrane foil peeled away, exposing the alumina substrate. The scale on the front of the
membrane could be readily brushed off with tissue paper.
137
Figure 5.4: Peeling of the palladium alloy foil from membrane panel #1
Three samples were cut from the palladium foil and analysed by a scanning electron microscope
(S EM) and ED X (energy dispersive x-ray) using a Hitac hi model S-2300 analyzer. S EM photographs
of the used palladium alloy foi l were taken at x300 (Figures 5.5 to 5.8), xlOOO (Figures 5.9 and
Figures A5. 2, A5. 3 and A5. 5 in Appendi x 5) and x3000 magnification (Figures A5. 4, A5. 6 and A5. 7
in Appendix 5). S EM images of fresh, unused P d
7 5
A g2 5 foil are also presented:
Fresh palladium alloy foi l - Note the smooth surface appearance in Figure 5.5 compared to the
subsequent images of the used foi l . The scratch-like marks may be due to c old rolling
imperfections.
Scaled front (retentate side) - S EM images show heavy scale deposits across the entire
membrane surface (Figure 5.6).
Polished front, exposing metallic foil (retentate side) - The surface morphology is much more
regular than the previous scaled image, but smaller scale deposits are still present on the surface
(Figure 5.7).
Back of membrane (permeate side) - Heavy, irregular deposits are interspersed with smoother,
metallic surfaces, covering approximately two-thirds of the surface area (Figure 5.8).
138
Figure 5.5: S EM of fresh Pd75Ag
2
5 foi l at x300 magnification
X 3Q 0 0000 2 0 1 0 0 P m
Figure 5.7: SEM of polished membrane foil (front) at x300 magnification

;
Is' if* ;
11
.* SSRrf v-SSC^Wt
- -. - > - , - : :
x30 0000 20NV 100^m
Figure 5.8: SEM of back of membrane foil at x300 magnification
14 0
The SEM image in Figure 5.9 is a xlOOO magnification of the back of the membrane foil. Two
distinct surface zones are readily apparent. The rectangular boxes indicate areas where separate EDX
scans were taken.
Figure 5.9: SEM of back of membrane foil at xlOOO magnification
Box 1 and 2 are areas of EDX scan #3 and #4 respectively
Data from four EDX scans of the used membrane are presented in Figure 5.10 below. Metal
concentrations varied considerably in the four zones analyzed.
Scan #1 - scaled front of membrane (Figure A5.8 in Appendix 5): It is apparent that most of the
scale on the front of the membrane is due to nickel, and to a lesser extent alumina, present in the
SMR catalyst. Very little palladium was detected.
Scan #2 - polished front of membrane (Figure A5.9 in Appendix 5): The surface of the foil is
detected in this scan, as evidenced by the large concentrations of palladium and silver. The
measured palladium to silver ratio is approximately 2. Significant amounts of nickel are present,
likely resulting from incomplete removal of the surface scale.
Scan #3 - smooth zone of back of membrane (box 1 in Figure 5.9, EDX scan in Figure A5.10 in
Appendix 5): This area is clearly the metallic foil area of the membrane. Some iron was also
detected, likely from the underlying stainless steel support. Note that almost equal amounts of
141
silver and palladium were detected, a much higher proportion of Ag than detected in scan #2
(polished front) or present in the original foil (25%). This is consistent with other research (Shu et
al., 1993, Amandusson et al., 2001) that indicates silver migration to the permeate membrane
surface. This has been explained as either a thermally induced process to minimize the free
energy of the surface, or induced by surface chemisorption.
Scan #4 - scaled zone of back of membrane (box 2 in Figure 5.9, EDX scan in Figure A5.11 in
Appendix 5): This area contained significant amounts of iron, nickel and chromium, with the
stainless steel sintered support being the obvious source. Palladium concentrations were also
high. Silver was detected, but at lower concentrations relative to palladium than in the original
foil.
1.Front (scaled) 2.Front (polished) 3.Back (smooth zone) 4.Back (scaled zone)
Figure 5.10: Summary of EDX analyses of used membrane foil removed from membrane #1
5.5 Discussion
All six of the membranes removed from the ICFBMR pilot plant appear to have developed leaks,
though it is not known whether all leaks can be attributed to service in the reformer (some may have
been caused by the rough handling required to. dissemble the reactor). From pilot plant results and
post-run permeation tests, it appears that there were no catastrophic membrane failures. Permeate
concentrations of non-hydrogen species were low. Instead, very small pinholes are likely to have
developed, though no pinholes were detected in the SEM scans of the used membranes.
Flux testing on two membranes indicated that permeation was greater after service in the pilot plant,
perhaps attributable to removable impurities, such as carbon, being initially present. It appears that
142
the heavy catalyst scale formed on the membrane surface did not significantly hinder permeation. The
hydrogen flux of the used membranes could be well described with a hydrogen partial pressure
exponent () of V i , indicating that diffusion of atomic hydrogen likely remained the main resistance to
hydrogen permeation.
SEM images of the backside of the membrane indicates the presence of a heavy metallic scale, likely
due to direct contact of the palladium foil with the stainless steel support. The alumina inter-layer
deposited on the sintered metal support was intended to prevent this. The metallic scale covered a
significant portion of the foil, roughly two-thirds in the SEM images. It is likely that this is the main
contributor to a reduction in the membrane permeation relative to that predicted by the Sievert's
permeation equation. The membrane foil may be only releasing hydrogen at the unsealed surface,
thus greatly reducing the effective membrane area. It is concluded that calculation of an effective
membrane area for each membrane, as in Chapter 2, is an appropriate means of characterizing the
loss in permeation.
The mode of pinhole development in the membranes is not known. Perhaps the adhesion of the
metallic scale to the backside of the membrane reduced the foil mobility and led to local stresses in
the palladium as it expanded and swelled with hydrogen and thermal expansion. What is clear is that
the very thin alumina layer deposited below the foil was inadequate to prevent contact between the
palladium and the stainless steel support. Since the ICFBMR membranes were fabricated, MRT has
increased the thickness and modified the composition of the alumina layer, and this has resulted in
membrane permeation areas remaining close to that expected from the geometry (Li, 2005).
143
Chapter 6. Process Simulation and Economics
A commercial process simulator was used to model the ICFBMR reactor and perform a
sensitivity analysis on the major reactor variables. The reactor model accounted for the
internal circulation of solids and gas, but did not include reaction kinetics or
hydrodynamics. A base case model was created for a unit producing 30 Nm
3
/h of high-
purity H2, which was then developed into a process flowdiagram. Performance parameters
and economics of the 30 Nm
3
/h unit are discussed.
6. 1 Introduction
The I CF B M R pilot plant results demonstrated the potential to produce high-purity H
2
, but hydrogen
recoveries were l ow due to the installed membrane area and, in some runs, poor catalyst performance.
In order to extrapolate pilot plant experience to a c ommerc ial design for small-scale hydrogen
production, process simulations were undertaken. The main objective was to create a design tool for
future reactor and process designs. The simulation was also used to reconcile data from the I CF B M R
pilot plant.
F ol l owi ng the experimental F B M R work of Adri s (1994) and R oy (1998), several reactor models
have been developed to simulate the F B M R process using two-phase fluidized bed reactor models:
Adris and co-workers (1997a, 1997b) presented findings from a fluidized bed reactor model,
identifying effects of permeation rate and pressure on methane conversion and hydrogen
production.
Model l i ng by Roy et al. (1998) studied various means of supplying heat to the F B M R process
and concluded that the new process had the potential to reduce capital and operating costs
compared to conventional S M R fixed bed reactors.
Ab b a et al. (2003) adapted a generalized fluidized bed reactor model to autothermal reforming in
a F B M R . Results indicated a significant reduction (-30%) in permeate H
2
when air rather than 0
2
144
is used as an oxidant in the well-mixed reactor. It was predicted that superficial gas velocities in
excess of 0.3 m/s would be of little benefit.
Dogan et al. (2003) summarized autothermal FBMR modelling results with direct oxygen
addition. Varying the steam-to-carbon ratio showed only a mild effect on hydrogen permeate
yield. The benefits of high temperature operation to produce higher H
2
membrane fluxes were
also highlighted, although the operating temperatures investigated (650 to 850C) are excessive
for the palladium-silver membranes of interest in my work. Rakib and Alhumaizi (2005) also
modelled oxygen addition to an FBMR.
Elnashaie and co-workers have published a number of modelling papers on a circulating fluidized
bed membrane reactor for reforming of natural gas and higher hydrocarbons (e.g. Prasad and
Elnashaie, 2002, Chen and Elnashaie, 2005).
In all of the above models, the kinetics of Xu and Froment (1990) were adapted and combined with
the hydrodynamics of a fluidized bed reactor. All assumed vertical membrane tubes (or U-tubes) and
considered permeate sweep gas to increase the hydrogen flux. In some cases, simulations have
suggested that the use of long vertical tubes in the FBMR would lead to reverse permeation of
hydrogen in the relatively cool freeboard of the reactor (e.g. Abashar et al., 2003). This can be
avoided with planar membrane modules that extract hydrogen over a more limited reactor height
interval.
The above studies also indicated that the kinetics of the SMR process are sufficiently rapid, at least
for temperatures larger than about 550-600C, that chemical equilibrium is very nearly achieved for
FBMR heights and catalysts which are likely to be of practical interest. In addition, the above models
indicate that for Pd membranes with current thicknesses (25 to 75 pm), the membrane flux is the
controlling parameter of the reactor performance. In view of this, it was decided to ignore the SMR
reaction kinetics and simulate the ICFBMR process using equilibrium reactors in a commercial
software environment (HYSYS, version 3.4) in order to create a flexible process design tool. A
commercial simulator permits rapid development of the overall process flow diagram and facilitates
sensitivity analyses and equipment sizing. The only hydrodynamic feature considered in the
simulation is internal circulation of solids, gas and heat.
6.2 Reactor Simulation
The HYSYS model included interna! circulation of catalyst and gas down the annulus and up the
reactor core. SMR equilibrium values from the HYSYS simulation were found to closely match those
predicted by an independent kinetic model. Details on the HYSYS reactor model are presented in
145
Table A6.1.1, Appendix 6.1. The ICFBMR was simulated with a series of Gibbs reactors and
hydrogen separators, as shown schematically in Figure 6.1. The HYSYS flowsheet and algorithm are
presented in Figures A6.1.1 and A6T.2, Appendix 6.1. The reactants modelled wereC H 4 , C
2
H6, CO,
C0
2
, H
2
and H
2
0. Carbon formation is not thermodynamically favoured at these conditions, and was
thus ignored.
I CF BMR
Preheated air)d 1
Core draft box
(10 repeated membrane/
reactor pairs)
Stream key
Gas stream
So lid stream

Heat stream
>
Preheated
C H4 /H2 Q
E. Gas split
D. Gibbs reacto r
(o xidant)
,9.10> <10.1
C10 Gibbs reacto r
(adiabatic)
<6.10> <10.9
B10. Membrane k?i ?
rb.n Gibbs reacto r"
1
L (adiabatic) I
j
-
B.n Membrane |-<^>
C1 . Gibbs reacto r
(adiabatic)
A. Gibbs reacto r
(adiabatic)
14 V-I Rxtr o f f -gas
Heat lo ss
Annul ar
circul ation
(recycle)
Permeate H^)
Figure 6.1: ICFBMR simulation schematic
Preheated steam and methane (1) are mixed with hot circulating solids (2) from the oxidation
zone (D) in a Gibbs reactor (A), representing the area immediately above the main feed
146
distributor. The circulating solids also drag down a portion of the gases (3) from the top of the
reactor (E). The temperature drops as methane and steam react adiabatically in the first Gibbs
reactor (A). Higher catalyst circulation reduces the temperature drop. The temperature at the exit
of the first Gibbs reactor (4) is considered to be the maximum operating temperature of the
membranes.
The gas stream (4) from the Gibbs reactor (A) then flows to the first membrane (Bi) in the draft
tube, where pure, low-pressure hydrogen is removed (8.1). The hydrogen removal shifts the SMR
equilibrium, and the non-permeate gases (6.1) and solids (5) further react in an adiabatic Gibbs
reactor (Ci).
A series of ten membrane / Gibbs reactor pairs then follows, each removing an equal fraction of
the permeate hydrogen. By using a series of reaction / separation steps, the partial pressure
driving force in each membrane set is known, allowing the membrane permeation area to be
calculated. Full chemical equilibrium is assumed for the product stream after each H
2
removal
stage.
Gas (9.10) and solids (10.10) from the last core Gibbs reactor (C.10) leave the core draft box.
These streams react with preheated air (11) in another Gibbs reactor (D). In order to account for
ambient reactor heat losses, a heat stream (12) is rejected by the oxidant reactor (D). The flow of
air (11) is adjusted until the reactor energy balance is satisfied. Note that the simulation reacts
methane with the oxygen, as this minimized the Gibbs free energy. In practise, a portion of the
hydrogen is also likely to be oxidized. In any event, the question of which chemical species is
oxidized is does not practically matter, as the reactor off-gas is combusted in a commercial
system to recover heat for raising steam and preheating feeds, as depicted in Figure 6.10.
Hot catalyst (2) is circulated back to the bottom of the reactor via the annular region of the
reactor. The solids mass flux (G
pcore
, kg/m
2
s) is assumed to be a function of the superficial gas
velocity in the core (Ucore, m/s) and the catalyst particle density (p
p
= 2,100 kg/m
3
), as described
by the correlation developed in Chapter 3 (Figure 3.20) for vertically-slotted panels. As discussed
in Chapter 5, this equation matched the deduced circulation rate in the pilot reactor within 10%:
G
p j a n
=- 0. 000103(^L /
c o r e
)
2
+0. 180(
P p
L /
c o r e
)- 11. 3 (6.1)
In order to set the solids circulation flow (m
pcore
, kg/s), the flow area in the core draft box (A
core
)
is required. This is calculated from the user-inputted superficial core velocity (U
core
) and the
volumetric flow of gas entering the core draft box (stream 4):
A r~* Qcore s~* ff\0\
p,core core p,core j j p,core v^'^v
147
The circulating solids act only as a heat carrier in the simulation. Calcium was selected to
represent the circulating catalyst solids, as AI2O3 was not available in the HYSYS property
database. Calcium is chemically inert in the simulation. As the specific heat of calcium in
HYSYS is slightly lower than that of alumina, the circulation rate expression (equation 6.2) was
multiplied by a specific heat adjustment factor (1.15) to match the heat flow of the circulating
alumina catalyst.
The gas leaving the oxidant Gibbs reactor (13) splits into two compositionally identical streams;
a reactor off-gas stream (14) and a stream recycled back to the bottom of the reactor with the
circulating solids (3). Cold model testing (Chapter 3) suggested that the volumetric downward
flow of gas was approximately equal to the volumetric flow of solids down the annulus. The
volumetric flow of the circulating gas is therefore set by dividing the solids circulation rate
(equation 6.2) by the catalyst bulk density (2,100 kg/m
3
).
The simulation application is somewhat limited as reaction kinetics and hydrodynamics are not
accounted for. In addition, the simulation does not address the following features of the ICFBMR
system:
A very small portion of the methane may flow up the annulus, bypassing the reactor core.
Some heat transfer must occur from the hot annulus zone to the cooler reactor core.
Heat conduction vertically along the membrane panels and supports is neglected.
The simulation effectively assumes plug flow (ten well-mixed stages) of gas and solids up the
reactor core. More than ten stages did not significantly alter the simulation results and added
to computation time. In cold model experiments, a small fraction of the gas and solids were
found to circulate from the oxidation zone to the upper sections of core.
The pressure drop in the reactor is ignored, i.e. the pressure in each of the compartments was
assumed to be the same.
The effective membrane area (A
e
j) for each of the permeation zones can then be calculated from the
simulation output using the hydrogen flux equation for Pd
75
Ag25:
-1
T Q
H
exp(
) ( P H , ? - P H ,
5
)
(6.3)
k
H
R T
where T is the membrane thickness (base case 50E-6 m).
Q
H
is the H
2
permeation per stage (base case 30 Nm /h/10 stages = 0.037 mol/s).
k
H
= 3.43E-7 mol/m s Pa
05
(see Chapter 2)
148
E
p
= 9,180 J/mol (see Chapter2)
T is the permeation temperature (K), assumed to be equal to the temperature of the
reactor gas entering each membrane separation stage.
P H I , is the hydrogen partial pressure in the reactor (Pa). For each permeation zone,
Put, is assumed to be the average of that zone's inlet and outlet equilibrium partial
pressures.
P
H
i is the hydrogen partial pressure in the permeate stream (Pa). The base case is
atmospheric pressure (101 kPa), without any sweep gas.
6.2.1 S i mul ati on Base Case
The main reactor simulation variables and their base values are listed in Table 6.1. A summary of the
main process streams for the base case is presented in Table 6.2. Refer to Figure 6.1 for
nomenclature. Full stream output data for the base case simulation are presented in Table A6.1.2,
Appendix 6.1.
As indicated in Table 6.1, the target value for the permeate hydrogen to methane molar ratio was2/2.
Higher hydrogen recovery is achievable if more membrane area is installed. However, when the
overall system is considered, a hydrogen recovery between2.5 to2.7 is likely to be an optimal, as the
reactor off-gas containing methane, CO and unrecovered H2 is combusted to preheat the reactor
feeds. If a higher hydrogen recovery were used, additional natural gas would be required to
supplement the burner duty. This process configuration is presented in Section 6.3.
The base case simulation output appears reasonable. The oxidation zone was calculated to be 18C
hotter than the inlet temperature of the reactor core (600C). The oxidation temperature is a function
of the solids circulation rate, the preheat temperature of the reactor feeds and the specified maximum
membrane temperature. The flow of oxidation air was adjusted to satisfy the reactor energy balance,
resulting in an 02:CH4 molar ratio of 0.39. Approximately 10%of the gases in the upper reactor were
estimated to recycle to the reactor core with the circulating solids. Due to hydrogen removal,
partially countered by the increase in molar flow due to reaction, the number of moles of gas leaving
the reactor core (excluding permeate H
2
) is approximately two-thirds of the gas entering the core.
149
Table 6.1: ICFBMR base case simulation
Variable description Base case Notes
Reactor pressure 2,500 kPa Max 1,500 kPa in ICFBMR pilot plant
<D
Total permeate H
2
flow 30 Nm
J
/h
Lower side for distributed H
2
market
J O
.2
Steam-to-carbon molar ratio of feed 3.0 Typical industrial value
a
> Permeate FbjCFL, ratio 2.5 Reasonable objective
c
<D
T 3
C
Superficial core velocity (U
core
) 0.25 m/s Based on cold model tests
u
D .
CU
TD
Max membrane operating temperature 600C Temperature of stream 4 in Figure 6.1
C
Feed preheat temperature 600C Assures energy integration
Reactor heat losses 2kW -10%of endothermic reaction heat
i
r
i
a
b
l
e
s

C H 4 flow 12Nm7h Set by H
2
flow and H
2
recovery
i
r
i
a
b
l
e
s

Steam flow
36NmVh Set by CFL, flow and H
2
0:CFL| ratio
TO
>
3
GvCFL, molar ratio 0.39 Adjusted by reactor heat balance
1)
-a
c
Solids circulation 1,356 kg/h Set by correlation with U
cor
e (Eq. 6.2)
a,
Q
Oxidation zone temperature 618C
Adjusted to match maximum
membrane operating temperature
Membrane thickness (r) 50E-6 m Readily commercially available
<8
c
Permeate sweep gas
None
Reduces connections and ensures
product impurities
M
e
m
l

Permeate pressure 101 kPa No vacuum equipment required
M
e
m
l

Membrane efficiency 100% Area predicted by Eq. 6.3
150
Table 6.2: Stream summary for 30 Nm Th reactor base case simulation
(Note: Stream numbers refer to Figure 6.1)
Stream 1 2 3 4 5 6.1 6.2 6.3 6.4 6.5 6.6 6.7 6.8 6.9 6.10 8.2
Mass Flo w [kg/h] 37.55 1558.98 5.33 42.88 1559 42.61 42.34 42.07 41.80 41.53 41.26 40.99 40.72 40.45 40.18 0.27
Vo lumetric f lo w [m3/h] 6.18 1.14 0.65 7.61 1.14 7.21 6.93 6.65 6.37 6.10 5.83 5.57 5.32 5.07 4.82 9.66
Mo lar Flo w [kmol/h] 2.14 38.90 0.22 2.62 38. 90 2.49 2.40 2.31 2.22 2.14 2.05 1.97 1.89 1.80 1.72 0.13
Temperature [C] 600 618 618 600 600 600 597 594 592 588 585 582 579 575 572 603
Pressure [kPa] 2500 2500 2500 2500 2500 2500 2500 2500 2500 2500 2500 2500 2500 2500 2500 101
Heat Flo w [kJ/h] -3.79E+05 7.63E+06 -3.27E+04 -3.86E+05 7.61E+06 -3.88E+05 -3.87E+05 -3.85E+05 -3.83E+05 -3.81 E+05 -3.79E+05 -3.77E+05 -3.75E+05 -3.72E+05 -3.70E+05 2.27E+03
Mo le f ractio n -CH4 0.25 0 0.0131 0.1551 0 0.1634 0.1607 0.1572 0.1530 0.1480 0.1421 0.1352 0.1274 0.1187 0.1086 0
Mo le f ractio n - CO 0 0 0.0154 0.0084 0 0.0088 0.0096 0.0103 0.0110 0.0116 0.0122 0.0128 0.0133 0.0137 0.0141 0
Mo le f ractio n - C02 0 0 0.1778 0.0578 0 0.0609 0.0718 0.0839 0.0973 0.1122 0.1288 0.1471 0.1672 0.1895 0.2140 0
Mo le f ractio n -H2 0 0.75 0 0.4095 0.5532 0 0.5830 0.5877 0.5913 0.5940 0.5959 0.5968 0.5961 0.5947 0.5925 0.5885 0
Mo le f ractio n - N2 0 0 0.3040 0.0252 0 0.0266 0.0276 0.0286 0.0298 0.0310 0.0323 0.0336 0:0351 0.0367 0.0384 0
Mo le f ractio n - 02 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
Mo le f ractio n - H2 0 0 0.0802 0.2003 0 0.1572 0.1428 0.1287 0.1150 0.1013 0.0878 0.0751 0.0623 0.0489 0.0365 1.000
Mo le f ractio n - Ca 0 0 0 0 1 0 0 0 0 0 0 0 0 0 0 0
Sream 9.1 9.2 9.3 9.4 9.5 9.6 9.7 9.8 9.9 9.10 10.1 11 12 13 14 15
Mass flo w [kg/h] 42.61 42.34 42. 07 41. 80 41. 53 41.26 40.99 40.72 40.45 40.18 1559 28.84 - 69.02 63. 69 2.70
Vo lumetric flo w [m3/h] 7.32 7.04 6.76 6.49 6.22 5.96 5.70 5.45 5.20 4.96 1.14 2.92 - 8.35 7.71 95.5
Mo lar Flo w [kmol/h] 2.53 2.44 2.36 2.27 2.19 2.10 2.02 1.94 1.86 1.78 38.90 1.00 - 2.81 2.60 1.34
Temperature [C] 597 594 592 588 585 582 579 575 572 569 597 600 618 618 593
Pressure [kPa] 2500 2500 2500 2500 2500 2500 2500 2500 2500 2500 2500 2500 - 2500 2500 101
Heat Flo w [kJ/h] -3.85E+05 -3.83E+05 -3.81 E+05 -3.79E+05 -3.77E+05 -3.75E+05 -3.73E+05 -3.70E+05 -3.68E+05 -3.65E+05 7.61E+06 1.76E+04 7.20E+03 -4.23E+05 -3.90E+05 2.23E+04
Mo le f ractio n -CH4 0.1522 0.1486 0.1443 0.1392 0.1333 0.1266 0.1190 0.1105 0.1008 0.0902 0 0 - 0.0131 0.0131 0
Mo le f ractio n - CO 0.0091 0.0097 0.0103 0.0109 0.0115 0.0120 0.0124 0.0128 0.0131 0.0133 0 0 - 0.0154 0.0154 0
Mo le f ractio n - C02 0.0680 0.0793 0.0918 0.1056 0.1209 0.1378 0.1562 0.1763 0.1987 0.2230 0 0 - 0.1778 0.1778 0
Mo le f ractio n -H20 0.5566 0.5589 0.5603 0.5606 0.5600 0.5582 0.5554 0.5515 0.5463 0.5400 0 0 - 0.4095 0.4095 0
Mo le f ractio n - N2 0.0261 0.0271 0.0281 0.0291 0.0303 0.0315 0.0328 0.0341 0.0356 0.0372 0 0.79 - 0.3040 0.3040 0
Mo le f ractio n - 02 0 0 0 0 0 0 0 0 0 0 0 0.21 - 0 0 0
Mo le f ractio n - H2 0.1881 0.1764 0.1652 0.1545 0.1441 0.1340 0.1243 0.1148 0.1055 0.0963 0 0 - 0.0802 0.0802 1
Mo le f ractio n - Ca 0 0 0 0 0 0 0 0 0 0 1 0 - 0 0 0
Figure 6.2 presents the temperatures and average hydrogen partial pressures for the ten membrane
permeation stages for the base case (stage 1 is at the bottom, 10 at the top). A significant temperature
drop (~30C) is predicted over the reactor core. Another item of note is the reduction in the hydrogen
partial pressure as gases flow up the reactor core, corresponding to a reduced permeation driving
force. The reactor-side H
2
partial pressure in the final permeation stage is -250 kPa, still well above
the base case permeate-side pressure (101 kPa).
600 600
200
1 8 10 2 3 4 5 6 7
Hydrogen removal stage
Figure 6.2: Permeation stage temperature and reactor hydrogen partial pressure (base case)
Each membrane stage in the simulation is assumed to permeate an equal flow of hydrogen. However,
as the temperature and hydrogen partial pressure are reduced as the gases pass upward through the
reactor core, the permeation area required for each stage increases (see "adiabatic"curve in Figure
6.3). The permeation area in the last stage is approximately twice that required for the first H
2
stage,
indicating that membrane panels at the bottom of the reactor would produce more H
2
than panels of
equal area located higher in the reactor core. The total permeation area (for the assumed 50 um thick
membrane) is the sum of the areas of all permeation stages, calculated to be 2.34 m
2
. As the
calculated permeation area (equation 6.3) is proportional to the membrane thickness, 25 urn thick
membranes would halve the required membrane.
If the internal solids circulation were very high, the reactor core would approach isothermal
operation. The effect of an isothermal core (600C) on membrane area is also presented in Figure 6.3
("isothermal"curve). The total membrane area is calculated to be 2.01 m
2
for the isothermal case,
14%less than calculated if the core operated adiabatically.
152
0.4
0 -I , , , 1 , 1 1 1 1
1 2 3 4 5 6 7 8 9 10
Hydrogen removal stage
Figure 6.3: Calculated permeation stage area (base case, 50 um Pd
75
Ag25 membrane)
6.2.2 Effect of Reac tor Vari ab l es
The influence of the major process variables on the ICFBMR design was investigated by parametric
studies using the HYSYS simulation. Perhaps the most important ICFBMR reactor design
characteristic is the required membrane area. As the ICFBMR reactor geometry is governed by the
membrane layout, the total reactor volume can be estimated based on the calculated membrane area.
One of the disadvantages of the ICFBMR design is that it tends to have a low overall space velocity
relative to fixed bed configurations. It is therefore important to reduce the membrane area in order to
produce a compact reactor design. In addition, the palladium membranes represent a significant
system cost.
Reactor pressure: Figure 6.4 demonstrates the strong effect of reactor operating pressure on the
predicted membrane area. Increasing reactor pressure above 2,500 kPa decreases the area only
marginally. The calculated membrane area is normalized to the base case (2.34 m
2
). The solids
circulation rate was assumed to be only a function of the superficial core velocity (equation 6.1,
above). If the core superficial velocity is held constant, increasing the reactor pressure reduces
the solids circulation rate as it decreases the flow area in the reactor core (A
core
). Decreasing the
solids circulation increases the temperature drop in the reactor core, increasing the membrane
area. The data in Figure 6.4 account for this effect.
Steam-to-carbon ratio: Also shown on Figure 6.4 is the effect of the steam-to-carbon ratio on the
normalized membrane area. Given the weak effect for the limited range considered, other issues
are likely to govern the preferred steam-to-carbon ratio, such as the potential for carbon
formation on the catalyst at low molar ratios.
153
2.5
1,000 1,500 2,000 2,500 3,000
Reactor pressure (kPa)
Figure 6.4: Effect of reactor pressure and steam-to-carbon ratio on normalized base case membrane
area (50 um Pd
75
Ag
25
membranes)
Hydrogen recovery: Figure 6.5 presents the influence of hydrogen recovery (moles of permeate
H
2
per mole of CFL, fed to the reactor) on the normalized membrane area at reactor pressures of
1,500 and 2,500 kPa. As expected, the membrane area requirement increases with increasing
hydrogen recovery. Hydrogen recoveries beyond a H
2
:CHt molar ratio of 3.0 become
progressively more difficult, as the hydrogen partial pressure in the reactor becomes very low,
and reaction kinetics may become limiting. Also shown in Figure 6.5 is the required 0
2
to CFL,
molar ratio as a function of hydrogen recovery. As more hydrogen is removed from the reactor,
the reaction duty increases, as more oxidation air is required to generate the heat needed for
autothermal operation.
H2 product:CH4 feed molar ratio (-)
Figure 6.5: Effect of hydrogen recovery on normalized base case membrane area
154
Membrane temperature: The base case assumes a maximum operating temperature of 600C. The
ICFBMR pilot reactor membranes operated at temperatures up to 650C. Increasing the
membrane operating temperature strongly decreases the membrane area as it increases the
specific membrane flux (see equation 6.3) and, more importantly, favourably shifts the SMR
equilibrium. However, operation at temperatures below 600C, and perhaps as low as 550C, is
likely needed for successful long-term operation of palladium-based membranes. Figure 6.6
clearly illustrates the incentive for the development of high-temperature membranes.
2.0
0.5 I , , 1 1
550 575 600 625 650
Maximum membrane operating temperature (C)
Figure 6.6: Effect of membrane operating temperature on normalized base case membrane area
Feed preheat temperature: The base case assumes that the feed streams (steam, methane and air)
enter the reactor at 600C. Figure 6.7 demonstrates that the normalized membrane area is
relatively insensitive to the feed preheat temperature, despite the significant change in the
required flow of oxidation air. This highlights how the ICFBMR facilitates circulation of heat
within the reactor, but not nitrogen from the oxidation air, which would otherwise reduce the H
2
flux through the membrane.
155
1.25
0.50
0.75
400
700 500 600
Feed preheat temperature (C)
Figure 6. 7: Effect of feed preheat temperature on normalized membrane area
Solids circulation rate: Increasing the solids circulation rate decreases the temperature drop in the
reactor core (Figure 6. 8). An isothermal core will result in higher fluxes and improved reactor
equilibrium in the upper reactor core. If solids circulation is lower than predicted in the
simulation, there is a penalty on the predicted membrane area. Increasing solids circulation
beyond the base case has only a modest effect on membrane area.
1.25
CU
k-
ro
0)
c
CO
I.
n
E
cu
E
TJ
CU
N
~m
E
i_
o
z
1.00
0.75
--Area
-o-Temperature
0 1 2 3 4
Normalized solids circulation (-)
Figure 6. 8: Effect of normalized solids circulation rate on normalized base case membrane area
Increased solids circulation transports more gas from the top of the reactor, diluting the hydrogen
in the reactor core, thus modulating the benefits of a more isothermal core. As noted above, it was
assumed here that the gas circulation is volumetrically equal to that of the catalyst circulation.
156
Hence, as solids circulation increases, more nitrogen is circulated to the core, thereby reducing
the hydrogen partial pressure. At very high solids circulation, the benefits of an increasingly
isothermal reactor core are slightly outweighed by the nitrogen dilution effect, and the area curve
turns slightly upward.
P ermeate pressure: Reducing the permeate H
2
partial pressure increases the driving force for
permeation, thus reducing the required membrane area. This may be achieved in membrane
reactors by utilizing permeate-side sweep gas. If a high-purity H
2
product were desired, the only
sweep gas that may be practical would be steam. However, the heat duty to generate sweep steam
reduces the overall thermal efficiency of the process, produces a wet hydrogen product, and
introduces impurities unless the water used to make the steam were to be subjected to rigorous
purification. A more practical method of enhancing the hydrogen flux may be to expose the
permeate stream to vacuum. However, there is a risk that vacuum operation could cause ingress
of air into the permeate H
2
, adding impurities to the hydrogen product and creating safety and
fiammabilify issues. Vacuum operation would also add to hydrogen compression costs. However,
as shown in Figure 6.9, there can be a significant reduction in membrane area with vacuum
operation.
X 2. 5 -i
RS
CO U. O "
E
z 0.0 -! ! 1 ' 1
0 50 100 150 200
Permeate H2 partial pressure (kPa)
Figure 6.9: Effect of permeate H
2
partial pressure on normalized base case membrane area
6.3 Design of a 30 Nm
3
/h ICFBMR
To assess the costs and performance of a commercial ICFBMR system, a design for a 30 Nm
3
/h
hydrogen production unit was developed with the HYSYS process simulator. This capacity is five
times larger than the nominal design rate of the ICFBMR pilot reactor, and would be sufficient to
support a fleet of about 150 fuel cell cars. The design assumes autothermal SMR operation using
157
direct air addition, with no external heat transfer to the reactor. At this capacity, the endothennic
SMR duty is approximately 20 kW, a reasonably large value for indirect transfer in a conventional
SMR design, but one that could be readily handled in an autothermal ICFBMR design.
6.3.1 Design Basis
The main feeds are natural gas, city water and atmospheric air (Table A6.1.3, Appendix 6.1). Based
on recent MRT operating experience (Li, 2005a), 25 um thick Pd
75
Ag25 membranes are chosen, but
are derated by 50%to account for membrane and reactor inefficiencies and thus modeled as 50 um
thick. The design assumes most of the reactor base case conditions presented previously.
Autothermal operation: The reactor is assumed to operate adiabatically through direct air
addition. Electrically powered heaters are installed for reactor start-up, but are not used for
normal operation. Preheating of steam and feed is accomplished through heat exchange with
combusted reactor off-gas.
Reactor conditions:
o 2,500kPa reactor pressure.
o 3.0 steam-to-carbon molar feed ratio.
o 2/4 moles of hydrogen product per mole of feed methane.
o 2 kW reactor heat loss.
Membranes:
o Maximum 600C operating temperature.
o 25 urn thick, palladium silver (25%) membranes, derated by 50%.
o Pure hydrogen product (i.e. no sweep gas).
o Maximum operating temperature of membranes of 600C.
o Permeate pressure is 101 kPa.
Hydrogen product:
o The hydrogen permeate stream is compressed to 3,000 kPa.
o Hydrogen storage and dispensing is outside the scope of the process design.
Reactor geometry and hydrodynamics:
o Superficial gas velocity within the range of 0.1 to 0.3 m/s, with the final velocity to be
determined by layout considerations,
o Membranes arranged with vertical communication slots between adjacent flow channels.
158
Burner. The non-permeate reactor off-gas has fuel value from residual C H 4 , CO and H
2
. It is
combusted to generate the high-temperature flue gas needed to raise steam and preheat the reactor
feed. The burner duty can be supplemented by fresh natural gas if necessary.
6.3.2 Process S i mul ati on
Several process options, mainly focused around heat integration, were considered in developing the
flowsheet. The process flow diagram and associated stream table are shown in Figure 6.10 and Table
6.3 respectively. Figure A6.1.4 in Appendix 6.1 presents the process flow schematic output from the
HYSYS simulation. The major unit operations included in the 30 NnvVh PFD include:
Water treatment: City water is treated in a mixed ion exchange bed to remove trace hardness and
organic compounds. Treated city water is combined with water recovered from the reactor off-
gas, then pumped to the process.
Natural gas treatment: Natural gas is desulfurized in two parallel beds of ZnO adsorbent.
Gas compression: Natural gas and oxidation are compressed to 100 kPa above the reactor
pressure. An adiabatic efficiency of 75%is assumed for the compressors. Inter-stage compressor
cooling is assumed to reject heat to ambient air.
Burner: Non-permeate reactor off-gas is combusted in a forced draft burner. Excess air is
adjusted to achieve the desired burner operating temperature. Increasing the burner temperatures
(i.e. minimizing excess air) results in higher overall system efficiencies. However, a maximum
burner operating temperature of 1,000C is imposed to allow standard materials of construction
to be used. A heat loss of 2 kW from the burner to the environment is assumed to account for
non-reactor heat losses. The bulk of the burner duty is provided by the reactor off-gas. A small
amount of natural gas is also combusted to represent the burner pilot flame.
Heat exchange: Steam is raised and the reactor feeds preheated through heat exchange with
reactor off-gas and burner gas.
ICFBMR: Preheated natural gas and steam react to form hydrogen, most of which is extracted by
the membranes to produce a high-purity H
2
stream. Sufficient air is added to allow the reactor to
operate adiabatically (with a 2 kW ambient heat loss allowance). After the non-permeate reactor
off-gas (ROG) leaves the reactor, it is cooled and condensed. Condensate is recycled back to the
feed water tank. The residual heating value in the cooled ROG is recovered in the burner.
H2 compression: The hydrogen permeate is compressed in a multistage compressor.
159
Table 6.3: Stream table for 30 Nm
3
/h flowsheet
Stream 1 2 3 4 5 7 8 9 10 11 13 14 15 16 20 21
Mass Flow [kg/h] 8.69 . 8.59 8.59 8.59 11.12 28.93 28.93 28.93 37.52 37.52 2.69 2.69 2.69 2.69 63.78 63.78
Actual Volume Flow [m3/h] 10.78 10.66 0.73 1.44 0.011 0.030 0.14 0.94 2.23 6.18 95.90 62.88 34.36 1.21 7.73 6.53
Molar Flow [kgmole/h] 0.541 0.535 0.535 0.535 0.617 1.606 1.606 1.606 2.142 2.142 1.332 1.332 1.332 1.332 2.603 2.603
Temperature [C] 15 15 160 564 15 68 226 226 203 600 601 300 40 50 618 482
Pressure [kPa] 120 120 2600 2600 300 2600 2600 2600 2600 2500 101 101 101 3000 2500 2500
Vapour Fraction 1 1 1 1 0 0 0.05 0.40 0.72 1 1 1 1 1 1 1
Molecular Weight 16.04 16.04 16.04 16.04 18.02 18.02 18.02 18.02 17.52 17.52 2.02 2.02 2.02 2.02 24.50 24.50
Mass Density [kg/m3] 0.81 0.81 11.71 5.96 1015 975 200 30.90 16.80 6.07 0.03 0.04 0.08 2.23 8.26 9.78
Viscosity [cP] 1.09E-02 1.09E-02 1.56E-02 2.48E-02 1.14E+00 4.13E-01 - - - 2.66E-02 1.97E-02 1.52E-02 9.16E-03 9.48E-03 3.27E-02 2.91E-02
Thermal ConductivityJW/m-K] 3.23E-02 3.23E-02 5.66E-02 1.33E-01 5.95E-01 6.61E-01 - - - 9.24E-02 3.79E-01 2.84E-01 1.82E-01 1.88E-01 8.03E-02 6.87E-02
Mass Heat Capacity [kJ/kg-C] 2.23 2.23 2.71 4.08 4.05 4.05 4.83 3.87 3.02 2.70 14.73 14.60 14.12 14.26 1.62 1.56
Heat Flow [kJ/h] -4.08E+04 -4.03E+04 -3.74E+04 -2.56E+04 -1.76E+05 -4.52E+05 -4.30E+05 -4.11E+05 -4.36E+05 -3.78E+05 2.25E+04 1.07E+04 5.67E+02 9.54E+02 -3.90E+05 -4.04E+05
Comp Mole Frac (Methane) 1 1 1 1 0 0 0 0 0.25 0.25 0 0 0 0 0.013 0.013
Comp Mole Frac (CO) 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0.015 0.015
Comp Mole Frac (C02) 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0.177 0.177
Comp Mole Frac (H20) 0 0 0 0 1 1 1 1 0.75 0.75 0 0 0 0 0.409 0.409
Comp Mole Frac (Nitrogen) 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0.304 0.304
Comp Mole Frac (Oxygen) 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
Comp Mole Frac (Hydrogen) 0 0 0 0 0 0 0 0 0 0 1 1 1 1 0.081 0.081
Stream 22 23 24 26 27 30 31 32 35. 36 37 38 39 40 41
Mass Flow [kg/h] 63.78 63.78 63.78 45.94 17.84 28.95 28.95 28.95 0.10 43.28 43.28 43.28 89.31 89.31 89.31
Actual Volume Flow [m3/h] 4.43 3.70 1.99 40.84 0.019 23.71 1.40 2.82 0.12 35.44 34.90 56.21 302.05 173.99 127.44
Molar Flow [kgmole/h] 2.603 2.603 2.603 1.614 0.990 1.003 1.003 1.003 0.006 1.500 1.500 1.500 2.995 2.995 2.995
Temperature [C] 250 177 100 92 100 15 160 600 15 15 21 200 952 432 245
Pressure [kPa] 2500 2500 2500 120 2500 101.3 2600 2600 120 101.325 105 105 101 101 101.3
Vapour Fraction 1 0.99 0.62 1 0 1 1 1 1 1 1 1 1 1 1
Molecular Weight 24.50 24.50 24.50 28.47 18.03 28.85 28.85 28.85 16.04 28.85 28.85 28.85 29.82 29.82 29.82
Mass Density [kg/m3] 14.41 17.22 32.06 1:12 949 1.22 20.73 10.25 0.81 1.22 1.24 0.77 0.30 0.51 0.70
Viscosity [cP] 2.13E-02 1.96E-02 2.79E-01 1.83E-02 2.49E-02 4.29E-02 1.09E-02 1.83E-02 1.86E-02 2.63E-02 4.99E-02 3.20E-02 2.57E-02
Thermal Conductivity [W/m-K] 4.81 E-02
- 3.72E-02 6.81E-01 2.52E-02 3.55E-02 6.06E-02 3.23E-02 2.52E-02 2.56E-02 3.71 E-02 8.01 E-02 5.04E-02 3.82E-02
Mass Heat Capacity [kJ/kg-C] 1.49 1.50 2.01 1.15 4.10 1.01 1.05 1.13 2.23 1.01 1.01 1.03 1.32 1.17 1.11
Heat Flow [kJ/h] -4.27E+05 -4.35E+05 -4.80E+05 -2.03E+05 -2.76E+05 -3.01E+02 3.89E+03 1.76E+04 -4.52E+02 -4.50E+02 -1.92E+02 7.71 E+03 -2.03E+05 -2.61 E+05 -2.80E+05
Comp Mole Frac (Methane) 0.013 0.013 0.013 0.021 0.000 0 0 0 1 0 0 0 0 0 0
Comp Mole Frac (CO) 0.015 0.015 0.015 0.025 0.000 0 0 0 0 0 0 0 0 0 0
Comp Mole Frac (C02) 0.177 0.177 0.177 0.285 0.001 0 0 0 0 0 0 0 0.181 0.181 0.181
Comp Mole Frac (H20) 0.409 0.409 0.409 0.048 0.999 0 0 0 0 0 0 0 0.123 0.123 0.123
Comp Mole Frac (Nitrogen) 0.304 0.304 0.304 0.491 0.000 0.79 0.79 0.79 0 0.79 0.79 0.79 0.660 0.660 0.660
Comp Mole Frac (Oxygen) 0 0 0 0 0 0.21 0.21 0.21 0 0.21 0.21 0.21 0.036 0.036 0.036
Comp Mole Frac (Hydrogen) 0.081 0.081 0.081 0.130 0.000 0 0 0 0 0 0 0 0 0 0
Heat stream H1 H2 H3 H4 H5 H6 H7
Heat Flow [kJ/h] 7,200 7,200 21,388 4,524 39,405 10,104 45,142
A pinch analysis was performed to look at possible heat recovery schemes (see Figure A6.1.3 and
Table A6.1.4, Appendix 6.1). The pinch temperature is 225C, the feed steam boiling point. The
reactor pressure has a significant impact on the pinch analysis, as it sets the boiling temperature of the
feed steam. The burner gases are vented to atmosphere at ~250C, ensuring a positive temperature
driving force to raise steam. Table 6.4 summarizes the PFD feed and utility consumptions. The molar
ratio of permeate (pure) hydrogen to total natural gas consumed is 2.48.
Table 6.4: PFD stream summary for 30 Nm
3
/h design
Description PFD value Notes
Natural gas 12.1 Nm7h 0.1 Nm
J
/h to burner, balance to reformer
T3
<U
<U
Air 56 Nm
J
/h Atmospheric air, 60%to burner, balance to reformer
lu
Water 11 kg/h Water recovery from ROG reduces consumption
<*>
Cooling water ~2 m
J
/h Air coolers could eliminate use of cooling water
'-*-
Nitrogen 0 Nm7h Used to purge system for start-up and shutdown
5
Electricity 21 kW Compressors
If electrical power is ignored, the energy efficiency of conversion of the methane to hydrogen is 80%,
based on the higher heating values of hydrogen and methane. The overall energy efficiency O7) is
calculated to be 69%, based on the electrical power consumed and higher heating values of methane
and hydrogen.
HHV
H2
(134kmol I h)(2S6MJ I kmol) _
Q 6 9
.
V
~ HHV
CH4
+ power ~ (0.536kmol / h)(S9lMJ / kmol) + (Q.021MJ/s)(3600s/h) ~
Table A6.1.5 (Appendix 6.1) summarizes the process losses. Waste heat from the compressors and
condensation of the reactor off-gas accounts for the bulk of the thermal inefficiency. It is difficult to
recover energy from these low-grade sources within the process, though most of the rejected heat
could be captured for domestic hot water and space heating.
6. 3. 3 R e a c t o r L a y o u t
Experience gained in design and fabrication of the ICFBMR pilot reactor (Chapter 4) showed that the
layout of the reactor internals poses a number of mechanical challenges. One of the biggest issues
was the numerous membrane tubes and instruments that had to be neatly fixed within the reactor and
sealed at the reactor shell. Minimizing the number of vessel connections is clearly important.
162
Another consideration is the size of commercially available palladium foil. It is difficult for suppliers
to cold-roll wide strips of very thin palladium. Foils of area 6"x 12"(0.15 x 0.30 m) are available
down to 25 urn thickness. Foils of 3"x 12" (0.076 x 0.30 m) are also now available down to 15 urn.
In order to minimize wastage of palladium, membrane panels based on a foil widthof 3" (0.076 m) or
6"(0.15 m) are likely to be preferred.
The base case simulation assumes a superficial core velocity of 0.25 m/s, from which the core flow
area is then calculated to be 0.0068 m
2
. Figure 6.11 presents one possible membrane layout, based on
a nearly-square core draft box and five staggered membrane panels of the same dimensions as in the
ICFBMR pilot reactor (83 mm wide, 6 mm thick). In order to reduce the core box dimensions, the
space between the membrane panels was set at 13 mm, slightly smaller than the panel spacing in the
pilot reactor and cold model (16 mm). The core box can fit within a 6"(0.15 m) reactor shell. The
area available in the core for flow of this layout is 0.0076 m
2
, corresponding to a superficial core
velocity of 0.22 m/s.
6"shell (0.15 m)-^
v
All dimensions in mm
Membrane
panel
Core box
Figure 6.11: Plan view of option 1 layout - 30 Nm
3
/h reactor (U
core
= 0.22 m/s)
64 membrane panels would be required to match the membrane area calculated for the base case
(2.34 m
2
) for the Option 1 layout. This would require 13 membrane panel stacks, making the core box
almost 4 m tall, an impractical dimension. Thinner membranes would reduce the membrane area,
reducing the reactor height. However, basing a design on 50 urn (or 25 um membranes working at
163
50%efficiency) is currently more realistic. Alternatively, the superficial gas velocity in the core
could be reduced from the original specification of 0.25 m/s. As the solids circulation flux varies
approximately linearly with superficial velocity, decreasing the core velocity will not likely penalize
the design significantly.
An alternative reactor layout is presented in Figure 6.12. In this layout, 6%"x 12"(0.16 x 0.30 m)
membrane panels are installed in a staggered pattern, 13 mm apart within the central zone of the
reactor. The area open to flow in the core in this layout is 0.014 m
2
, corresponding to a core velocity
of 0.12 m/s. The circulating solids travel in two opposing segments rather than in an annular region.
30 membrane panels in six stacks provide the membrane area. The membrane area can be
accommodated in an 8"(0.20 m) diameter, ~2.6 m tall reactor (Figure 6.13). This layout has a lower
proportion of the area for return of solids than in the pilot plant reactor, and additional cold model
testing would be required to verify that sufficient solids circulation could be achieved with this
layout. Figure 6.13 shows the permeate H
2
connecting through the top flange, but the side flange
configuration presented in Figure 4.21 (Chapter 4) could also be used.
164
Off-gas
CH4 /H2 0
Wind
box
i L
Filter
Disengagement zo ne
Settled catalyst bed
Oxidant distributo r
Co re bo x
Membrane
panels (30)
8" (0.31 m) shell
Figure 6.13: Elevation drawing for Option 2-30 NmVh reactor (U
core
= 0.12 m/s)
As the reactor is not heated externally, conventional stainless steel can be used for the reactor shell.
In order to accelerate heat-up of the reactor, several small tubular heaters could be installed in both
solids return zones.
165
6. 3. 4 Ec onomi c s
A simplified economic analysis was performed to estimate costs to build and operate the 30 NmVh
ICFBMR unit. It should be noted that the values presented here are not optimized and are for a one-
off system. Costs to produce multiple units of a production-type design would be significantly less
than values presented, as engineering, capital and fabrication costs could be reduced and amortized
over many units. However, the economic analysis gives a starting point for comparison of the
ICFBMR technology against other emerging small-scale H
2
technologies. Unless otherwise noted, all
costs are in 2006 Canadian dollars.
6.3.4.1 Equipment Costs
A simplified piping and instrumentation drawing (PID) is presented in Figures A6.2.1 and A6.2.2 of
Appendix 6.2. An equipment list, which includes nominal sizing, materials of construction and
estimated capital costs, is presented in Table A6.2.1, Appendix 6.2.
In Chapter 2, the cost to produce the 50 urn thick Pd7sAg
25
membranes used in the ICFBMR pilot
plant was estimated at $40,700/m
2
. Given the larger number of membranes (30), a larger palladium
area and thinner Pd material (25 um) compared to the pilot ICFBMR, the capital cost estimate for the
30 NmVh design assumes a fabricated membrane cost of $10,000/m
2
CAD. Note that the palladium
value in the 25 um membranes is approximately $2,000/m
2
at the average Pd price for the last five
years ($279US/oz, average 2002-2007). This implies that the fabricated membrane cost should be
relatively insensitive to small variations in the spot palladium market.
Bare equipment cost is estimated at $220,000CAD, the breakdown of which is presented in Figure
6.14. Membranes represent -10%of the estimated bare equipment cost. The three gas compressors
are the largest component of the equipment capital. By applying a Lang factor of 3.5 to the bare
equipment cost, the total capital cost to supply the first 30 NmVh ICFBMR unit is estimated to be
$770,000. Use of a simple Lang factor is not appropriate for estimating costs of multiple production
units, as it overestimates engineering and installation costs, but can be justified for the first ICFBMR
skid.
166
Burner
Miscel l aneous
Reactor
(excluding
membranes)
Membranes
Figure 6.14: Estimated 30Nm /h bare equipment cost components (values listed in Table A6.2.1)
6.3.4.2 Operating Costs
The list of assumptions (Table A6.2.2, Appendix 6.2) of the economic analysis of the 30 NmVh base
case includes:
8,000 hours of operation/year, at an average production rate of 85%.
The membranes are replaced annually. No credit is given for recycling palladium, as this
represents only a portion (likely less than 10%) of the membrane replacement costs.
Catalyst and desulfurizer adsorbent are replaced annually.
Inflation rate of 2% applied to consumables and utilities.
Annual maintenance costs are estimated at 5%of bare equipment cost, plus an additional $5,000
for each membrane changeover.
Other miscellaneous expenses, such as insurance and annual taxes, are assumed to be 5%of bare
equipment cost.
Based on the above assumptions, the variable operating costs are estimated to be $5.00/kg of Fb, the
breakdown of which is presented in Figure 6.15 (see data in Table A6.2.3, Appendix 6.2). When gas
and electricity are excluded, the variable operating costs are estimated to be $2.88/kg H
2
. Membrane
replacement represents the largest operating cost component, slightly larger than the cost of natural
gas. Clearly there is a significant economic incentive to reduce operating costs by extending
membrane service life and reducing fabricated membrane costs.
167
Natural gas
(base case, values listed in Table A6.2.3)
6.3.4.3 Cost Recovery
A cash flow analysis was performed to calculate the hydrogen selling price required to recover the
capital and operating costs. Assumptions included:
Cost of capital 10%.
Capital depreciated (double-declining) over the 10-year service life.
Margin tax rate of 38%.
No scrap value for equipment.
The cash flow analysis is presented in Tables A6.2.3 and A6.2.4, Appendix 6.2. Capital recovery was
estimated at $7.00/kg H
2
, which when combined with operating costs, gave a selling price of $ 12.7/kg
H
2
. Given the one-off nature of this design, it is not surprising that the break-even H
2
price is very
high (see Figure 1.2 in Chapter 1 for current H
2
delivery costs). Government subsidies or other
financial incentives would likely be required to make the first ICFBMR unit economically viable.
An alternate economic analysis was performed to compare the ICFBMR technology with
conventional small-scale reformers on a similar footing. Costs for the 30NmVh ICFBMR unit where
compared to estimates for a 222 NmVh small-scale conventional SMR filling station using the same
cost scaling parameters from a recent hydrogen study (Table E-35 in "The Hydrogen Economy",
National Academy of Engineering, 2004). The basis and output from this analysis are presented in
Appendix 6.3.
Using the NAE methodology, the cost of hydrogen production, which included capital recovery, was
calculated to be $4.12 and $6.73/kg H
2
for small-scale conventional SMR and the 30NmVh ICFBMR
168
systems respectively. This estimated cost for the ICFBMR system is approximately half that
estimated using the NPV analysis presented above, with the reduction mostly a result of aggressive
capital cost factors appropriate for a multiple production unit.
A portion of the estimated price difference between the conventional SMR (222 Nm
3
/h) and
ICFBMR (30 Nm
3
/h) systems is due to relatively higher capital costs of a lower capacity system.
However, increased variable costs, mainly attributable to annual membrane replacement, represent
the main extra expense of the ICFBMR system. It should be noted that the analysis assumes that the
ICFBMR uses approximately 25%less natural gas than the conventional SMR, but this saving is
more than offset by membrane replacement costs.
6.4 Discussion
The membrane flux characteristics (i.e. foil thickness) and the reactor operating conditions determine
the required membrane area. The membrane area is a key design parameter of the ICFBMR
configuration, as this controls reactor sizing and strongly influences both capital and operating costs.
Simulation shows that high reactor pressure (> -2,500 kPa) and low permeate pressure (< -100 kPa)
are the major reactor parameters that can be used to reduce membrane requirements. Increasing the
reactor temperature significantly reduces membrane area, but operating conditions are likely to be
governed by maximum allowable membrane temperatures (<600C). There is a clear incentive to
develop high-flux (i.e. thin) membranes that can operate at higher temperatures and larger pressure
differentials.
Modelling suggests that the ICFBMR design is relatively tolerant to variations in feed preheat
temperatures and solids circulation. The amount of nitrogen internally circulated within the ICFBMR
does not significantly influence membrane requirements, indicating that there is little economic
benefit of using oxygen in place of oxidation air. This finding also tends to discount the financial
merits of incorporating oxygen-permeable membranes within the reactor, unless they were cheaper to
operate than an air compressor. However, if the non-permeate reactor off-gas was to be treated to
remove C0
2
for sequestration, oxygen addition might be attractive.
The 30 NmVh flowsheet predicts that relatively high system efficiencies (-69%, based on HHV) can
likely be achieved for small-scale H
2
production with the ICFBMR design. As the required membrane
area and superficial gas velocity tend to make the reactor tall and narrow, minimization of the
membrane area is needed to obtain a practical design. In order to reduce the reactor diameter, it may
169
be desirable to reduce the downflow (annular) area of the ICFBMR. Study of alternate reactor
membrane layouts may be useful to determine the effect on solids circulation.
Table 6.5 presents several figures of merit for the 30 Nm
3
/h ICFBMR unit compared to a large-scale
and small-scale conventional SMR system. The ICFBMR system efficiency compares favourably
with conventional SMR systems. The relative reactor volume of the ICFBMR is significantly larger
than for a conventional SMR primary reformer. However for a fairer comparison, the volume of the
shift reactors and PSA should also be included in the conventional SMR values.
Table 6.5: Figures of merit for 30 Nm
3
/h H
2
ICFBMR and conventional SMR production units
Figure of merit Large-scale
conventional SMR
Small-scale
conventional SMR
(NAE, 2004)
Proposed 30 NmVh
ICFBMR design
H
2
:CH4 molar ratio 2.5 1.91 2.48
Overall thermal
efficiency
70-80%(steam export)
-60%(no steam export)
56%(incl. power, no
steam export)
80%excluding power
69%including power
Catalyst
productivity
-3,000 NmVh H
2
/m
3
(primary reformer only)
500 NmVh H
2
/m
3
Reactor
productivity
-1,000 Nm
J
/hH
2
/m
J
(primary reformer
furnace only)
375 NmVh H
2
/m
J
Membrane H
2
productivity
N/A N/A 13 NmVh m
2
Estimated H
2
cost
with capital
recovery ($CAD)
$1.62/kg
(267,000NmVh, Table
E-19, NAE, 2004)
$4.12/kg
(222 NmVh, see
Appendix 6.3)
$6.73/kg
(30 NmVh, see
Appendix 6.3)
The economic analyses clearly demonstrate that the capital and operating costs of membranes are
significant. Reducing the initial capital cost of the membranes is important, but membrane longevity
may be a more important cost factor. If membranes can be shown to operate for two or more years,
the ICFBMR unit economics improve significantly.
Finally, it should be noted that the hydrogen produced in the ICFBMR has the potential to be of
higher purity than H
2
produced from a conventional SMR system. A cost premium for the membrane
hydrogen may be warranted.
170
Chapter 7. Conclusions and Recommendations
7.1 Conclusions
The main objective of this study was to evaluate the ICFBMR concept for production of high-purity
H
2
to serve the emerging distributed H
2
market. Although the results from the pilot plant work were
somewhat below expectations due to catalyst performance and the limited installed membrane area,
the potential for the ICFBMR to supply fuel-cell quality H
2
from a small-scale ATR process has been
demonstrated. Some specific achievements and conclusions from this study:
Double-sided planar membranes using 50-um thick palladium alloy foil (25%silver) were
successfully prepared using proprietary techniques of Membrane Reactor Technologies Ltd
(MRT). Sievert's Law could be used to characterize the panel membrane flux. The calculated
active permeation area of the membrane panels was a fraction (from VA to VA) of the panel
permeation geometry. Post-run analysis suggest that the reduction in permeation area was likely
due to inter-diffusion of the palladium foil with the stainless steel substrate. MRT has
subsequently improved their process for depositing the inter-diffusion barrier.
There were no significant membrane failures during the 14 days of hot operation in the fluidized
bed pilot reactor. High-purity hydrogen was produced (>99.999%H
2
, excluding N
2
) from the in-
situ membranes for the first 180 hours of pilot testing. Although several small leaks developed,
all of the membranes survived the reactor testing intact (up to 650C with no protective covers),
and relatively high quality hydrogen (-99.8%dry basis, excluding N
2
) was produced for the
remainder of the pilot testing. Traces of steam were also likely present in the permeate H
2
at the
end of the testing, but this was not measured. No decrease in permeation was seen in the
membranes, despite heavy deposits of catalyst on the membrane surface.
Catalyst solids were proven to internally circulate up the reformer core and down the annulus in
both the cold model and hot pilot reactor. Results from cold model testing indicate that the solids
flux increases proportionally to the main gas feed flow the core to a superficial velocity (U
core
) of
-0.3 m/s, and that the solids flux levelled off at superficial velocities above -0.5 m/s. It is
postulated that this levelling was due to a gradual transition from bubbling to turbulent
171
fluidization. The addition of a small amount of secondary air to the bottom of the annulus
increased the solids circulation significantly.
Cold model testing showed that communication slots are required between the flow channels in
the membrane core in order to prevent maldistribution of gas and solids.
Solids flux correlations obtained from cold modelling closely matched the measured solids flux
in the pilot reactor, providing some confidence that dimensionless scaling of cold model data to
reformer conditions is valid.
The estimate of the effective membrane area during the pilot reforming tests with no N
2
-sweep
was close to the actual permeation area. This suggests that the "effectiveness"of the membrane
area was close to 100%. The N
2
sweep enhanced H
2
permeation, but was not as fully effective as
predicted from modelling,
The reformer was successfully operated under both SMR (external heating only) and ATR (direct
air addition) conditions. The reactor operation was very stable. Six membrane panels were
installed in the pilot reactor, less than half the full complement, and as a result, the reactor
performance was very much flux-limited. The maximum measured permeate hydrogen
production was 1.06 NmVh at 589C. The highest measured H
2
recovery was 1.17 Nm
3
/Nm
3
of
natural gas feed. The reactor was operated up to 650C, but low catalyst activity hindered reactor
performance. As expected, H
2
production increased with increasing temperature and lower
permeate H
2
partial pressure. The overall reactor performance could be adequately simulated with
a simple equilibrium model coupled with a permeation equation.
Helium tracer studies in both the cold model and hot pilot reformer indicated that only a portion
of the gas in the upper reactor (-10%) is circulated to the reactor core with the returning solids.
This ensures that only a portion of the nitrogen in the oxidation air reaches the permeation zone.
This was confirmed in ATR testing, where it was found that air addition to the top of the reactor
had little effect on the hydrogen flux, indicating that the ICFBMR system requires less membrane
area than a well-mixed ATR reactor using air. It also suggests that the ICFBMR system operating
with air can have similar membrane area as ATR reactors using oxygen or oxygen-permeable
membranes.
The deactivation of the NiO on alumina SMR catalyst initially used in the pilot reactor was not
unexpected, as this material is known to be intolerant of the cyclical oxidizing conditions present
172
when air is fed to the reformer. However, the poor performance of the novel ATR was a
disappointment, and curtailed the pilot plant program. The cause of the low ATR catalyst activity
is not known, as there was a non-analysis agreement in place for this material.
A commercial simulation program (HYSYS) was used to create a model of the ICFBMR based
on a series of equilibrium reactors. The effect of the main process variables on reactor
performance was investigated. When coupled to cold model solids flux correlations, the model
shows that the ICFBMR geometry permits enough solids circulation to match the thermal
demand of the reforming reaction with direct air addition (ATR).
Simulation of a 30 NmVh H
2
ICFBMR production system indicated that high thermal efficiencies
could potentially be achieved. Economic analysis suggests membrane cost and membrane
longevity are key areas for the viability of this process.
7.2 Alternative Reactor Applications
Membrane reactors tend to be flux-limited, and thus the required membrane area governs the reactor
geometry. This results in a larger solids volume than required for catalysis. Higher flux membranes
would reduce the reactor volume, lowering reactor, metal and catalyst costs.
Distributed reforming using a natural gas feedstock may not meet long-term environmental goals.
However, it is likely that novel autothermal reforming technology, of which ICFBMR is an example,
will play a role in the transition to a hydrogen economy. In addition, this technology can likely be
applied to alternative methane sources that are "greener"than natural gas, such as anaerobic digester
gas. It is also possible that higher hydrocarbons (C 3+) can be successfully reformed in this reactor
configuration. The ICFBMR continually moves catalyst between reforming and oxidation zones,
which may alleviate coking problems that can occur when reforming higher hydrocarbons in
conventional fixed bed reactors.
Another possible variation on the ICFBMR reformer is sorption-enhanced reforming (SER), where
calcium-based solids, such as limestone or dolomite, are used to capture C0
2
from the reforming
zone. Recent experimental work at UBC (Johnsen et al., 2006) showed experimentally the potential
for SER to be carried out in a bubbling bed reactor to produce relatively high-purity hydrogen. This
concept could be extended to a fluidized bed membrane reformer, where both C0
2
and H
2
removal
from the reforming zone would shift the thermodynamic equilibrium. C0
2
could then be separately
removed from the calcium solids in a separate calciner or calcining zone. A schematic of a possible
173
configuration is presented in Figure 7.1. Absorption of C0
2
is exothermic, which would help supply
most or some of the reforming heat. Heat, and perhaps stripping steam, would be added to the
calciner to desorb C0
2
. The bed solids, a mix of SMR catalyst and C0
2
-sorbent, is continually
circulated between the beds. A C0
2
-rich stream is produced for sequestration. A similar configuration
using an external solids circulation loop was proposed by Prasad and Elnashaie (2004). This SER
concept highlights the unique ability of fluidized beds to move heat and solids from separate reaction
zones.
Calciner
(C02 desorption)
| Heat
-|CQ2/Stearrj>
-| Off-gas >
/
P "
CaC03,
Catalyst
1
1
i , ,
, H2f
Membranes '
llllilli
CaO,
Catalyst
Bed surface
Reformer
(SMR reaction, H2
separation and
C02 absorption)
H2 >
j Steam ;>
|CH4/Steam>
Figure 7.1: Sorption-enhanced ICFBMR concept
In this study, the ICFBMR has been applied to high-purity hydrogen production from steam methane
reforming. One could also envision applying this fluidized bed membrane system to a number of
other high-temperature catalytic processes, such as propane dehydrogenation, where hydrogen needs
to be removed and heat transfer is important.
7.3 Recommendations
The follow areas merit further study:
Reactor Geometry:
174
o Additional cold modelling to determine whether reactor sizing can be reduced (space-
time yield increased) by using different layouts (e.g. 2 chord returns instead of an
annulus).
o Optimization of feed distributors and catalyst return geometry,
o Side-mounted membrane flanges for ease of reactor assembly.
o Investigate the effect of other reactor geometries on the rate of solids circulation,
including reactor height and membrane spacing.
Membranes:
o Determine longevity of Pd membranes in a fluidized bed environment at varying
temperature and fluidization velocities (both covered and uncovered).
o Find long-term flux stability of membranes to ensure that palladium - substrate inter-
diffusion does not occur.
o Investigate whether membrane efficiency remains high when H
2
recovery is increased to
economically practical values.
Catalysis:
o Long-term testing of a fluidizable ATR catalyst.
C0
2
sequestration:
o Evaluate the application of ICFBMR to sorbent enhanced reforming.
Finally, it is re-emphasized that membranes remain the key to the successful development of any
membrane reactor. Although it is believed that the ICFBMR concept greatly facilitates the use of H
2
-
permeable membranes, without development of robust, high-flux, cost-effective membranes that can
tolerate the high temperatures and pressures in the reforming process, the ICFBMR concept will fail
to compete with conventional reforming processes.
175
References
Aasberg-Petersen, K., Nielsen, C.S., Jorgensen, S.L., "Membrane reforming for hydrogen", Catalysis
Today, Vol. 46, 193-201 (1998).
Abashar, M.E.E., Alhumaizi, K.I., Adris, A.M., "Investigation of methane-steam reforming in
fluidized bed membrane reactors", Trans. IChemE, Vol. 81, Part A, No. 11, 251-258 (2003).
Abba, I.A., "A generalized fluidized fed reactor model across the flow regimes", Ph.D. Thesis,
University of British Columbia, Vancouver, Canada (2001).
Abba, I.A., Grace, J.R., Bi, H.T., "Application of the generic fluidized-bed reactor model to the
fluidized-bed membrane reactor process for steam methane reforming with oxygen input", Industrial
and Engineering Chemistry Research, Vol. 42, No. 12, 2736-2745 (2003).
Adris, A.M., "Fluidized-bed membrane reactor for steam-methane reforming: Experimental
verification and model validation", Ph.D. Thesis, University of British Columbia, Vancouver (1994).
Adris, A.M., Grace, J.R., Lim. C.J., Elnashaie, S.S., "Fluidized bed reaction system for
stream/hydrocarbon gas reforming to produce hydrogen", US Patent 5,326,550 (1994).
Adris, A.M., Pruden, B.B., Grace, J.R., Lim, C.J., "On the reported attempts to radically improve the
performance of the steam methane reforming reactor", Canadian Journal of Chemical Engineering,
Vol. 74, 177-186(1996).
Adris, A.M., Grace, J.R., "Characteristics of fluidized-bed membrane reactors: scale-up and practical
issues", Industrial and Engineering Chemistry Research, Vol. 36, No. 11, 4549-4556 (1997a).
Adris, A.M., Lim, C.J., Grace, J.R., "Fluidized-bed membrane reactor for steam methane reforming:
Model verification and parametric study", Chemical Engineering Science, Vol. 52, No. 10, 1609-
1622 (1997b).
Adris, A.M., Grace, J.R., Lim, C.J., Elnashaie, S.S.E., "Fluidized bed reaction system for
steam/hydrocarbon gas reforming to produce hydrogen", Canadian patent CA 2,081,170 (2002).
Amandusson, H., Ekedahl, L.-G., Dannetun, H., "Hydrogen permeation through surface modified Pd
and PdAg membranes", Journal of Membrane Science, Vol. 193, 35-47 (2001).
Armor, J.N, "The multiple roles for catalysis in the production of H
2
", Applied Catalysis A: General,
Vol. 176, No. 2, 159-176(1999).
Armor, J.N, "Catalysis and the hydrogen economy", Catalysis Letters, Vol. 101, No. 3-4, 131-135
(2005).
Ayabe, S., Omoto, H., Utaka, T., Kikuchi, R. Sasaki, K., Teraoaka, Y., Eguchi, K., "Catalytic
autothermal reforming of methane and propane over supported metal catalysts", Applied Catalysis A:
General, Vol. 241 261-269 (2003).
Balachandran, U., Kleefisch, M.S., Kobylinski, T.P., Morissette, S.L., Pei, S., "Oxygen ion-
conducting dense membrane ceramic membranes", US Patent 5,639,437, assigned to Amoco (1997).
176
Benes, N.E., Verweij, H., "Comparison of macro- and microscopic theories describing
multicomponent mass transport in microporous media", Langmuir, Vol. 15, No. 23, 8292-8299
(1999).
Bi, H.T., Ellis, N., Abba, A., Grace, J.R., "A state-of-the-art review of gas-solid turbulent
fluidization", Chem. Eng. Sci., Vol. 55, No. 1, 1-37 (2000).
Biegler, L. T., Jiang, L., Fox, V.G., "Recent advances in simulation and optimal design of pressure
swing adsorption systems", Separation and Purification Reviews, Vol. 33, No. 1, 1-39 (2004).
Bolthrunis, CO., Silverman, R.W., Ferrari, D., "The rocky road to commercialization: Breakthroughs
and challenges in the commercialization of fluidized bed reactors", Fluidization XI, eds. Arena, U.,
Chirone, R., Miccio M., Salatino, P., Engineering Conferences International, NY, (2004).
Boyd, T., Grace, J., Lim, C.J., Adris, A.M., "Hydrogen from an internally circulating fluidized bed
membrane reactor", International Journal of Chemical Reactor Engineering, Vol. 3, A58 (2005).
Buxbaum, R.E., Kinney, A.B., "Hydrogen transport through tubular membranes of palladium-coated
tantalum and niobium", Industrial and Engineering Chemistry Research, Vol. 32, No.2, 530-537
(1996).
Chen, X., Honda, K., Zhang, Z., "A comprehensive comparison of CH4-CO2 reforming activities of
NiO/Al
2
0
3
catalysts under fixed- and fluidized-bed operations", Applied Catalysis A: General, Vol.
288, No. 1-2, 86-97, (2005).
Chen, Z., Elnashaie, S.S.E.H., "Autothermal CFB membrane reformer for hydrogen production from
heptane", Chemical Engineering Research and Design, Vol. 83, No. 7, 893-899 (2005).
Chu, C.Y., Hwang, S.J., "Attrition and sulfation of calcium sorbent and solids circulation rate in an
internally circulating fluidized bed", Powder Technology, Vol. 127, 185-195 (2002).
Corella, J., Orio, A., Aznar, P., "Biomass gasification with air in fluidized bed: Reforming of the gas
composition with commercial steam reforming catalysts", Industrial & Engineering Chemistry
Research, Vol. 37, No. 12, 4617-4624 (1998).
Coronas, J., Santamaria, J., "Catalytic reactors based on porous ceramic membranes", Catalysis
Today, Vol. 51, 377-389 (1999).
Cromarty, B.J, Hooper, C.W., "Increasing the throughput of an existing hydrogen plant",
International Journal of Hydrogen Energy, Vol. 22, No. 1, 17-22 (1997).
Davidson, J.F., Clift, R., Harrison, D., "Fluidization", 2
nd
edition, Academic Press, London (1985).
Deshmukh, S.A.R.K., "Membrane assisted fluidized bed membrane reactor: experimental
demonstration for partial oxidation of methanol", Ph.D. Thesis, University of Twente, Netherlands
(2004).
Deshmukh, S.A.R.K., Laverman, A.H.G., van Sint Annaland, M., Kuipers, J.A.M., "Development of
a membrane-assisted fluidized bed membrane reactor. 1. Gas phase back-mixing and bubble-to-
emulsion phase mass transfer using tracer injection and ultrasound experiments", Industrial and
Engineering Chemistry Research, Vol. 44, No. 16, 5955-5965 (2005).
177
Deshmukh, S.A.R.K., Heinrich, S., Mori, L., van Sint Annaland, M., Kuipers, J.A.M., "Membrane
assisted fluidized bed reactors: Potential and hurdles", Chemical Engineering Science, Vol. 62, 416-
436 (2007).
Dogan, M., Posarac, D., Grace, J., Adris, A.M., Lim, C.J., "Modeling of autothermal steam methane
reforming in a fluidized bed membrane reactor", International Journal of Chemical Reaction
Engineering, Vol. 1, Article A2 (2003).
Dixon, A.G., "Recent research in catalytic inorganic membrane reactors", International Journal of
Chemical Reactor Engineering, 1, Review R6.
Dyer, P.N., Richards, R.E., Russek, S.L., Taylor, D.M., "Ion transport membrane technology for
oxygen separation and syngas production", Solid State Ionics, Vol. 134, 21-33 (2000).
Edlund, D., "Hydrogen separation and purification using dense metallic membranes", IdaTech Corp.,
presented at DOE Hydrogen Separations Workshop (2004).
Edlund, D., "A versatile, low-cost, and compact flue processor for low-temperature fuel cells",
IdaTech Corp. website: www.idatech.com/technology/publications/fcbull_101199.pdf (1999).
Ellis, N., "Hydrodynamics of Gas-Solid Turbulent Fluidized Beds", Ph.D. Thesis, University of
British Columbia, Vancouver, Canada (2003).
Ewan, B.C.R., Allen, R.W.K, "A figure of merit assessment of the routes to hydrogen", International
Journal of Hydrogen Energy, Vol. 30, No.8, 809-819 (2005).
Galuszka, J., Fouda, S., Pandey, R., Ahmed, S., "Process for producing syngas and hydrogen from
natural gas using a membrane reactor", US Patent 5,637,259, assigned to Natural Resources Canada
(1997).
Gavalas, G.R., Megiris, C.E., Nam, S.W., "Deposition on H
2
-permselective Si0
2
films", Chem. Eng.
Sci., Vol. 44, No. 9, 1829-1835 (1989).
Glicksman, L.R., "Scaling relationships for fluidized beds", Chemical Engineering Science, Vol. 39,
No. 9, 1373-1379(1984).
Glicksman, L.R., Hyre, M., Woloshun, K., "Simplified scaling relationships for fluidized beds",
Powder Technology, Vol. 77 (2), 177-199 (1993).
Grace, J.R., "Fluidized bed hydrodynamics", Chap 8.1 in Handbook of Multiphase Systems, ed.
Hetsroni, G., Hemisphere, Washington (1982).
Grace, J.R., "Contacting modes and behaviour classification of gas-solid and other two-phase
suspensions", Canadian Journal of Chemical Engineering, Vol. 64, 353-362 (1986).
Grace, J.R., Elnashaie, S.S.E.H., Lim, C.J., "Hydrogen production in fluidized beds with in-situ
membranes", International Journal of Chemical Reactor Engineering, Vol. 3, A41 (2005).
Grace, J.R., Lim, C.J., Adris, A.M., Xie, D., Boyd, D.A., Wolfs, W.M, Brereton, C.M.H., "Internally
circulating fluidized bed membrane reactor system", US Patent 7,142,231, assigned to Membrane
Reactor Technologies Ltd. (2006).
178
Gryaznov, V., "Metal containing membranes for the production of ultrapure hydrogen and the
recovery of hydrogen isotopes", Separation and Purification Methods, Vol. 29, No. 2, 171-187
(2000).
Haider, A., Levenspiel, O., "Drag coefficient and terminal velocity of spherical and nonspherical
particles", Powder Technology, Vol. 58, No. 1, 63-70 (1989).
He, Y.L., Lim, J.L., Grace, J.R., "Scale-up studies of spouted beds", Chemical Engineering Science,
Vol. 52, No. 2, 329-339 (1997).
Heydorn, B., Schwendener, H., Mori, S., "Hydrogen", Chemical Economics Handbook, SRI
International, Menlo Park, USA (1994).
Holleck, G.L., "Diffusion and solubility of hydrogen in palladium and palladium-silver alloys",
Journal of Physical Chemistry, Vol. 74, No. 3, 503-511 (1970).
Horio, M., Nonaka, A., Sawa, Y., Muchi, I., "A new similarity rule for fluidized bed scale-up",
AIChE Journal, Vol. 150, No. 9, 1466-1481 (1986).
Hurlbert, R.C, Konecny, J.O., "Diffusion of hydrogen through palladium", Journal of Chemical
Physics, Vol. 34, No.2, 655-658 (1961).
Hseih, H.P., Bhave, R.R., Fleming, L.L, "Microporous alumina membranes", Journal of Membrane
Science, Vol. 39, Issue 3, 221-241 (1988).
Imai, H., Morimoto, H., Tominaga, A., Hirashima, H., "Structural changes in sol-gel derived Si0
2
and Ti02 films by exposure to water vapour", "Journal of Sol-Gel Science and Technology, Vol. 10,
No.l, 45-54 (1997).
Islam, M.T., "Palladium coated high-flux tubular membranes for hydrogen separation at high
temperatures and differential pressures", M.Sc. Thesis, University of Calgary, Canada (1997).
Jarosch, K., de Lasa, H.I., "Novel riser simulator for methane reforming using high temperature
membranes", Chemical Engineering Science, Vol. 54, No. 10, 1455-1460 (1999).
Jarosch, K., de Lasa, H.I., "Permeability, selectivity, and testing of hydrogen diffusion membranes
suitable for use in steam reforming"Industrial and Engineering Chemistry Research, Vol. 40, No. 23,
5391-5397 (2001).
Johnsen, K., Ryu, H.J., Grace, J.R., Lim, C.J., "Sorption-enhanced steam reforming of methane in a
fluidized bed reactor with dolomite as C0
2
-acceptor", Chemical Engineering Science, Vol. 61, 1195-
1202 (2006).
Juda, W., Krueger, C. W., Bombard, R. T., "Diffusion-bonded palladium-copper alloy framed
membrane for pure hydrogen generators and the like and method of preparing the same", US patent
5,904,754, assigned to Walter Juda Associates (1999).
Judd, M.R., Dixon, P.D., AIChE Symp. Ser. 74 (176) 38 (1978).
Jung, D.S., Ron, S.A., Kim, S.D., Guy, C, "Regeneration characteristics of hydrodesulfurization
catalyst by combustion in an internally circulating fluidized bed", Fluidization XI, eds. Arena, U.,
Chirone, R., Miccio M., Salatino, P., Engineering Conferences International, NY, (2004).
179
Kast, W., Hohenthanner, C.R., "Mass transfer within the gas-phase of porous media", International
Journal of Heat and Mass Transfer, Vol. 43, 807-823 (2000).
Kelkar, V.V., Ng, K.A., "Development of fluidized catalytic reactors: Screening and scale-up",
AIChE J., Vol. 48, No. 7, 1498-1518 (2002).
Klassen, A., Membrane Reactor Technologies Ltd., personal communication (2005).
Knapton, A.G., "Palladium alloys for hydrogen diffusion membranes - A review of high permeability
materials", Plat. Met. Rev., Vol. 21, 44-50 (1977).
Knowlton, T.M., Karri, S.B.R., Issangya, A., "Scale up of fluidized-bed hydrodynamics", Powder
Technology, Vol. 150, No. 2, 72-77 (2005).
Kunii, D., Levenspiel, O., "Fluidization Engineering", 2
nd
edition, Butterworth-Heinemann, Newton,
MA (1991).
Kurungot, S., Yamaguchi, T, "Stability of Rh-Y-Al
2
0
3
catalyst layer by ceria doping for steam
reforming in an integrated catalytic membrane reactor system", Catalyst Letters, Vol. 92, No. 3-4,
181-187(2004).
Lewis, F.A., "The palladium hydrogen system", Academic Press, London (1967).
Li, A., Membrane Reactor Technologies Ltd., personal communication (2003).
Li, A., Membrane Reactor Technologies Ltd., personal communication (2005a).
Li, A., "Diffusion bonding for metallic membrane joining with metallic module", US Patent
Application, 20050109821 (2005b).
Lin, Y.S., "Microporous and dense inorganic membranes: current status and prospects", Separation
and Purification Technology, Vol., 25, 39-55 (2001).
Lin, Y.S., Kumakiri, I., Nair, B.N., Alsyouri, H., "Microporous inorganic membranes", Separation
and Purification Methods, Vol. 31, No. 2, 229-379 (2002).
Marschall, K.J., Mleczko, L., "CFD modeling of an internally circulating fluidized-bed reactor",
Chemical Engineering Science, 51, 2085-2093 (1999).
Matsen, J.M., "Design and scale-up of CFB catalytic reactors" in "Circulating Fluidized Beds",
Grace, J.R., Avidan, A.A., Knowlton, T.M., (Eds.), Chapman and Hall, London, 489-503 (1997).
Milne, B.J., Berruti, F., Behre, L.A., de Bruijn, T.J.W., "The internally circulating fluidized bed
(ICFB): A novel solution to gas bypassing in spouted beds", Canadian Journal of Chemical
Engineering, Vol. 70, 910-915 (1992).
Minet, R.G.; Vasileiadis, S.P.; Tsotsis, T.T., "Experimental studies of a ceramic membrane reactor
for the steam/methane reaction at moderate temperatures (400-700C)", Preprints - Division of
Petroleum Chemistry, American Chemical Society, Vol. 37, No. 1, 245-251 (1992).
Mleczko, L., Ostrowski, T., Wurzel, T., "A fluidized bed membrane reactor for the catalytic partial
oxidation of methane to synthesis gas", Chemical Engineering Science, Vol. 51, No. 11, 3187-3192
(1996).
180
Morreale, B.D., Ciocco, M.V., Enick, R.M., Morsi, B.L, Howard, B.H., Cugini, A.V., Rothenberger,
K.S., "The permeability of hydrogen in bulk palladium at elevated temperatures and pressures",
Journal of Membrane Science, Vol. 212, 87-97 (2003).
Morreale, B., Chen, L., Killmeyer, R.P., Dorris, S.E., Lee, T.H.; Balachandran, U. "Dense cermet
membranes for hydrogen separation" 2005 AIChE Spring National Meeting, Conference
Proceedings, 2005AIChE Spring National Meeting, Conference Proceedings, p. 1645 (2005).
Mukainakano, Y., Li, B., Kado, S., Miyazawa, T., Okumura, K., Miyao, T., Naito, S., Kunimori, K.,
Tomishage, K., "Surface modification of Ni catalysts with trace Pd and Rh for oxidative steam
reforming of methane", Applied Catalysis A, 318, 252-264 (2007).
Nam, S.W., Gavalas, G.R "Stability of H
2
-permselective Si0
2
films formed by chemical vapour
deposition", AIChE Symp. Series, 85 (268), 68-74 (1989).
Namkung, W., Guy, C, Boisselle, F., Legros, R., "Effect of temperature on gas bypassing and solids
circulation rate in an internally circulating fluidized bed", Canadian Journal of Chemical Engineering,
Vol. 78, 1025- 1031 (2000).
National Academy of Engineering, "The hydrogen economy: opportunities, costs, barriers, and R&D
needs", National Academies Press (2004).
Natural Resources Canada, "Canadian hydrogen survey - 2004/2005", prepared by Dalcor
Consultants Ltd and Camford Information Services Inc. (2005).
Nijmeijer, A., "Hydrogen-selective silica membranes for use in membrane steam reforming", Ph.D.
thesis, University of Twente, Netherlands (1999).
Ogden, J.M., "Developing an infrastructure for hydrogen vehicles: a Southern California case study",
International Journal of Hydrogen Energy, Vol. 24, Issue 8, 709-730 (1999).
Ogden, J.M., "Review of small stationary reformers for hydrogen production", Center for Energy and
Environmental Studies, Princeton University (2001).
Ohashi, H., Ohya, H., Aihara, M., Youichi, N., Semenova, S., "Hydrogen production from hydrogen
sulphide using membrane reactor integrated with porous membrane having thermal and corrosion
resistance", Journal of Membrane Science, Vol. 146, 39-52 (1998).
Onstot, W.J., Minet, R.G., Tsotsis, T.T., "Design aspects of membrane reactors for dry reforming of
methane for the production of hydrogen", Industrial and Engineering Chemistry Research, Vol. 40;
No. 1,242-251 (2001).
Paglieri, S.N., Way, J.D., "Innovations in palladium membrane research", Separation and Purification
Methods, Vol. 31, No. 1, 1-169 (2002).
Pal, V., Singh, M., Gupta, B., "Analysis of thermal expansion coefficients under the effect of high
temperature for minerals", Journal of Physics and Chemistry of Solids, Vol. 60, 1895-1896 (1999).
Patil, C.S., "Membrane reactor technology for ultrapure hydrogen production", Ph.D. thesis,
University of Twente, Netherlands (2005).
Patil, C.S., van Sint Annaland, M., Kuipers, J.A.M., "Design of a novel autothermal membrane-
assisted fluidized-bed reactor for the production of ultrapure hydrogen from methane", Industrial
Engineering Chemical Research, Vol. 44, 9502-9512 (2005).
181
Pena, M.A., Gomez, J.P., Fierro, J.L.G., "New catalytic routes for syngas and hydrogen production",
Applied Catalysis A: General, Vol. 144, No. 1-2, 7-57 (1996).
Prasad, P., Elnashaie, S.S.E.H., "Novel circulating fluidized-bed membrane reformer for the efficient
production of ultraclean fuels from hydrocarbons", Industrial and Engineering Chemistry Research,
Vol. 41, No. 25, 6518-6527(2002).
Prasad, P., Elnashaie, S.S.E.H., "Novel circulating fluidized-bed membrane reformer using carbon
dioxide sequestration", Industrial and Engineering Chemistry Research, Vol. 43, 494-501 (2004).
Qi, A., Wang, S., Fu, G., Ni, C, Wu, D., "La-Ce-Ni-O monolithic perovskite catalysts potential for
gasoline autothermal reforming system", Applied Catalysis A, Vol. 281, No. 1-2, 233-246 (2005).
Rakib, M.A., Alhumaizi, K.I., "Modelling of a fluidized bed membrane reactor for the steam
reforming of methane: advantages of oxygen addition for favourable hydrogen production", Energy
and Fuels, Vol. 19, 2129-2239 (2005).
Ridler, D.E., Twigg, M.V., "Steam Reforming" in Catalyst Handbook, edited by Twigg, D.E., 2
nd
edition, Manson publishing, London (1996).
Romm, J.J., "The hype about hydrogen", Issues in Science & Technology, Vol. 20, No. 3, 74-81
(2004).
Rostrup-Nielsen, J.R., "Catalytic Steam Reforming", Catalysis Science and Technology, Vol. 5,
Springer, Verlag, Berlin (1984).
Rostrup-Nielsen, J.R., "Production of synthesis gas", Catalysis Today, Vol. 4, 305-324 (1993).
Rostrup-Nielsen, J.R., "Syngas in perspective", Catalysis Today, Vol. 71, 243-247 (2002).
Rothenberger, K.S., Cugini, A.V., Howard, B.H., Killmeyer, R.P., Ciocco, M.V., Morreale, B.D.,
Enick, R.M., Bustamante, F., Mardilivich, I.O., Ma, Y.H., "High pressure hydrogen permeance of
porous stainless steel coated with a thin palladium film via electroless plating", Journal of Membrane
Science, Vol. 244, 55-68 (2004).
Roy, R., Davidson, J.F., "Similarity between gas-fluidized beds at elevated temperature and
pressure", Fluidization VI, edited by Grace, J.R., Shemilt, L.W. Bergougnou, M.A., Engineering
Foundation, New York, 293-300 (1989).
Roy, S., "Fluidized bed steam methane reforming membrane with high-flux membranes and oxygen
input", Ph.D. Thesis, University of Calgary, Canada (1998).
Roy, S., Pruden, B., Adris, A.M., Grace, J.R., Lim, C.J., "Fluidized bed steam methane reforming
with oxygen input", Chem. Eng. Sci., Vol. 54, 2095-2102 (1999).
Roy, S., Cox, B.G., Adris, A.M., Pruden, B.B., "Economics and simulation of fluidized bed
membrane reforming", International Journal of Hydrogen Energy, Vol. 23, No. 9, 745-752 (1998).
Rowe, P.N., Partridge, B.A., "An x-ray study of bubbles in fluidised beds", Chemical Engineering
Research and Design, Vol. 43a, 157-175 (1965).
Schwartz, M., White, J.H., Sammels, A.F., "Solid state oxygen anion and electron mediating
membrane and catalytic membrane reactor containing them", Assigned to Eltron Research Inc., US
Patent 6,033,632 (2000).
182
Shih, H.H., Chu, C.Y., Hwang, S.J., "Solids circulation and attrition rates and gas bypassing in an
internally circulating fluidized bed", Industrial and Engineering Chemistry Research, Vol. 42, No. 23,
5915-5923 (2003).
Shu, J., Grandjean, B.P.A., Van Neste, A., Kaliaguine, S., "Catalytic palladium-based membrane
reactors: a review", Canadian Journal of Chemical Engineering, Vol. 69, 1036-1060 (1991).
Shu, J., Bongondo, B.E.W., Grandjean, B.P.A., Adnot, A., Kaliaguine, S., "Surface segregation of
Pd-Ag membranes upon hydrogen permeation", Surface Science, Vol. 291, No. 1, 129-138 (1993).
Soliman, M.A., Elnashaie, S.S.E.H., Al-Ubaid, A.S., Adris, A.M., "Simulation of steam reformers
with methane", Chemical Engineering Science, Vol. 43, No. 8, 1801-1806 (1988).
Song, B.H., Kim, Y.T., Sang, D.K., "Circulation of solids and gas bypassing in an internally
circulating fluidized bed with a draft tube", Chemical Engineering Journal, Vol. 68, 115-122 (1997).
Spath, P.L., Mann, M.K., "Life cycle assessment of hydrogen production via natural gas steam
reforming", National Renewable Energy Laboratory, report TP-570-27637 (2001).
Sperling, D., Ogden, J., "The hope for hydrogen", Issues in Science and Technology, Vol. 20, No. 3,
82-86 (2004).
SRI Consulting, Suresh, B., Inoguchi, Y., Schlag, S., "CEH Report: Hydrogen", Menlo Park,
California (2004).
Stitt, E.H., Abbott, P.E.J., Cromarty, B.J., Crewdson, B.J., "Emerging trends in syngas and
hydrogen", CatCon 2000, Houston, TX (2000).
Stoll, R.E., von Linde, F., "Hydrogen - what are the costs?", Hydrocarbon Processing, Vol. 79, No.
12,42-46(2000).
Thomas, C.E., Kuhn, I. F., James, B., Lomax, F., Baum, G., "Affordable hydrogen supply pathways
for fuel cell vehicles", International Journal of Hydrogen Energy, Vol. 23, No. 6, 507-516 (1998).
Tomishige, K., Nurunnabi, M., Maruyama, K., Kunimori, K., "Effect of oxygen addition to steam and
dry reforming of methane on bed temperature profile over Pt and Ni catalysts", Fuel Processing
Technology, 85, 1103-1120, 2004.
Tong, H.D., Gielens, J.G., Gardeniers, J.G.E., Jansen, H.V., Berenschot, J.W., de Boer, M.J., van
Rijn, C, Elwenspoek, M., "Microsieve supporting palladium-silver alloy membrane and applications
to hydrogen separation", Journal of Microelectromechanical Systems, Vol. 14, No.l, 113-124 (2005).
Tosti, S., Bettinali, L., Violante, V., "Rolled thin Pd and Pd-Ag membranes for hydrogen separation",
International Journal of Hydrogen Energy, Vol. 25, 319-325 (2000).
Tosti, S., "Supported and laminated Pd-based metallic membranes", International Journal of
Hydrogen Energy, Vol. 28, 1445-1454 (2003).
Touloukian, Y.S., Kirby, R.K., Taylor, R.E., Desai, P.D., "Thermal expansion - metallic elements
and alloys"in Vol.12 of "Thermophysical properties of matter", IFI/Plenum, New York (1970).
Tsuru, T., Yamaguchi, K., Yoshioka, T., Asaeda, M., "Methane steam reforming by microporous
catalytic membrane reactors", AIChE Journal, Vol. 54, No. 11, 2794-2805 (2004).
183
Uemiya, S., Matsuda, E., Kikuchi, E., "Hydrogen permeable palladium-alloy membrane supported on
porous ceramics", Journal of Membrane Science, Vol. 56, No. 3, 315-325 (1991).
Uemiya, S., "Brief review of steam reforming using a metal membrane reactor", Topics in Catalysis,
Vol. 29, No. 1-2, 79-84 (2004).
Usami, Y., Fukusako, S., Yamada, M., "Heat and mass transfer in a reforming catalyst bed:
Analytical prediction of distributions in the catalyst bed", Heat Transfer - Asian Research, Vol. 32,
No. 4,367-380 (2003).
Van Beurden, P., van Dijk, E., van Delft, Y., van der Brink, R., Jansen, D., "Catalysts for hydrogen
production in membrane and sorbent reformers", Energy Research Centre of the Netherlands,
www.ecn.nl.
Vankelecom, I.F.J., Jacobs, P.A., "Dense organic catalytic membranes for fine chemical synthesis",
Catalysis Today, Vol. 56, 147-157 (2000).
Ward, T.L., Dao, T., "Model of hydrogen permeation behaviour in palladium membranes", Journal of
Membrane Science, Vol. 153, 211-231 (1999).
Watson, J., Daly, F., "Steam reforming catalysts for microchannel reactor", Velocys Inc.,
www.velocys.com.
Xie, D., "Experimental study of gas and particle recycling in an internally circulating fluidized bed
membrane reactor, Report No.5", Internal report, Membrane Reactor Technologies Ltd. (2002).
Xu, J, Froment, G.F., "Methane steam reforming, methanation and water gas shift: I. Intrinsic
kinetics", AIChE Journal, Vol. 35 (1), 88-96 (1989).
Xu, J, Froment, G.F., "Methane steam reforming, methanation and water gas shift: II. Diffusional
limitations and reactor simulation", AIChE Journal, Vol. 35 (1), 97-103 (1989).
Yasuda, I., Shirasaki, Y., Mori, T., Maeda, K., Furuta, H., Kondo, T., "Development and
demonstration of highly-efficient hydrogen production from natural gas for fuel cell vehicles",
presented at GASEX 2004, Singapore (2004).
Yates, J.G., "Effects of temperature and pressure on gas-solid fluidization", Chemical Engineering
Science, Vol. 51, No. 2, 167-205 (1996).
Yi, K. B., Harrison, D.P., "Low-pressure sorption-enhanced hydrogen production", Industrial &
Engineering Chemistry Research, Vol. 44, No. 6, 1665 -1669 (2005).
Zaika, Z.D., Minet, R.G., Tsotsis, T.T., "A high temperature catalytic membrane reactor for propane
dehydrogenation", Journal of Membrane Science, Vol. 77, 221-232 (1993).
Zakkay, V., Sellakumar, K. M.; Radhakrishnan, R.; McClung, J. D., "Vertical heat exchanger for
high pressure fluidized bed coal combustors", Energy Progress, Vol. 6, No. 4, 248-253 (1986).
184
Appendix 1 - Introduction Details
Steam:carbon molar ratio
Temperature (C)
Figure Al . 1: Equilibrium methane conversion in SMR as a function of steam-to-carbon ratio and
temperature (pressure = 1,000 kPa, graph contours are lines of constant conversion)
Table A 1.1: Steps employing catalysts in SMR (Armor, 1999)
Operation Temperature (C)
1 Sulfur conversion (HDS) 290-370
2 H
2
S removal (ZnO) 340-390
3 Chloride removal (Alumina) 25-400
4 Pre-reforming 300-525
5 Steam methane reforming 850
6 High temperature water gas shift 340-360
7 Low temperature water gas shift 200
8 Methanation 320
9 NOx removal (ammonia, SCR) 350
Table A 1.2: SMR reactions with oxygen input (Abba et al., 2003 after Xu and Froment, 1990)
SMR reaction with oxygen addition Rate
RI CH
4
+ H
z
O <- CO + 3H
2 hi
R2 CO + H
2
0 C0
2
+ H
2
R3 CH4 + 2H
2
0 <-> C0
2
+ 4H
2
k
r3
R4 CFL, + 20
2
*+ C0
2
+ 2H
2
R5 CH
4
+ 1.5H
2
0-CO + 2H
2
0 k
r5
185
Table A 1.3: SMR reaction rates (Abba et al., 2003 after Xu and Froment, 1990)
Reaction rate equation
RI
r
\
=
^ri (PCH4PHIO 1 PHI ~ PHI PCO 1 K
EQL
) / K
R2
r
i
=
kr i(PQOPHIO 1 PHI ~ PHIPCOI 1 K
eq2
)/
K
R3 r
_ t / p p2 p 3 5_ p 05n IV- X( \ , 2
'3
A
>3V
J
CHA
1
HIO
1
H2
1
H2
1
C02 '
1
^ e q, \
1
^ e q,2 )
1N
~
R4
'4
N
-
R
4
A
CH4
A
02
R5
r -k r
0
'
5
Y
0 7 5
'5
A
'r5
A
C/ / 4
A
02
where K = 1 + K
co
P
co
+ K
H2
P
H2
+ K
CH4
P
CH4
+ K
H20
P
H20
1P
H2
Table A1.4: SMR reaction rate parameters (Abba et al., 2003 after Xu and Froment, 1990)
Rate/
adsorption
constant
Pre-exponent factor Activation energy / heat of
adsorption (kJ/mol)
Ki
8.34E17(molPa
us
/kgs) 240.1
kr2
1.22E1 (mol/kg s Pa) 67.1
k
r3
2.01E17(mol Pa
6
'/kg s) 243.9
k
r4
1.26E12(mol/kg s) 170.3
k
rS
3.08E10(mol/kg s) 139.7
K-co
8.23E-10 (Pa
1
) -70.65
K-CH4
6.65E-9 (Pa
1
) -38.28
KH20
1.77E5 (-) -88.68
KH2
6.12E-14(Pa"') -82.90
Keq.l
1.2E23(TV) 223.10
Keq.2
1.77E-2 (-) -36.58
186
Appendix 2 - Membrane Details
JM Base Pr i c e s Palladium From: J u l 1992
US$ Monthly Av er age To: Jan 2007
in*,
; ;
1992 I 1993 I 1994 I 199S I 1996 I 1997 I 1998 I 1999 I 2000 I 2001 I 2002 I 2003 I 2044 I 200S I 2006 I
Figure A2.1: Palladium pricing 1992-2007 (source: Johnson Matthey website)
187
SideB Side A
Side A
Panel #1
3/16"
tube
3/16"
tube
Side B Side A
lo ts o f
small
creases,
especially
o n LHS
Side B Side A
Panel #5
Panel #3
3/16"
tube
3/16"
tube
J
\
1
faint
crack
numero us
surf ace
bumps,
due to
alumina?
Side B
small '
crease
small
number o f
surf ace
bumps,
due to
alumina?
Panel #4
ladder-like
|marks faintly
visible fro m
substate
Side B Side A
Panel #6
Side B
Panel#8
Panel A is not shown, but was clear both sided
Figure A2. 2: Crease defects in membrane panels installed in I CF B MR
(after bonding, but before service in the I CF B MR pilot reactor)
188
Table A2.1: Permeation rig components
Tag Description Size/
Capacity
Model / Manufacturer
V-10 316SS pressure vessel 10"IDx25" Axton Manufacturing
H-10 Semi-cylindrical ceramic
fiber heaters (2)
3.5 kW/
240VAC
Watlow, model VS112A18
FIC-01 Feed mass flow controller 0-6 SLM H
2
Brooks, model 5850S
FIC-02 Sweep mass flow controller 0-2 SLM H
2
Brooks, model 5850S
FI-03 Permeate mass flow meter 0-1 SLM N
2
Omega, model FMA-A2306SS
FI-04 Rotameter (CHE3495A) Calibration in
figure below
Fisher-Porter
VP-10 Vacuum pump
l
A HP Fisher Technical, model LAV-3
Table A2.2: Gas chromatograph details
GC#1 GC#2
Application Permeation rig testing Permeate from ICFBMR
ICFBMR ROG testing pilot plant
Model Shimadzu GC-8AIT Shimadzu GC-8AIT
(CHE4116A) (CHE3577A)
Detector type TCD TCD
Detector current 60 mA 60 mA
Sample introduction Automatic sampling valve Syringe injection (0.1 m)
Column Hayesep DB 30' x 1/8"OD, Supelco 15' x 1/8"OD, Carboxen
100/120 mesh, Lot 154 1000, Lot 080797
Injector temperature 150C 110C
Column temperature 120C 100C
Carrier / reference gas Argon Argon
Carrier / reference flow 22 / 33 ml/min
Integrator Shimadzu CR601 (CHE4116B) Shimadzu C-R3A (CHE4116B)
Integrator settings
Width 5 5
Slope 29.76 15
Drift 0 0
Chart speed 4 mm/min 6 mm/min
Min. area 1 100
Tvpical gas factors
H2 3.9min/3.643E-05 3.86 min/3.9302E-5
N2 4.52 min / 4.820E-04 4.52 min / 6.859E-4
CO 4.78 min/3.567E-04 4.78 min/4.706E-4
CH4 6.29 min / 1.326E-04 6.28 min / 1.441E-4
C02 8.95 min / 4.632E-04 8.84 min / 5.036E-4
189
Table A2. 3: Hydrogen permeation data for Panel A - effect pf hydrogen partial pressure
Data
point
Permeation vessel conditions Sweep
argon
(SLM)
Permeate
pressure
(kPa)
H2flux
(SLM)
[H2] in
permeate
(vol%)
Permeate
H2 partial
pressure
(kPa)
Sq. root
H2 partial
pressure
(Pa
A
0.5)
Data
point H2 feed
(SLM)
Temp (C) Pressure
(kPa)
H2 partial
pressure
(kPa)
Sweep
argon
(SLM)
Permeate
pressure
(kPa)
H2flux
(SLM)
[H2] in
permeate
(vol%)
Permeate
H2 partial
pressure
(kPa)
Sq. root
H2 partial
pressure
(Pa
A
0.5)
N
o

s
w
e
e
p

1 3.0 549 134 134 0 101.3 0.78 100% 101.3 47.5
N
o

s
w
e
e
p

2 6.0 543 170 170 0 101.3 1.41 100% 101.3 94.5
N
o

s
w
e
e
p

,3 6.0 549 205 205 0 101.3 1.91 100% 101.3 134.4
S
w
e
e
p

g
a
s

4 6.0 543 170 170 0.40 101.3 1.88 83% 83.6 123.6
S
w
e
e
p

g
a
s

5 6.0 543 170 170 0.67 101.3 2.03 75% 76.2 136.7
S
w
e
e
p

g
a
s

6 6.0 543 170 170 0.93 101.3 2.10 69% 70.1 148.1
S
w
e
e
p

g
a
s

7 6.0 543 170 170 1.20 101.3 2.15 64% 65.0 157.9
V
a
c
u
u
m

8 6.0 548 170 170 0.0 67.5 2.26 100% 67.5 153.1
V
a
c
u
u
m

9 6.0 548 170 170 ' 0.0 50.5 2.70 100% 50.5 188.0
V
a
c
u
u
m

10 6.0 548 170 170 0.0 33.6 3.18 100% 33.6 229.5
Table A2.4: Effect of temperature on permeation for Panel A
(pure hydrogen in permeation vessel, no sweep gas to permeate)
Temperature
( C)
Measured H2 flux (SLM) Permeate
pressure
(kPa)
Temperature
( C) Vessel pressure
Permeate
pressure
(kPa)
Temperature
( C)
238 kPa 307 kPa 376 kPa
Permeate
pressure
(kPa)
455 1.39 2.06 2.64 101
502 1.76 2.42 3.03 101
538 1.85 2.61 3.32 101
564 1.91 2.71 3.53 101
Table A2.5: Effect of temperature on permeation for Panels 1-8 (pure hydrogen in permeation vessel,
no sweep gas to permeate, vessel at 300 kPa, permeate at 101 kpa)
Panel 1 Panel 3 Panel 6
Temp ( C) Flux (SLM) Temp ( C) Flux (SLM) Temp ( C) Flux (SLM)
463 1.44 463 1.14 463 0.93
483 1.53 485 1.20 532 0.96
505 1.74 503 1.39 545 1.03
536 1.87 536 1.53 570.5 1.17
555 2.02 554 1.69
Panel 4 Panel 8 Panel 5
Temp ( C) Flux (SLM) Temp ( C) Flux (SLM) Temp ( C) Flux (SLM)
463 0.69 450 1.14 463 1.69
515 1.07 450 0.99 482 1.77
537 1.13 474 1.21 507 2.13
547.5 1.25 505 1.42 536 2.23
568.5 1.45 530 1.52 555 2.42
544 1.51
191
Appendix 3.1
Cold Model Installation Instruction
Figure A3.1.1 presents a schematic of the cold model and include part numbers listed in the
instructions below. Wear appropriate personal safety protection.
1. Disassemble full column:
Drain catalyst from column a nozzle on the lower column section
Close return standpipe valves <1>
Disconnect return standpipe from column <2>
Remove main 6"feed pipe <3>
Unbolt and remove windbox <4>
Remove lower 4' column section
2. Install internals:
Assemble empty core box
o Remove all panels <5> from the core box <9>
o Insert VS" location tube <11> through top of box. This tube is about 11"long so as to
fit in the column and will act as the guide to the Vi" rod <10>, which secures the core
box.
o Install
l
A" filter impulse connections <23> onto core box channels
o Locate box <9> on the floor directly under the 12"column
Feed rope <17> from 2"angled nozzle <8> at the top of column through to the open bottom
and tie to middle of VS" box support tube <11>
Feed Vi" plastic impulse connection lines <from upper column ports through open bottom of
12"column, ensuring that they are not tangled
Connect impulse lines to the appropriate impulse filters <23> on the core box <9>
Tie wrap impulse feed lines <18> as needed
Lift / raise box into the column in increments:
o Always tie off support rope <17>
o Pull slack of Vi" impulse tubes <18> through the connection ports on column wall
o Ensure impulse lines <17> are not tangled
Secure box support by inserting 3/16"hanging tube <10> through VS" support tube <11> and
through the external Plexiglas bosses. Secure 3/16"tube with Swagelok port connections
<12> to NPT drilled bosses
Center and level core box with Vi" lateral tubes <21>, both east-west and north-south and
secure with Swagelok fittings <22>
Pull final slack of Vi" impulse lines <18> and seal Swagelok fittings on column wall
Pull rope <17> tight and secure to the inside of the column nozzle <8> so as to permit the
internals to be lowered during disassembly
Slide in the core box panels <5> from the bottom and secure in place
3. Install oxidant feed line
Insert a Vi" steel guide through the column with the opposing port connections
Push the 3/16"oxidant distributor <6> over one end of the Vi" guide and feed the distributor
through the column to the opposing port
192
Secure the distributor with Swagelok port connections <7> to the Plexiglas bosses on the
column wall
Attach distributor to oxidant feed line
4. Install secondary feed distributor:
Center, and secure distributor <16> in each of the four quadrants
Secure
l
A" distributor feed lines <15> with Swagelok port connections <14> to Plexiglas
bosses
Attach both distributor feed lines <15> to building air supply
5. Install windbox:
Last check of internals
Make sure the two distributor plates <20> are oriented so the drilled holes in the plates match
Lift and bolt the windbox <4> to the column, ensuring that the square feed hole pattern
matches the orientation of the core box <9>
Reattach the 6" feed line <3> to the windbox <4> and to the flexible connection on the
building air supply
6. Solids addition:
Add a small flow of gas to distributors to reduce solids back sifting and aid bed settling
Remove the steel exit elbow <13> on top of the column
Using a funnel, fill the column with F CC until the settled bed level is 25 mm above the core
box <9>
Reattach steel exit elbow <13>
7. Instrumentation:
Connect V" impulse lines <18> to appropriate pressure transmitters <19>
With no gas flow to column, check the calibration of the pressure transmitters <19> on the
data acquisition computer and zero if necessary
8. Column disassembly:
Drain solids from column via nozzle near bottom of column
Remove main 6" feed pipe <3>
Unbolt windbox <4> and remove remaining solids - this can be messy
Remove secondary distributor < 14-16>
Remove oxidant distributor <6-7>
Remove core box panels <5> by unbolting setscrews at the bottom of the box <9> assembly
Disconnect impulse lines <18> connected to core box <9>
Open 2" angled nozzle <8> near top of column and tie off the rope <17> attached to the core
box
Remove the 3/8" tube <10> securing the core box to the column
Using the rope <17>, slowly lower the core bolt out the bottom of the column
193
<13> exit no zzle elbo w
Cyclo nes
<17> ro pe to raise co re bo x
<8> angled no zzle (2")
<7> o xidant fitting (2)
<6> 0.375" o xidant distributo r
12> co re bo x suppo rt fitting (2)
<10> 0.375" co re bo x suppo rt ro d
<11>14" co re bo x lo catio n tube
<16> seco ndary distributo r (4)
<14> 2 distributo r fitting (2)
<15> %" distributo r f eed
<20> distributo r plates
<1> cyclo ne return
valves
V
V
<2> standpipe return
^ P T ^ <19> pressure
transmitters
<18> V*" plastic impulse tubing
<9> Plexiglas co re bo x
<23> pressure filter fitting (many)
<5> co re panels (8)
<21 > VA" centering tubes (6)
<22> centering tube fitting (6)
<3> main f eed pipe (6")
Figure A3. 1. 1: Cold model assembly schematic
194
Appendix 3.2 - Cold Model Testing Details
6.35
/To p
distr
typ' "I T / plate
5 8
_ ^ L_ / distributo r
^ . 38 pm
II i i II M II l i , I
" 6 4 _J L_ \ Bo tto m
6.35 ? .1 I distributo r
W Section A-A plate
(all dimensions in mm)
Figure A3. 2. 3: Cold model main distributor plate
Oxidant
feed
-182-
Settled bed depth
of FCC particles
75
50
25
r
Oxidant distributor
(12 mmOD, 2x13 holes,
1 mmdiam)
Oxidant
I feed
To p of core box
Co lumn shell
(285 mm ID)
Figure A3. 2. 4: Elevation view of cold model oxidant distributor (all dimensions in mm)
196
Table A3.2.1: Cold model feed air rotameters
Tag Service Scale Model Material
FI-OT Main air feed (1) 0-600SLM air Omega FL-1658-SS Glass body, SS float
FI-02 Main air feed (2) 0-236 SLM Omega FL-1656-SS Glass body, SS float
FI-03 Secondary air
feed
3-30LPM air Cole Parmer
U-32461-56
Acrylic body, SS float
FI-04 Oxidant air 30-280LPM air Cole Parmer
U-3 2461-64
Acrylic body, SS float
re
Q.
OL
3
Si
- 1
a
1
c
"55
0 A-
0 100 200 300 400 500 600 700
Air Flow (SLM)
Figure A3.2.5: Pressure drop over cold model main distributors
800
o Sec ondary (per tube)
Oxidant
0 <!>-
20 80
Fi)
40 60
Air flow (SLM)
;ure A3.2.6: Pressure drop over cold model secondary and oxidant distributors
100
197
Table A3. 2. 2: Cold model pressure transducer data
Description Type Tag Channel Calibrated full
scale range (kPa)
Over main distributor plate Pd 18 20 14.8
Bottom of North Quadrant
Pg
5 11 15.6
Freeboard (c/w atmosphere) Pd 1 6 3.2
Core bottom channel 4 (c/w atmosphere) Pd 6 0 14.9
Core bottom channel 5 (c/w atmosphere) Pd 13 21 96.9
Core mid channel 1 Pg
12 1 96.5
Core mid channel 2
Pg
23 3 16.0
Core mid channel 3
Pg
14 15 15.9
Core mid channel 4 Pg
9 13 15.9
Core mid channel 5
Pg
8 7 14.8
Core mid channel 6
Pg
7 9 15.8
Core mid channel 7
Pg
22 2 15.6
Core mid channel 8
Pg
4 5 16.4
Core top channel 4 (c/w freeboard)
Pg
0 4 3.2
Core top channel 5 (c/w freeboard) Pd 17 17 3.1
Core top channel 6 (c/w freeboard) Pd 16 12 3.2
Note: Pd = differential pressure, Pg = absolute pressure, c/w = connected with
routed up south
quadrant
Figure A3. 2. 7: Plan view of cold model.pressure tap connections with vertically slotted panels
198
Freebo ard ^@
(Elev 2090)
To p co re channel (5) (^)-
Mid co re channels (1,3,5,7) (&^>
Bo tto m co re channel (5) (@^
Annular sample
po ints (4)
(elev = 325)
No rth quadrant ^gg
(elev = 70)
Windbo x
Co re
bo x
Windbo x
Elevatio n view lo o king East
All dimensio ns in mm
(^) To p co re channels (4,6)
Mid co re channels (2,4,6,8)
{ ) Bo tto m co re channel (4)
To p co re
pressure taps
(elev= 1494)
Mid co re
pressure taps
(elev = 862)
Bo tto m co re
pressure taps
(elev = 230)
Distributo r (elev
= 0)
Figure A3. 2. 8: Elevation view of cold model pressure tap connections (looking east)
199
0 0.0025 0.005 0.0075 0.01 0.0125 0.015
Velocity (m/s)
Figure A3.2.9: Cold model pressure drop vs. superficial air velocity for SMR (NiO) catalyst
2.0
1.5
Q.
Q.
O
D 1.0
0
3
co
Q)
0.5
A
A
/ A A A A A

A /
A f
A /
7
A increasing flow
decreasing flow
r Umf = 0.0030
0.0
0.0000 0.0025 0.0050 0.0075 0.0100
Superficial velocity (m/s)
Figure A3.2.10: Cold model pressure drop vs. superficial air velocity for ATR catalyst
200
120
0
0 20 40 60 80 100
Rotameter Reading (bottom ball)
Figure A3. 2. 11: Calibration of FI-06 used for helium injection in cold model testing at 207 kPag
as measured against a mass flow meter operating with helium
12
0.35 0.40 0.45 0.50 0.55
Si gnal (volts)
Figure A3. 2. 12: Typical calibration curve of thermal conductivity detector (TCD) with helium
used in cold model system (TCD #2 on 050426, xlOO amplification)
201
9
7
O '
>
c
s
*
(0
3
cr
c
? 3
x
re
1
0
Figure
x
x
x
x
x
x
x x
X X
X
X
X
X
X
X
X
M
X
X
X
X
X
X
x
x
x
*x
&X
X
X
X
X
X
*x
X
100 200 600 700 300 400 500
Main air flow (SLM)
A3.2.13: Ratio of maximum to minimum quadrant solids velocity for cold model data
800
(0
Q.
J
Q .
O
<u
3
(A
(A
d)
Q .
- 7
0)
c
c
ra
xz
O
horizontally slotted panels
y = -0.0027X + 8.77
R
2
= 0.994
A

30 SLM annular air
20 SLM annular air
O 10 SLM annular air
- Linear (20 SLM annular air)
100 200 300 400 500
Main Feed (SLM)
600 700 800
Figure A3.2.14: Pressure drop over channel 4 in cold model core with horizontally slotted panels
(95% confidence interval)
202
94 SLM main air
Frequency (Hz)
0 2 4 6 8 10
Frequency (Hz)
236SLM main air
0 2 4 6 8 10
Frequency (Hz)
236SLM main air
0 2 4
Frequency (Hz)
480SLM main air
0 2 4
Frequency (Hz)
480SLM main air
0 2 4 6 8 10
Frequency (Hz)
2 4 6 8 10
Frequency (Hz)
800SLM main air
0 2 4 6
Frequency (Hz)
713 SLM main air
0 2 4 6 8 10
Frequency(Hz)
(a) Solid panels (b) Vertically slotted panels
Figure A3.2.15: Gage pressure at mid4ieight of cold model channel 4, 20SLM air to annulus
203
12.07
10.0 -! 1 . 1 : !
10.0 10.5 11.0 11.5 12.0 12.5
Corrected pressure in bottom of channel 4 (kPa)
Figure A3.2.16: Pressure of annulus vs. channel 4 pressure in cold model with vertically slotted
panels (corrected for elevation difference)
204
Figure A4. 1. 1: I CF B MR main distributor drilling pattern
200
CL
^ 150
Q.
O
o 100
a)
i _
3
tn 50
o
i_
CL
0 i
A
A
A oxidant
annular
main
0 20 40 60 80
Air flow at ambient conditions (SLM)
Figure A4. 1. 2: I CF B MR pressure drops for three gas distributors
100
205
206
NOZZLE SCHCDUL C
Figure A4.1.4: I CF BMR external pressure vessel drawing (1)
Figure A4.1.5: ICFBMR external pressure vessel drawing (2)
w . f t * a s t a u ; s
AX row
7 . ft
J / L L Of MATERIAL S
i\ )/< I ii iff V r w r t ft) ?/r* 'ma to tmT~
* 7542A03
j f t ' - t f t n c w r i n wo t .
)/f-11UNC. il/t-UXiriaHig:
S i n BAI w a o s ra > y
' OA sureKHcip dt w u w w ; yuam.
I 1 I ) B L O C K T H I C K N E S S A N D C A P F R O M S A * B L A D E T H I C K N E S S .
I 1 2 ) B O R E D t A U E T I R T O W A T C H 0 . 0 . O F 3 * N P S P F E .
I 1 3 ) R E M O V E A L L 8 U R R S A N D S H A R P E D G E S . R O U N D O F F S H A R P C O R N E R S .
I 1 4) F O U R (4) C A S T E R S e / M O U N T I N G H A R D W A R E S U P P U E D B T N OR A M .
CD 5 ) A L L F I L L E T W E L D S T O B E V M I N I M U M U N L E S S O T H E R W I S E N O T E D .
CD 6 ) Aa I T E M S T O B E P R E P A R E D A N D P A I N T E D . I N S T R U C T I O N S T O F O L L O W .
I I 7 ) M A X I M U M D E S I G N L O A D - 7 0 0 0 l b s .
8 ) T R W . m V E S S E L T O F R A M E P R I O R T O S H I P P I N G .
I ' Sf fit. 5X'
M 1
C L E A N I N G k P A W T W C :
S U R F A C E P f t F P . - S U R F A C E S M U S T B E C L E A N A N D F R E E
O F L O O S E R U S T , M I L L S C A L E . D E T E R I O R A T E D P R E V I O U S
C O A T I N G S . D I R T , O R , G R E A S E A N D C H E M I C A L C O N T A M I N A N T S .
A B R A S I V E B L A S T I N G S R C D M U E N D E D .
P R I M E R - ( 1 ) C O A T 7 0 6 9 R E D P R I M E R .
F J N J S t J - I N D U S T R I A L E N A M E L . G R E Y C O L O U R . F O L L O W
M A N U F . I N S T R U C T I O N S F O R C O V E R A G E .
< f Q 0 T | r C A W - E71T-1
(l-D)GMAW => ER70S-6
iVWvfACTUKD 1:
N O R A M E N C W E E R 1 N G A N D C O N S T R U C T O R S L T D .
f o r
U B C I C F B M R
I N T E R N A L C I R C U L A T I N G F L U l D I Z l N G B E D
M E M B R A N E R E F O R M E R
M O B I L E S U P P O R T F R A M E D E T A I L S
Figure A4. 1. 6: I CF BMR support steel drawing
Figure A4.1.7: ICFBMR internal vessel drawing (1)
Figure A4. 1. 8: I CF BMR internal vessel drawing (2)
Figure A4.1.9: ICFBMR main distributor mechanical drawing
V COIL A (9 TURNS)
H' COIL 8 (9 TURNS)
H"COIL C (9 TURNS)
NOZZLE SCHEDULE
KSM MPS SCM IfWWC
DESIGN CODES AND SPECIFICATIONS
VESSEL aw. BE OESICWD A M FABROIED IN ACCORDANCE fir*
- ASK Ml D(V 1. 7001 EDITIOH.
- U" STA* REOD.
DESIGN CONDITIONS
CONTEXTS: PROCESS CAS k WIROCEN SwfEP
SPECK CRAW. 0.01
UTERKAL OESCN PRESSURE 0 TEltfEJWWtE: 50) PStt I WOT
ECTDBW DESKN PRESSURE 4 TEMPERATURE 15 PSK O MOT
ommcPRESSURE TEKPGUTIME:
CO P9C O 4C0T
UMHJM C O O HP* TEMPERATURE: 3J T SCO rac
RADWOWItt: N01 JKT0 ASPER UH*-J3(B) MC W-11(c)
OMRCr M T TESTMCi NOT KE0TJ AS PER U*-5l(BHlXl>) AND W3-M(a)(lXb)
POST QJ> HEAT IKEArUENT: MOT urnsAS pa uai UCS-MNOTE p) w m-iotooXd)
CORROSOI mcnfHS: NONE
0E9CN M) SPEED: NOT A OESCN ffiOUREMENT
SEKWCr NOT A OtSCN REOUWEVENT
MATERIALS OF CONSTRUCTION
SfCLL: SAt yon B. SEAMLESS PIPE
KAft SAW GRADE iPB PFE CAP
NOZZLE: SAiDJ SEAMLESS Ftft (PER SOCDULE)
FIANCES.' SA-105(EXCEPT AS NOTED)
REPADS: N/A
SUPPORTS N/A
MIFJQW. ATOMS;
SA KI CRADE A
EITERWL FTTTMS: SA 202 GRADE A
VAMMr OC: SA-105
STUDS / NUTS SA-1H-B7 / SA-1M-JH
CASKETS: CtLON JStO
WEIGHT, CAPACITY &AREA
GENERAL NOTES
i
NORAM
PROirct MD ?(MM DATE
INTERNAL CIRCULATING
FLUIDIZED BED MEMBRANE REFORMER
UBC ICFBMR
3 COIL CAST PREHEATER BLOCK
2
rwrcufn
APPtKWEO EOT TEW [t-W IIIV-
N.T.S. 1 1 OF 1 | ZO845-40OJ | A
Figure A4.1.10: I CF BMR internal preheater
Al l dimensions in mm
Material : 304L SS
VA Swagel ok nuts wel ded
to the box to hold support
guide from upper flange
r
2. 7-
CD
OO
83
88
V
V
CN
Pl an view Elevation
Figure A4. 1. 11: I CF B MR draft core box
214
1407
305
Dummy
305
Membrane
22-
63.50 305
Membrane
64 305
Membrane
View 1: Membrane assembly
before sealing strips
Membrane
co nnecto r (part 2)
1524
1422
r
Dummy Membrane Membrane Membrane
Co re draft box
View 2: Membrane assembly
with sealing strips
Six co mmunicatio n slots (57 x 22 mm)
Part C: Membrane backing strip
(graphite gasket underneath)
Figure A4.1.12: Membrane assembly general arrangement (dimensions in mm)
0.50-H
Part 3 - 4 Req'd
304/316SS (%" Thick)
Note: Faces do not need to be machined
Figure A4.1.13: Dummy membrane panel (all dimensions in inches)
3.25-
1/8" thick 304 SS
8x3/16" thru'
C - 8
backing
strips
'/ thick 304 SS
16x3/16" thru'
0.1875--j--
0. 1875-|
D -1 dummy panel
No tes:
All SS materials supplied
All dimensio ns in inches
Dims to ho le centres
2.875
Figure A4.1.14: Membrane backing strips and full-length dummy panel (all dimensions in inches)
217
CO
82. 55
| Part 2 - Connector Piece (4 Required)
o>
No tes:
1. All dims are inches
1. Man 316 o r 304 SS
3. 3Wx ZV* sheet supplied
UBC Chemical & Bio lo gical Engineering
No tes:
1. All dims are inches
1. Man 316 o r 304 SS
3. 3Wx ZV* sheet supplied
I C F BM R Me mb r a ne C o nne c to r Pi e c e
Designed /Drawn By: T. Bo yd
SIZE
A
FSCMNO DWG NO
ICFBMR-CNT-001
REV
B
DWG NO
ICFBMR-CNT-001
REV
B
Date: No v. 18. 2003
SCALE 1:1 | [SHEET 3 OF 16
Figure A4.1.15: Membrane connector piece (all dimensions in mm)
218
P U R O C W I R O C C N S W E E P U r m O C E N
t
5
M O T E S :
1 . E S D - E M E R G E N C Y S h V T D O W N .
NORAM MEMBRANE REACTOR Techno lo gies
U.B.C PILOT PLANT
CYLINDER SHED / GAS COMPRESSOR
KTS 1 10F3 1 D-Z0MS-H11 1 A
Figure A4.1.16: P&I D for pilot plant (gas cylinders)
N O T E S :
1 . ' C C " D E N O T E S C O N N E C T I O N T O C A S C H R O M A T O G R A P H
2 . A L L T U B * I S I / * " S S S W A C O . O K U N L E S S O T H E R W I S E N O T E D
3 . R U P T U R E D G K R A T E D 3 5 0 P S B O2TC. 2 5 0 P S l C O 1 W C
NORAM MEMBRANE REACTOR Technologies
U.B.C PILOT PLANT
FEED SYSTEMS
Figure A4.1.17: P&I D for pilot plant (feeds and condensers)
Figure A4.1.18: P&I D for pilot plant (external preheater)
222
Table A4.1.1: ICFBMR thermocouples
Tag Location Measurement location Tag Location
A B C D
TE-114 Annulus (quadrant 1) 25 mm below
core box
508 mm above
point A
508 mm above
point B
584 mm above
point C
TE-115 Annulus (quadrant 2) 25 mm below
core box
508 mm above
point A
508 mm above
point B
584 mm above
point C
TE-116 Annulus (quadrant 3) 25 mm below
core box
508 mm above
point A
508 mm above
point B
584 mm above
point C
TE-117 Core (channel 1) 25 mm below
core box
508 mm above
point A
508 mm above
point B
584 mm above
point C
TE-118 Core (channel 4) 25 mm below
core box
508 mm above
point A
508 mm above
point B
584 mm above
point C
TE-119 Reactor freeboard 25mm above
core box
152 mm above
point A
152 mm above
point B
X
Table A4.1.2: ICFBMR pressure transducers
Tag Service Model Range
DP-01 Differential pressure in reactor (various points) Omega PX750 0-2.54 m WC
DP-02 Differential pressure in reactor (various points) Omega PX750 0-2.54 m WC
PT-121 Outer reactor (V-01) pressure (gauge) Omega PX182 0-3,449 kPa(g)
PT-272 Inner reactor (V-02) pressure (gauge) Omega PX503 0-2,069kPa(g)
Table A4.1.3: ICFBMR pressure tap and sample points
Tag Service / Location Filter on tip?
PT-A Freeboard, 150mm below top flange No
PT-B Splash zone, 140 mm above core box Yes
PT-C Adjacent to oxidant distributor Yes
PT-D Top of center flow channel Yes
PT-E Mid4ieight of center flow channel No
PT-F Bottom of center flow channel No
PT-G Annular quadrant 3 top - 127 mm below top of core box No
PT-H Annular quadrant 3 bottom - 127 mm above bottom of core box No
PT-I Annular quadrant 1 top - 127 mm below top of core box Yes
PT-J Annular quadrant 1 bottom - 127 mm above bottom of core box Yes
223
4 point annular
thermo co uples (3)
TE-114/115/116
3 point splash zo ne
thermo co uple
rm
4 point co re
thermo co uples (2)
TE-117/118
TC point C
TC point B
TC point A
TC point D
PT-A
TC point C
TC point B H
TC point A
Figure A4.1.20: I CF B MR instrument locations
224
Table A4. 1. 4: Equipment list for I CF B M R pilot plant
Tag Name Size Materials Description
C-1 Gas compressor 50SLM at 20MPa
- Fuelmaker model P30
DSU Desulfurizer vertical cylindrical vessel 0.65m
x0.1m OD
SS vessel Cylindrical vessel filled with sulfur adsorbant
(CalgonSulfasorb-8 activated carbon pellets
impregnated with 8%copper oxide, mesh size 4x10)
DIU Deionizer 3 cylinders Fibreglass US Filter (activated carbon bed followed by 2 cation
exchange resin beds)
V302A/B Water pump 0.71mx0.11mOD 316 SS N2 padded vessels
E-1 Interchanger Shell: 1.22m x 0.22 OD 316 SS Rating 1.35MPa
E-1 Interchanger
Tubes: 6.2mm OD x2.4m 316 SS Area = 0.047 m2
E-2 Condenser Shell: 1.22m x 0.22 OD 316 SS Rating 1.35MPa
E-2 Condenser
Tubes: 6.2mm OD x1.2m 316 SS Area = 0.024 m2
E-3 External preheater Outer shell: 0.29m ID x1.52m CS Rating 1.64 MPa
E-3 External preheater
Inner shell: 0.1m ID x1.3m 316 SS Rating 1.28 MPa
E-3 External preheater
Heater: 2 x6 kW (240V) -
H-1 Internal preheater Block: Lead See equipment drawing
H-1 Internal preheater
Tubes: 3 tube coils 316 SS See equipment drawing
H-1 Internal preheater
Heater: 2 x 6 kW (240V) ceramic fibre 2xWatlowVS108A18T
H-2 Reactor heater A oriqinal: 2 x4.3 kW (240V) ceramic fibre 2x Watlow VS108A30S
H-2 Reactor heater A
revised: 2 x 5kW (240V) Incoloy tubes 2x WatlowRDN134J10S
H-3 Reactor heater B oriqinal: 2 x4.3 kW (240V) ceramic fibre 2 xWatlow VS108A30S
H-3 Reactor heater B
revised: 2 x 5kW (240V) Incoloy tubes 2xWatlowRDN134J10S
V-02 Internal reactor O.135/0.256m ID x2.31m 304/310SS See equipment drawings
V-01 External reactor 0.41 m OD x 3.64m overall CS See equipment drawings
tijl, Overview.cim
0
File View Help
to
Figure A4.1.21: ICFBMR pilot plant control screen #1
Figure A4.1.22: I CF B MR pilot plant control screen #2
Figure A4. 1. 23: I CF B M R pilot plant control screen #3
to
to
so
% FBMR. cim
File View Help
m
0
FEEDS r~~~F9MR
OFF-OAS
V-01 Pressure
[3453 Wag
PI-121
F B MR Pr essur e Ba l a nc e
13964kpa
T i . i i 3 h 372.0C
Oxidation Zone
TMio|i372.QtC
V-01
:
| j V-02
| ;
1372.0C
1-511 kpag
12(01/200514:58:29
HYDROGEN
X V- 131
-|1372.QC
1372.0oCTic-iQ9
P R E HE AT E D F E E D
TI-111
1372.0C
1372.0C
NITROGEN
FL UI D B E D A N N U L U S
1372.0C
1372.0C
1372.0C
1372.0C
T M 1 4
TI -11S
Tl - 116
TI-117
TE M P E R A TU R E
P R O F I L E S
P R E S S U R E T A P S
[3<Tl kpa
DPI-001
35.4
k
P
a DPI-002
[23.5 kpa s ma i i D P
0.S SLPM
1372.0C T i c - n o
OA S / S T E A M
Figure A4. 1. 24: I CF B M R pilot plant control screen #4
%, TRIPS, t.im
t-ue view Help
to
O
j t YA WCOl *
["""FSR*"""
TRIPS TUNING,
ESDI TRIPS
PAHH305 1340.1 | -504.6
PAHH272 1349.9 | -4BS.9
PAHH202 1340.1 j -479.3
TAHH108 800.0 | 1372.0
TAHH109 i 600.0 1372.0
TAHH114A 6S0.0 [ 1372.0
TAHH114B 750.0 | 1372.0
TAHH114C S50.0 | 1372.0
TAHH1UD [ 6500 | 1372.0
TAHH115A | 650.0 | 1372.0
TAHH115B | 650,0 1372.0
TAHH115C | 725.0 | 1372.0
TAHH1150 675.0 1372.0
TAHH116A | 675.0 | 1372.0
TAHH116B | 675.0 1372.0
TAHH116C 650.0 1372.0
TAHH116D I 650.0 | 1372.0
ESD4 TRIPS
TAHH110 | 750.0 | .1372.0
TAHH220
TAHH225
TAHH230
TAHH235
ES D 2 T R I P S
- TAHH117A
TAHH117B
TAHH117C
TAHH117D
TAHH118A
TAHH118B
TAHH118C
TAHH118D
TAHH119A
TAHH119B
TAHH119C
TAHH111
TAHH112
TAHH113
E SD 5 TRIPS
1373.0 | 1372.0
400.0 21.5
650 0 23.0
650.0 | 21. 5,
675.0 1372.0
675.0 1372.0
675.0 1372.0
675.0 1372.0
675.0 1372.0
650.0 1372.0
675.0 1372.0
675.0 1372.0
675.0 1372.0
650.0 1372.0
650.0 1372.0
ESD'3 TRIPS
650.0
650.0
1372.0
1372.0
12/0112005 14:58:41
TRI P S T AT US
R ES ET S
ES D 2
ES D 3
ES D 4
| 650.0 | 1372.0
Note: The resets refer only to Trip "Causes"and not "effects"
If a one of the trips is active, the effects of that and all subsequent trips are activated.
Figure A4.1.25: ICFBMR pilot plant control screen #5
118" chamf er o n
each co rner
3" x 3/8" sheet
(typ' 5) equally
spaced
{ 3/8" * |
4 x 'A" OD rings
o n bo x centreline
4 x 1/8" thick tab
1/8" ho le,
o n bo x centrelines
Connec ti on T a b s
Al l dimensions in inches
Al l materials carbon steel
Figure A4.1.26: I CF B MR dummy internals for commissioning
231
200
0 50 100 150 200 250 300
Nitrogen flow (SLM)
Figure A4.1.27 ICFBMR off-gas filter pressure drop
(Pure N
2
flow to reactor, 20C, ambient pressure downstream of filter, no catalyst in reactor)
Table A4.1.5: Natural gas analysis
Sample Location: BC Gas, Tilbury Gate Station, Delta BC (2002)
Analyzer: On-line Daniel gas chromatograph
Component Mole Percent (Volume Percent)
Nitrogen 0.7
Carbon Dioxide , 0 . 2
Methane 95.5
Ethane 2.9
Propane 0.5
iso-Butane 0.05
n-Butane 0.1
Pentanes 0.04
Hexanes 0.01
Total 100.00
Gross Heating Value (MJ/m
3
) 38.60 @ 15.0C and 101.325 kPa
Relative Density 0.580 @ 15.0C and 101.325 kPa
Average Molecular Weight 16.78
*Total Sulphur (mg S/m
3
) Approx. 15 (11 ppm)
Hydrogen Sulphide (mg/m
3
) Approx. 2 (1.5 ppm)
Water Content (mg/m
3
) Approx. 30 (40 ppm)
*Note: The total sulphur includes naturally occurring sulphur compounds plus added odorant
(approx. 5 mg S/m
3
or 3.5 ppm) plus hydrogen sulphide.
232
Appendix 4.2 - ICFBMR Assembly Procedure
1. General Notes
It is important that appropriate safety gear be worn during assembly. As a minimum, steel-toed boots,
eye protection, hardhat, work gloves and work clothes should be worn. Dust masks must be worn
when using insulation and other dusty materials.
Kaowool and ceramic blanket and paper insulation were used to insulate the inside of the carbon steel
outer reactor. Installers should be aware that the paper insulation has organic binders that release
vapour on heat-up. Care should be taken to bake these binders before closing up the reactor as the oils
can accumulate, leading to heater failure and condensation in vent tubing. All flange bolts should be
tightened in the appropriate "star"pattern.
2. Reactor to Horizontal
For the following instructions, it assumed that the reactor cradle swings north-south and that the
reactor is lowered due south.
Two people are required to lower the ICFBMR reactor to the horizontal position safely.
The main reactor support frame must be anchored to the ground to prevent movement. This can
be achieved by drilling screwed Hilti anchors into the cement floor. For the Gas Gun installation,
the reactor must be moved away from its location adjacent to the pilot plant, as there is
insufficient overhead and horizontal clearance.
Two block and tackles (or high quality chain pullers) are required to lower and raise the reactor.
See Figure A4.2.1. The reactor is balanced on the main support frame on the four horizontal
pipes. In order to lower, the reactor must first be pulled off vertical (Tackle #1) before the weight
is supported by the lowering tackle (Tackle #2).
Tackle #1: This is used to pull the reactor off vertical. Attach the fixed end of a block and tackle
(min 5 tonne capacity) to the horizontal bar opposite the side the reactor is being dropped. An
appropriately rated chain or lifting strap can be used. The hook of the tackle is then attached to
the eyebolt on the main lower flange at the due south position. Make sure that the tackle does not
bind when raised or lowered. Exert slight tension.
Tackle #2: This supports the weight of the reactor once it is pulled off vertical. Attach the fixed
end of a block and tackle (min 5 tonne capacity) to the horizontal bar side on which the reactor is
being lowered. An appropriately rated chain or lifting strap can be used. The hook of the tackle is
233
then attached to the lowest eyebolt located on the preheater wye pipe support guide. Make sure
that the tackle does not bind when raised or lowered. Apply slight tension.
Remove the two northern U-clamps that hold the main column supports. Loosen (do not remove!)
the two southern U-clamps so that the supports can pivot.
Put an operator on each tackle. Make sure that there is a clear escape route for each operator if
needed.
Slowly pull the reactor the reactor off vertical with Tackle #1. Tackle #2 MUST be tightened at
the same time to ensure that there is no slack.
At about 5, the reactor will be teeter as the weight shifts onto Tackle #2. Lower the reactor
slowly with Tackle #2. Take in the slack with Tackle #1.
A wheeled support leg is strapped to the upper reactor. Keep lowering the reactor onto the
support leg and then install the two horizontal guides to anchor the support leg to the main frame.
3. Main Flange Removal
Top flange (weight 145 kg): Attach a moveable crane to the flange eyebolt. Be careful to protect
the top flange gasket surface.
Remove the bottom flat flange (weight 145 kg). Attach a moveable crane to the flange eyebolt
with a tie rope to the bottom of the flange to prevent the flange from swinging out when it is
unbolted. Be careful to protect the top flange gasket surface.
Remove the preheater support section (wye) with an appropriately sized crane. The wye weighs
185 kg when empty, about 250 kg if the preheater is installed. Make sure the reactor is anchored
when removing to prevent the reactor shifting.
The reactor anchors can now be removed and the reactor assembly wheeled to the desired
location.
4. Internal Preheater Assembly (HI)
The preheater assembly consists of three separate stainless steel coils (two 3/8" tubes, one V" tube)
embedded into a cast lead block shaped into an annular block. One of the coils melted during the
block pour, so a separate coil for the oxidant supply was inserted tightly inside the preheater core.
The procedure below was used for the preheater assembly, but should not have to be repeated unless
there is a failure of some of the components. Figure A4.2.2 is a photograph of the complete preheater
assembly ready to be attached to the main reactor wye.
234
Place the two hemi-spherical Watl ow ceramic heaters adjacent to the pre-heater block. Attac h to
the block with metal strapping on the ceramic shoulders.
Attac h pigtail tubing to upstream end of pre-heater block. The tubing should have several corners
between the wy e end-cap and preheater to al l ow for thermal expansion between these two fixed
points.
Support wye end cap in the vertical position.
Install blanket insulation into bottom of wye end cap and around heaters.
Place the preheater b loc k assembly into wye piece end cap and rest onto the end support tabs. The
three tube ends should protrude through the wy e end. Bol t preheater in.
Place heater leads next to the wye shell and bring out lead ends through the main flange
connection. Insulate between heaters and the vessel. .
F rom outside, slip N P T tube fittings over preheater inlets and tighten to shell. Put tube fitting and
ferrules over tubes and tighten to seal. Teflon ferrules may be used to make the system
removable.
Li ft and bolt the wy e assembly to the main reactor flange
5. Main Column Insulation Liner and Power Lead Pass-Throughs
T wo insulated stainless sheaths are installed in the 16" (0.41 m) diameter c olumn. The following
procedure outlines how the sheaths and power leads were installed. Barri ng a failure, this should not
need to be repeated.
Drop the big wy e assembly.
Wrap and tape the two 13" (0.33 m) diameter stainless steel liners separately with blanket / paper
insulation until diameter of the 16" (0.41 m) c olumn is achieved.
Insert the longer liner from the bottom flange top until the top is about 23" (0.58 m) from the top
flange. The two lower nozzles (B and C) should be accessible from the inside.
There are six 240 V A C heater elements installed, each with two leads. The leads are brought through
three N P T - Conax fittings on Nozzl e B . Eac h fitting holds four insulated wire leads.
Place additional insulation, for example Teflon tubing, on the Conax leads that wi l l be inside the
reactor.
Make sure each end of the pass-through lead is labelled and then install the three N P T - Conax
fittings on the flange.
The 12 leads from the Conax fitting should be secured to the vessel wal l with aluminium tape and
directed towards the bottom open flange (M2).
235
There are a number of pass-through thermocouples on Nozzle C:
Place additional insulation, for example Teflon tubing, on the thermocouple leads inside the
reactor.
Make sure each end of the thermocouple is labelled and then install the Conax thermocouple
fittings on nozzle C.
The thermocouples should be secured to the vessel wall with aluminium tape and the wire sent
towards the bottom open flange (M2).
The shorter insulated stainless sheath is now installed in the 16" (0.41 m) column:
Insert the shorter insulated liner from the bottom flange top until it mates the upper liner
Take care that the power and thermocouple leads remain in place against the column wall
The thermocouple for the preheater block can now be placed (TE-110) into the drilled hole in the
end of the cast block
Raise and install the wye.
6. Internal Reactor Assembly
The internal reactor is made from 304 / 310 stainless steel. The system is designed for the main body
of the reactor to remain in the outer reactor, while internals are changed after removal via the top
flange.
Position the four Watlow tubular heaters on the internal reactor. Try to have the heater terminals
insulated and as far away as possible from the reactor. Attach the heaters with stainless steel
strapping. Figure A4. 2. 4 is a photograph of the four heaters strapped to the reactor, prior to
insulation wrapping.
Place the reactor wall thermocouple into the well (TE-108 top, TE-109 bottom). Bring the
thermocouple leads down past the bottom flange.
Attach the high temperature N i power leads to the heater terminals. Ensure that the terminals are
well insulated.
Insulate top of the heaters and upper reactor with ceramic paper and blanket until the diameter of
the insulation is about 12!4" (0.32 m) so as to slip into the stainless liner already installed in the
pressure vessel. Ensure that the heater and thermocouple leads are outside the insulation and are
taped down with aluminium tape. The heater leads are brought to the bottom of the assembly.
Screw in the stainless threaded rod supports into the 4 tabs on top of the internal reactor. The rods
should project about 19" (0.48 m) above the inner reactor flange.
236
With the top and bottom flanges off, insert the J-shaped lifting jig into the internal reactor from
the top. Lift the reactor with the jig with a crane.
Before inserting the reactor, place a 10' (3 m) long 3/8"(9.5 mm) OD tube in the sheath. This
will become line transferring oxidant gas from the preheater to the top of the internal reactor.
Insert the internal vessel into the pressure vessel via the top flange. If the insulation is tight, it
may be worthwhile to attach a rope or cable puller to the bottom flange to help insert the reactor.
Take care not to rip or detach the heater and thermocouple leads.
Take care not to rip the insulation on the inner reactor on the internal pressure vessel tabs. The
internal reactor has to be twisted slightly several times to allow the top flange to pass the tabs on
the pressure vessel.
Insert the internal reactor until it meets the top of the stainless sheath. Secure the four support
rods onto the internal taps with nuts.
When the distributor assembly is ready to be installed, place the gasket and bottom flange via the
bottom manway (M2). Use anti-seize on the bottom bolts. The flange bolt heads have been
shaved to lock on the backside of the flange when pulled, but might require a little playing while
bolting.
7. Heater Connections
All heater and power leads are now in the bottom wye. Connect the appropriate heater leads with
the Conax leads with heavy-duty connectors. Insulate the connections well and secure the wire
assemblies to the uninsulated shell of the wye.
Drill out the back of the electrical box to match the positions of the three Conax lead fittings on
nozzle B. Mount box to nozzle
Attach Conax leads to the appropriate slot on the terminal strip.
Check the resistances of each heater set. Check resistance to ground and the other heaters.
Connect the two reactor wall thermocouples (TE-108, TE-109) to the Conax plugs from nozzle
C.
8. Preheater Connections
The three outlets from the preheater are connected to the distributors. Remember to use anti-seize on
all tubing connections.
Connect the appropriate thermocouple into a tubing tee to measure the preheat temperature (TE-
111 main feed, TE-112 secondary feed, TE-113 oxidant).
Make sure that the connections have a couple of bends to allow for thermal expansion.
237
Pressure test and insulate lines.
9. Insertion of Reactor Internals
Insertion of the reactor internals can be tricky due the space constraints in the vessel headspace.
As many connections should be made as possible before inserting the internals.
Place the top inner gasket, and insert the reactor internals. Make sure the orientation is correct.
(See Figure A4. 2. 3).
Place and tighten top flange of the inner reactor.
The large diameter tubing in the top headspace should be tackled first:
Rel i ef / pressure line from the internal reactor (3/8", 9.5 mm) out through nozzle D
Reactor outlet from internal reactor filters (3/8", 9.5 mm) out through nozzle D
Rel i ef line from the external reactor (1", 25 mm): cap with screen to prevent plugging and bring
out through nozzle D
Filter backflush connections, i f required QA", 6 mm through nozzle D )
The reactor internals may consist of the following and are connected through the inner reactor top
flange:
Oxidant distributor: Connect to the preheat tube extending up the internal cladding.
Membrane panels wi th inlet (1/8", 3 mm) and outlet (Vi ", 6 mm). Connect with mating tubing
brought through nozzles E and D .
Pressure taps: Most easily brought out by the 1/8" (6 mm) Conax fittings. The taps are then
connected in the head space with 1/8" (6 mm) tubes
Thermocouples (1/8", 6 mm): Multipoint thermocouples are passed through the Conax split
fitting on nozzle G . Assemble fitting once all thermocouples are in place.
Final button-up:
Insulate branch nozzles once al l of the connections are made.
Pressure test the internal reactor and fittings. Chec k top and bottom connections.
10. Raise Reactor
I f not already done, the reactor needs to be raised to the vertical. This is done in the reverse order of
how it is lowered (described previously, see Figure A4. 2. 5). I f no overhead crane is available, it may
be preferable to attach the top flange ( M l ) before lifting. It can be swung open again once vertical.
238
The reactor can now be rolled to its final location and the four corners of the support structure
anchored. The internal reactor needs to be level, note that this may not be the same as levelling the
external vessel. Use shims under the main supports or the jackscrews. The main reactor and frame
needs to be connected to ground.
Once catalyst is filled, the top and bottom headspaces can be insulated and the top (Ml) and bottom
(M2) flanges placed. Pressure test the external vessel prior to operation.
11. Final External Connections
Make sure the 240VAC heater controllers are locked out. Attach the 240VAC leads and grounds
to the heater terminal box.
Connect three feed lines to preheater.
Connect nitrogen purge to preheater wye cap.
Plug in all thermocouples to the PLC
Connect pressure taps to transmitters and purge meters
Connect membrane sweep and permeate lines
Connect ROG (non-permeate reactor off-gas) outlet
Connect rupture disks and pipe to outdoors
If required, connect filter backslash piping.
Figure A4.2.1: ICFBMR block positions - Tackle #1 is right (north), Tackle # 2 is left (south)
239
Figure A4. 2. 2: ICFBMR preheater (HI) - note the three exit connections and heater leads
Figure A4.2.4: ICFBMR internal reactor shell and heaters (H2 and H3)
Appendix 4.3 - ICFBMR Operating Procedures
Pre-Operation
1 Gas chromatography (GC)
a. Ensure gas GC is on and calibrated.
b. Run gas standard.
2 Start P L C and control system:
a. Turn on 120 V A C power switch in heater control cabinet. The P L C indication lights
should go on.
b. Turn on 120 V A C power switch to solenoids in heater control cabinet.
c. Turn on 24 V D C breaker in P L C cabinet. Green light should go on the 24 V D C
power supply.
d. Turn on 120 V A C breaker in P L C cabinet to power the solenoids (push red button).
e. Power up the Human Machine Interface (HMI) computer.
f. Start HMI I CF B MR control program by clicking "Pilot Plant- I CF MB R " icon.
g. Check that inputs and outputs are connected on working.
h. If desired, shutdown and restart P L C data logger.
3 Ensure all cylinders in the outside shed are full and connected.
4 Ensure that fuel lines (hydrogen and methane) are purged to expel any oxygen.
5 Open flow of cooling water to the condenser E2 and check drain to confirm the flow.
6 Line up permeate:
a. Ensure that all permeate outlet valves are fully open.
b. Close all sweep rotameter valves.
c. Close all sweep inlet valves.
d. Ensure combined permeate line is vented.
7 Open nitrogen supply and adjust regulators:
a. Process (200 psig).
b. Purge (200 psig).
c. Sweep (20 psig).
8 F i l l water tanks:
a. Open vent solenoid valve of desired tank and throttle flow with manual valve.
b. When pressure is vented, open manual and solenoid water supply valves.
c. Monitor HMI and close water supply solenoid valve when tank is full.
d. Close vent valves.
242
9 Check level in E2 - should be small heel of water present for condensation of ROG.
10 Ensure that reactor off-gas (ROG) pressure control valve is fully open in manual (PCV-
272) and that valve bypass is open. Route ROG to vent.
11 External preheater:
a. Ensure preheater output is turned off in PLC.
b. Hook 120VAC power to the preheater magnetic switch in electrical cabinet and
energize switch.
c. Turn on 220 VAC preheater power supply in electrical cabinet.
12 ICFBMR heaters:
a. Ensure the ICFBMR heater controllers are in manual at 0%.
b. Ensure the supply switches to the three heaters are off on the ICFBMR heater control
box.
c. With the 480 VAC supply isolated, measure the resistance of the six ICFBMR
heaters at the supply box. (HI ~ 14 Q., H2 and H3 ~ 12 Q.).
d. Measure the resistance to ground for each heater set. It should ideally be greater than
0.2 MQ.
e. Turn on the 480 VAC supply to the transformer. Supply light should illuminate on
the transformer switch box.
f. Turn on the 240 - 480 VAC transformer via the transformer switch box. Power
supply should be indicated on the transformer switch box and the ICFBMR heater
control box.
Operation Start-up
1 Purge nitrogen:
a. Open flow to purge meters.
b. Slowly pressurize the external preheater to 75 psig (520 kPag) with the vent valve
closed.
c. Pressurize the two water tanks using manual and solenoid valves.
d. Make sure that the manual vent from the external ICFBMR vessel is closed.
e. Open nitrogen to the external ICFBMR pressure regulator, which should maintain the
pressure in the vessel at about 15 psig (100 kPag) over the internal reactor pressure.
2 Introduce process nitrogen:
a. Ensure that secondary feed line is lined up to branch from main feed line.
b. Ensure process nitrogen 3-way valve is routed to main feed line.
24 3
c. Ramp process nitrogen flow to 15- 20 S L M .
d. Open nitrogen supply to oxidant flowmeter and maintain small flow through the
oxidant distributor.
Purge permeate lines:
a. Open all sweep isolation valves to membranes.
b. Crack open sweep rotameters to trickle nitrogen through the membranes. It is
important to keep the permeate pressure very low to prevent reverse pressure on the
membranes.
Start heat-up:
a. Turn on external preheater control to 300C.
b. Turn on I CF B MR heater power supply (HI , H2 and H3) and put on low fire (5-15%).
c. Heat up the reactor at a rate of <2C/min, paying special attention to the core
membrane temperatures.
F i l l natural gas tanks:
a. Check pressure of the two natural gas tanks. The first tank (fill tank) should be at
about 2,000 psig and the second (feed tank) at about 1,000 psig.
b. If not to pressure, fill each tank to the desired pressure with the natural gas
compressor:
i . Open inlet valves to compressor.
i i . Line up compressor discharge to correct cylinder.
i i i . Start compressor and fill to desired pressure.
iv. Stop compressor and isolate tank and compressor.
c. Depending on the gas usage, the gas cylinders wi l l need periodic filling while
running. The Fuelmaker compressor has a capacity of about 53 S L M .
Introduce hydrogen:
a. Open the hydrogen supply and set regulator at 200 psig (1,400 kPag).
b. Open the hydrogen supply solenoid.
c. Once the core reactor has stabilised at 250C, gradually introduce hydrogen up to a
composition of 15-20% hydrogen. Process nitrogen can be cut back as the reactor
heats up to conserve supplies.
Raise temperature:
a. Heat the reactor at a rate of <3C/min, paying special attention to the core membrane
temperatures.
24 4
b. Once the core has reached about 500C, increase the reactor pressure to about 30
psig (200 kPag). Watch the external I CF B MR pressure to see if it follows
automatically. I f it does not, investigate the operation of the tracking regulator.
8 Introduce steam:
a. Check the R OG temperature exit El , which wi l l likely start to show increased
temperature.
b. Ensure water control valve is closed.
c. Open water feed manual / automatic valves on one of the tanks.
d. Crack open the water control valve to feed water at a low rate (2-3 kg/h).
e. Monitor the feed line temperatures and pressures to ensure that the feed to the reactor
is fully vaporized.
f. Supply steam for 30 minutes and check R OG composition for any carbon reduction.
9 Introduce methane:
a. Line up the second (fill tank) gas cylinder (fill tank at 500 (3,450 kPag) to 1,000
(6,900 kPag) psig) and isolate the connection between the two cylinders.
b. Set the gas regulator in the cylinder shed at 200 psig (1,400 kPag)
c. Open the methane supply valve in the cylinder shed.
d. Open the methane isolation valve upstream of the gas controller.
e. Open the methane supply solenoid via the HMI .
f. Crack the methane flow and gradually increase to match desired steam-to-carbon
ratio.
10 Stabilize operations:
a. Maintain temperature uniformity in bed by adjusting heater settings.
b. Take samples of the ROG using the direct sample line to GC#1. Once CO or C0
2
shows up in the ROG to confirm reaction, the hydrogen supply can be closed:
i . Shut hydrogen controller via the HMI .
i i . Close hydrogen supply solenoid via the HMI .
i i i . Close isolation valve in cylinder shed and isolate hydrogen cylinders.
c. Take GC analyses of the ROG until reproducible values are achieved.
d. Watch the I CF B MR pressure and stabilise operations.
e. Sweep nitrogen flows can be gradually increased, but always ensure that the
permeate pressure is well below the reactor pressure.
245
Shutoff heaters (4):
a. Turn off the three ICFBMR heaters on the HMI.
b. Shut the three ICFBMR heaters switches on the control box.
c. Turn off ICFBMR transformer and 480 VAC supply.
d. Turn off external process heater on HMI.
e. Turn off 120 VAC supply to external preheater magnetic switch.
f. Turn off 240 VAC supply to external preheater.
Reduce NG and steam flows in tandem to a minimum value. The endothermic reforming
reaction can be used to help reduce the reactor temperature.
Introduce hydrogen to the feed with the H2 mass flow controller.
Reduce pressure:
a. Slowly reduce the reactor pressure to 30 - 45 psig (200 - 300 kPag). This can be
done in conjunction with feed flow reduction.
b. As preheater feed pressure drops, manually vent pressure from external preheater
shell while reducing nitrogen padding regulator.
c. TR-123, the ICFBMR tracking regulator, should vent pressure in the outer ICFBMR
vessel to follow the internal pressure, but this has been known not to work. Watch the
pressure balance and manually vent pressure if necessary. Note that the rupture disk
between the two ICFBMR vessels is designed to relieve at 100 psi (690 kPa)
differential pressure.
Reduce sweep nitrogen flows to minimum value to conserve nitrogen.
Shutoff NG and steam:
a. Open process nitrogen to about 10 SLM (ensure it is connected to the main feed line)
and adjust hydrogen flow to give desired concentration.
b. Shut NG flow via controller:
1. Shut NG feed solenoid via the HMI.
2. Close manual valve just upstream of the NG controller.
3. Close NG delivery valve in the cylinder shed.
4. If not done already, stop gas compressor and isolate suction and discharge.
5. Close and isolate NG delivery tanks.
c. Stop steam flow several minutes after NG:
1. Close water feed throttling valves.
2. Close manual and solenoid valve on feed delivery from water tanks.
24 6
3. Close steam feed isolation valve.
4. I f shutting down for a lengthy period, isolate nitrogen pad from both water
tanks and vent pressure.
d. It is important that all steam be purged from the preheater and reactor. Maintain gas
flow for at least 2 hours after steam shutoff.
7 Once the reactor pressure has been reduced to less than 60 psig (400 kPag), fully open
the vent from the outer I CF B MR vessel and external preheater.
8 Reduce the reactor core temperature to 250C. Depending on the process flows this can
take many hours. It is important that a significant partial hydrogen of hydrogen is
maintained in the reactor during this time to prevent membrane damage. It is also
preferable to maintain a small positive pressure (15-30 psig, 100-200 kPag) to ensure that
the membrane is pressed onto its support.
9 Stop hydrogen once the membrane temperature has reached 250C:
a. Shutoff hydrogen flow controller via the HMI .
b. Close hydrogen supply solenoid valve via the HMI .
c. Close manual valve just upstream of the hydrogen controller.
d. Close hydrogen delivery valve in the cylinder shed and isolate cylinders.
10 Maintain process and purge hydrogen for several hours to purge hydrogen from the
membranes and reactor.
11 Stop sweep nitrogen:
a. Keep membrane outlets open.
b. Close membrane sweep inlets.
c. Isolate nitrogen sweep cylinders and feed valve in cylinder shed.
12 Shutoff process nitrogen:
a. Fully open R OG pressure valve (PCV-272) and open manual bypass.
b. Reduce and stop process nitrogen via HMI controller. Close process nitrogen supply
valve and isolate cylinders in shed.
13 Close purge nitrogen suply valve and isolate cylinders in shed.
14 Shutoff cooling water to E2.
247
Operation Running Checklist
Below is a list of operating tasks required to keep the pilot plant running. These tasks are in addition
to any experimental activities.
Table A4.3.1: Operator task checklist
Task Frequency
1 Check cylinder pressures, especially nitrogen:
Once new cylinder is on, check on post-
regulator pressure as small differences can make
differences, for example the water flow from the
tanks
Every 30 mins
2 Check for low levels in water tanks on computer and fill
when switching:
Make sure second tank is full, close vent
(manual and solenoid valve) and open nitrogen
pad (manual and solenoid valve)
Open discharge solenoid on second tank
Open manual discharge valve on the second tank
and at the same time close the discharge on the
first tank
Close water discharge solenoid valve on first
(empty) tank
Vent empty tank via manual and solenoid valves
When empty, open manual and solenoid water
fill valves
When HMI indicates as full, open manual and
solenoid water fill valves
Close vent on filled tank (manual and solenoid)
and open nitrogen pad. Tank is now ready to be
placed on-line
When low level alarm shows
on HMI
3 Drain E2 - do not drain fully empty as heel of water is
used for condensation. Take care of the hot water under
pressure.
Every time new water tank is
introduced
4 Check permeate line temperatures to ensure no large
leaks
Hourly
5 Check preheater shell pressure. Manually pad or vent if
necessary to maintain a shell overpressure of 15-45 psi
30 mins or more frequently
when changing reactor
pressure
6 Check external ICFBMR pressure and manually vent if
necessary
30 mins or more frequently
when changing reactor
pressure
248
Appendix4. 4 - Catalyst Microreactor System
A microreactor test stand owned by Membrane Reactor Technologies Ltd. was used to evaluate the
catalysts used in the ICFBMR pilot reactor. Rigorous catalyst testing was not undertaken; rather
simple, standard experiments were conducted to check the reactivity of catalyst samples before and
after pilot plant runs. Both the nickel-based SMR and noble metal ATR catalysts were tested.
Figure A4.4.1 presents a flow schematic of the microreactor. Mass flow controllers set the gas and
water flows. The feed was heated and water vaporized in an electrical preheater prior to being
introduced into the heated microreactor. The system could run unattended and was connected to a
supervisory computer, which logged data and performed safety shutdowns. Reactor exit gases were
analyzed in a gas chromatograph. Figure A4.4.2 presents details of the downflow microreactor.
Vent
GC
Figure A4.4.1: Microreactor flow schematic
249
F l o w i n
Watlow ceramic
cylindrical heater
(550W, 372" OD,
ID, 12"long)
Thermocouple
Thermocouple
(1/16"OD, moveable)
Thermocouple
sheath (1/8"OD)
Reactor tube
(3/8"OD, %"ID)
Ceramic microspheres
(1 mm diam)
Quartz wool
Catalyst sample
Alumina powder
Quartz wool
Ceramic microspheres
F l o w out
Figure A4. 4. 2: Microreactor geometry
250
Appendix 4.5 - Commissioning
Plan
-133-
u
VA" (6 mm) ring heater
Section
18
Single 0.6 mm orifice at each
of the 4 distribution points
VJ" (6 mm) feed line
Figure A4. 5. 1: Original pilot I CF B MR secondary distributor (dimensions in mm)
VA" (6 mm) SS tube
fitting for inlet
Heavy wall %"
(15 mm) SS pipe
14-1 mm diameter orifices
(7 per side)
Figure A4. 5. 2: Original pilot I CF B MR air distributor
251
4
2
y = 4.77E-04X
2
+ 2.67E-02x + 2.52E-01
R
2
= 0.9998
A
.
A
A "
0 10 20 30 40 50 60
Ro tameter Reading
Figure A4.5.3: Calibration of helium rotameter (CHE 4251C) at 1,380 kPag
252
Appendix 4.6 - ICFBMR Pilot Plant Data
Table A4. 6. 1: Gas chromatograph analyses from I CF B MR helium tracer testing (reactor at 1,100 kPa,
core at ~595C, natural gas feed = 42 S L M , steam-to-carbon ratio = 3.0, no air, N
2
content due
to purges to pressure impulse lines)
Sample lo catio n GC analysis (dry) CH4
co nversio n
Sample lo catio n
H2 N2 CO CH4 C02 He
CH4
co nversio n
Reacto r off-gas 45.76 7.29 0.89 29.84 15.61 0.610 35. 6%
Po int 1 (annulus) 45.01 20.75 6.53 10.36 17.06 0.295 69. 5%
Po int E (bottom slot 2) 51.66 10.10 3.11 21.41 13.69 0.030 4 4 . 0%
Po int D (top slot 2) 39.61 30.81 3.46 13.00 13.07 0.043 56. 0%
Po int H (top slot 3) 48.24 11.58 3.39 20.04 16.73 0.031 50. 1%
Table A4. 6. 2: Membrane flux testing during run #5
(Pure H2 feed to reactor, no sweep to permeate)
Reactor Permeate H2 feed to Measured Predicted fluxfor Effective Effective /
Reactor pressure pressure reactor H2 flux area = 0.0258 m2 permeation theoretical
Membrane Date Time temp. (C) (kPa a) (kPa a) (SLM) (SLM) (SLM) area (m2) area
#5 July 11 05 2023 555 206 101 19.1 1.91 2.70 0.0183 70.8%
All 6 July 11 05 2049 555 266 101 19.1 11.29 3.93 0.0742 47.9%
All 6 July 11 05 2053 555 250 101 19.1 10.59 3.62 0.0756 48.8%
#3 July 11 05 2103 555 250 101 19.1 1.81 3.62 0.0129 50.2%
#4 July 11 05 2102 555 250 101 19.1 1.38 3.62 0.0099 38.2%
#1 July 11 05 2109 555 250 101 19.1 2.02 3.62 0.0144 55.8%
#8 July 11 05 2114 555 250 101 19.1 1.74 3.62 0.0124 48.0%
#6 July 11 05 2115 555 250 101 19.1 1.12 3.62 0.0080 30.9%
#5 July 11 05 2119 555 250 101 19.1 2.47 3.62 0.0176 68.4%
All 6 July 11 05 2127 555 150 101 19.1 4.94 1.38 0.0924 59.7%
#3 July 11 05 2154 555 150 101 19.1 0.64 1.38 0.0119 46.2%
#4 July 11 05 2150 555 150 101 19.1 0.57 1.38 0.0106 41.2%
#1 July 11 05 2157 555 150 101 19.1 0.87 1.38 0.0163 63.3%
#8 July 11 05 2204 555 150 101 19.1 0.55 1.38 0.0103 39.8%
#6 July 11 05 2206 555 150 101 19.1 0.37 1.38 0.0070 27.1%
#5 July 11 05 2210 555 150 101 19.1 1.03 1.38 0.0193 74.7%
Membrane number #1 #3 #4 #5 #6 #8
Average 0.0154 0.0124 0.0102 0.0184 0.0075 0.0113
Standard deviation 0.0014 0.0007 0.0005 0.0008 0.0007 0.0015
253
Table A4. 6. 3: Membrane flux testing during run #6
(Pure H
2
feed to reactor, no sweep to permeate)
Membrane Date Time
Reactor
temp. ("C)
Reactor
pressure
(kPa a)
Permeate
pressure
(kPa a)
H2 feed to
reactor
(SLM)
Measured
H2 flux
(SLM)
Predicted flux for
area = 0.0258 m2
(SLM)
Effective
permeation
area (m2)
Effective /
theoretical
area
#4 Aug 18 05 1300 551 164 101 10.0 0.59 1.72 0.0089 34.6%
#4 1306 553 174 101 10.0 0.70 1.96 0.0092 35.6%
#3 1310 553 180 101 10.0 0.96 2.11 0.0117 45.4%
#3 1315 553 182 101 10.0 0.96 2.15 0.0115 44.5%
#1 1322 560 180 101 10.0 1.16 2.13 0.0141 54.7%
#1 1322 560 180 101 10.0 1.17 2.13 0.0141 54.8%
#8 1326 562 178 101 10.0 0.48 2.09 0.0059 22.9%
#8 1328 562 178 101 10.0 0.49 2.09 0.0061 23.6%
#8 1346 570 208 101 13.6 0.81 2.81 0.0075 28.9%
#8 1348 570 213 101 13.6 0.92 2.92 0.0082 31.7%
#8 1350 570 213 101 13.0 0.90 2.92 0.0079 30.7%
#6 1353 570 217 101 13.0 0.90 3.01 0.0077 29.8%
#6 1355 570 217 101 13.0 0.96 3.01 0.0083 32.0%
#5 1357 569 219 101 13.0 1.95 3.05 0.0165 64.0%
#5 1357 569 219 101 13.0 1.80 3.05 0.0152 58.9%
#3 1410 565 199 101 13.0 1.26 2.59 0.0125 48.5%
#3 1411 565- 199 101 13.0 1.31 2.59 0.0130 50.5%
#4 1416 565 201 101 13.0 1.05 2.63 0.0103 40.0%
#4 1417 567 201 101 13.0 1.01 2.64 0.0099 38.4%
#1 1419 565 201 101 13.0 1.52 2.63 0.0149 57.8%
#1 1420 567 201 101 13.0 1.54 2.64 0.0150 58.2%
#8 Aug 19 05 1219 576 204 101 12.0 0.67 2.75 0.0063 24.4%
#8 1??5 576 204 101 12.0 0.69 2.75 0.0065 25.2%
#6 1227 574 204 101 12.0 0.56 2.74 0.0052 20.3%
#6 1228 573 204 101 12.0 0.52 2.73 0.0049 19.0%
#5 1231 572 201 101 12.0 1.54 2.66 0.0149 57.8%
#5 1233 572 201 101 12.0 1.59 2.66 0.0154 59.8%
#3 1237 570 204 101 13.0 1.26 2.72 0.0120 46.4%
#3 1238 570 204 101 13.0 1.26 2.72 0.0120 46.4%
#4 1242 570 201 101 13.0 1.07 2.65 0.0104 40.3%
#4 1243 570 201 101 13.0 1.07 2.65 0.0104 40.3%
#1 1246 570 201 101 13.0 1.32 2.65 0.0128 49.7%
#1 1247 570 201 101 13.0 1.33 2.65 0.0130 50.2%
#6 repeat 1251 570 201 101 13.0 0.52 2.65 0.0051 19.6%
#6 1252 570 201 101 13.0 0.51 2.65 0.0050 19.4%
#8 Aug 20 05 1130 585 196 101 13.0 1.09 2.60 0.0108 41.8%
#8 1131 585 196 101 13.0 1.08 2.60 0.0107 41.6%
#8 1135 585 196 101 13.0 0.97 2.60 0.0097 37.5%
#6 1139 585 199 101 13.0 0.78 2.67 0.0076 29.4%
#6 1140 585 199 101 13.0 0.77 2.67 0.0075 29.0%
#5 1143 585 199 101 13.0 1.93 2.67 0.0187 72.4%
#5 1144 585 199 101 13.0 1.88 2.67 0.0182 70.6%
#3 1150 585 203 101 13.0 1.16 2.76 0.0108 41.9%
#3 1151 585 203 101 13.0 1.14 2.76 0.0107 41.4%
#4 1146 587 197 101 13.0 1.03 2.63 0.0101 39.3%
#4 1147 587 197 101 13.0 0.97 . 2.63 0.0096 37.1%
#1 1155 586 203 101 13.0 1.58 2.76 0.0148 57.2%
#1 1156 586 I 203 101 13.0 1.56 2.76 0.014E 56.3%
Membrane number #1 #3 #4 #5 #6 #8
Average 0.0142 0.0118 0.0099 0.0165 0.0064 0.0080
Standard deviation 0.0009 0.0008 0.0006 0.0016 0.0015 0.0019
254
Table A4. 6. 4: Summary of Selected I CF B MR Pilot Tests (Sheet 1)
# Run Date Time Catalyst Feed flow (SLM) Steam:
carbon
ratio
02: ROG (dry basis)
# Run Date
Type Activity NG H20 N2 Air
Steam:
carbon
ratio
carbon
ratio
H2 N2 CO CH4 C02 Flow
SLM
1 2 Aua 10/04 1951 NiO OK 41.97 109.7 3.9 0 2.61 0 37.024 5.322 0.282 46.590 10.783 72.80
2 2 Aug 10/04 2028 NiO OK 41.99 128.5 3.8 0 3.06 0 37.681 5.169 0.293 45.245 11.611 73.47
3 2 Aug 10/04 2209 NiO OK 35.79 141.1 11.7 0 3.94 0 26.831 19.479 0.000 49.958 9.733 59.96
4 2 Aug 10/04 2224 NiO OK 41.99 128.5 4.8 0 3.06 0 30.801 7.088 0.137 50.957 11.017 67.60
5 2 Aug 11/04 1518 NiO OK 42.22 134.8 9.2 0 3.19 0 39.923 10.723 0.430 36.698 12.227 85.54
6 2 Aug 11/04 1536 NiO OK 42.24 134.8 9.2 0 3.19 0 39.293 10.863 0.408 37.263 12.174 84.74
7 2 Aug 11/04 1956 NiO OK 42.22 128.5 7.3 0 3.04 0 30.216 10.241 0.261 48.013 11.270 70.91
8 2 Aug 11/04 2008 NiO OK 42.22 128.5 7.8 0 3.04 0 26.212 11.466 0.319 51.525 10.477 67.75
9 2 Aug 11/04 2148 NiO OK . 42.19 128.5 10.6 0 3.05 0 32.018 13.632 0.385 41.918 12.047 77.63
10 2 Aug 12/04 1619 NiO OK 42.12 122 14.4 70.4 2.90 0.35 22.947 48.115 0.253 17.442 11.243 145.55
11 2 Aug 12/04 1638 NiO OK 42.14 122 15.1 70.4 2.90 0.35 23.310 48.057 0.310 17.296 11.027 147.17
12 2 Aug 12/04 1952 NiO OK 42.12 125 13.5 70.4 2.97 0.35 18.157 50.854 0.130 20.211 10.649 135.92
13 2 Aug 12/04 2020 NiO OK 42.09 125 13.3 70.3 2.97 0.35 17.680 51.092 0.120 20.482 10.627 134.78
14 2 Aug 12/04 2145 NiO OK 42.07 122 14.3 70.2 2.90 0.35 16.780 51.914 0.070 20.811 10.427 134.38
15 2 Aug 12/04 2206 NiO OK 42.09 122 13.5 70.1 2.90 0.35 17.008 51.499 0.095 20.791 10.607 133.65
16 3 Sep 20/04 1548 NiO OK 15.0 45.1 1.7 0 3.0 0.0 46.271 5.327 0.500 34.033 13.869 31.05
17 3 Sep 20/04 1616 NiO OK 15.0 45.1 1.9 0 - 3.0 0.0 48.407 5.808 0.723 30.650 14.413 32.83
18 3 Sep 20/04 1740 NiO OK 15.0 45.1 2.3 0 3.0 0.0 46.042 7.049 0.909 30.363 15.637 32.04
19 3 Sep 20/04 1809 NiO OK 15.0 45.1 2.3 0 3.0 0.0 46.287 7.187 0.883 30.003 15.640 32.30
20 3 Sep 20/04 1841 NiO OK 15.0 45.1 2.4 0 3.0 0.0 46.044 7.336 0.893 30.019 15.708 32.24
21 3 Sep 20/04 1917 NiO OK 1S.0 45.1 2.3 0 3.0 0.0 47.217 7.061 0.888 29.648 15.187 32.87
22 3 Sep 20/04 2219 NiO OK 15.0 45.1 2.0 0 3.0 0.0 46.999 6.318 0.912 29.662 16.109 32.20
23 3 Sep 21/04 1338 NiO OK 15.0 58.5 3.3 0 3.8 0.0 35.523 11.582 0.412 34.627 17.857 28.41
24 3 Sep 21/04 1430 NiO OK 15.0 35.5 6.2 0 2.4 0.0 30.744 20.317 0.384 30.263 18.292 30.71
25 3 Sep 21/04 1450 NiO OK 15.0 31.9 6.6 0 2.1 0.0 34.289 20.131 0.366 26.989 18.226 32.97
26 3 Sep 21/04 1545 NiO OK 15.0 47.3 5.2 0 3.1 0.0 41.349 15.040 0.499 22.552 20.561 34.46
27 3 Sep 21/04 1645 NiO OK 15.0 50.8 5.3 0 3.4 0.0 40.297 15.581 0.550 25.974 17.598 34.06
28 3 Sep 21/04 1734 NiO OK 15.0 60.1 7.9 0 4.0 0.0 39.598 20.881 0.496 22.049 16.976 38.03
29 3 Sep 21/04 1805 NiO OK 15.0 33.1 8.5 0 22 0.0 34.327 23.690 0.608 25.569 15.807 35.80
30 3 Sep 21/04 1905 NiO OK 15.0 45.1 7.0 0 3.0 0.0 39.270 19.236 0.506 24.257 16.731 36.22
31 3 Sep 21/04 2016 NiO OK 15.0 45.1 5.6 0 3.0 0.0 41.152 16.035 0.576 23.234 19.003 35.11
32 3 Sep 21/04 2054 NiO OK 20.0 60.1 8.5 0 3.0 0.0 39.520 18.027 0.412 27.136 14.905 47.18
33 3 Sep 22/04 1330 NiO OK 20.1 60.2 3.2 0.0 3.0 0.00 40.430 8.174 0.348 33.611 17.437 39.01
34 3 Sep 22/04 1423 NiO OK 20.1 60.2 3.5 11.4 3.0 0.12 32.433 26.014 0.384 25.392 15.774 48.26
35 3 Sep 22/04 1450 NiO OK 20.1 60.2 5.6 22.9 3.0 0.24 25.376 40.426 0.220 19.297 14.681 58.63
36 3 Sep 22/04 1550 NiO OK 20.1 602 6.7 33.9 3.0 0.36 23.105 48.120 0.216 14.571 13.987 69.68
37 3 Sep 22/04 1642 NiO OK 20.1 602 6.9 45.6 3.0 0.48 20715 54.028 0.167 11.445 13.646 79.38
38 3 Sep 22/04 1741 NiO OK 20.1 60.2 7.3 45.6 3.0 0.48 21.765 53.466 0.160 11.144 13.466 80.95
39 3 Sep 22/04 1807 NiO OK 20.1 60.2 7.9 58.2 3.0 0.61 19.132 58.932 0.163 8.395 13.379 91.40
40 3 Sep 22/04 1848 NiO OK 20.1 60.2 7.6 58.2 3.0 0.61 19.471 58.609 0.166 8.445 13.308 91.47
41 4 Oct 26/04 1600 NiO OK 30 90 5.4 0 3.0 0.0 37.214 9.529 0.459 39.706 13.093 56.33
42 4 Oct 26/04 2043 NiO OK 30 90 3.7 0 3.0 0.0 37.132 6.832 0.660 40.286 15.090 53.54
43 4 Oct 26/04 850 NiO OK 30 90 5.2 0 3.0 0.0 32.246 9.996 0.4888 44.186 13.084 51.94
44 4 Oct 26/04 916 NiO OK 30 90 4.3 0 3.0 0.0 32.185 8.5022 0.4789 45.608 13.226 50.58
45 4 Oct 26/04 2155 NiO OK 30 114 11.0 0 3.8 0.0 24.256 20.319 3.191 38.198 14.036 54.13
46 4 Oct 27/04 1018 NiO OK 30 114 3.6 0 3.8 0.0 38.908 6.5729 0.4161 40.634 13.469 55.03
47 4 Oct 27/04 1054 NiO OK 30 114 3.6 0 3.8 0.0 38.083 6.6012 0.4086 40.99 13.917 54.23
48 4 Oct 27/04 521 NiO OK 30 66 6.2 0 2.2 0.0 27.949 12.36 0.5435 45.645 13.503 50.26
49 4 Oct 27/04 618 NiO OK 30 66 5.8 0 2.2 0.0 23.613 12.376 0.4649 50.138 13.408 46.87
50 4 Oct 27/04 716 NiO OK 30 66 5.1 0 2.2 0.0 26.642 10.712 0.5099 49.853 12.283 47.89
51 4 Oct 27/04 745 NiO OK 30 66 4.6 0 2.2 0.0 26.804 9.7475 0.5046 50.611 12.333 47.26
52 4 Oct 27/04 1553 NiO uncertain 20 60 4.2 0 3.0 0.0 37.356 10.953 0.9318 33.303 17.456 38.69
53 4 Oct 27/04 2041 NiO uncertain 30 114 4.9 0 3.8 0.0 45.123 7.7139 1.08 29.648 16.436 63.61
54 4 Oct 27/04 2103 NiO uncertain 30 114 5.5 0 3.8 0.0 44.531 8.5386 1.0883 29.464 16.378 63.92
55 4 Oct 27/04 2213 NiO uncertain 30 66 5.8 0 2.2 0.0 31.026 11.161 1.1048 42.614 14.095 51.89
56 4 Oct 27/04 2252 NiO uncertain 30 66 5.8 0 2.2 0.0 31.732 11.06 1.0399 41.678 14.491 52.44
57 4 Oct 28/04 50 NiO uncertain 30 114 5.0 0 3.8 0.0 43.372 8.0838 1.0349 30.248 17.261 61.80
58 4 Oct 28/04 124 NiO uncertain 30 114 5.3 0 3.8 0.0 43.077 8.5152 1.0154 30.275 17.118 61.97
59 4 Oct 28/04 335 NiO uncertain 30 114 5.9 0 3.8 0.0 41.172 9.6645 1.2132 33.386 14.565 61.02
60 4 Oct 28/04 403 NiO uncertain 30 114 5.8 0 3.8 0.0 40.839 9.5992 1.1945 33.856 14.512 60.53
61 4 Oct 28/04 500 NiO uncertain 30 114 5.1 0 3.8 0.0 39.12 8.8884 1.2827 34.897 15.812 57.70
62 4 Oct 28/04 531 NiO uncertain 30 114 5.0 0 3.8 0.0 40.592 8.4913 1.2083 33.88 15.828 58.92
63 6 Aug 18705 ATR OK 20.0 60 1.0 0 3.0 0.0 37.942 2.839 0.649 44.455 14.116 33.77
64 6 Aug 18/05 ATR OK 20.0 60 1.0 0 3.0 0.0 41.199 2.696 0.762 40.233 15.111 35.65
65 6 Aug 18/05 ATR OK 20.0 60 0.9 0 3.0 0.0 42.982 2.497 0.855 38.256 15.411 36.68
66 6 Aug 18/05 ATR OK 20.0 60 0.9 0 3.0 0.0 41.870 2.591 0.884 37.545 17.111 36.01
6? 6 Aug 18/05 ATR OK 20.0 60 0.9 0 3.0 0.0 41.860 2.540 0.899 37.405 17.297 35.97
66 6 Aug 18/05 ATR OK 20.0 60 1.5 0 3.0 0.0 34.524 4.460 0.596 46.147 14.275 32.78
6S 6 Aug 18/05 ATR OK 20.0 60 1.5 0 3.0 0.0 35.639 4.460 0.584 45.345 13.972 33.39
7C 6 Aug 18/05 ATR OK 20.0 60 1.4 0 3.0 0.0 38.052 4.104 0.574 41.301 15.969 34.58
71 6 Aug 19/05 ATR maybe low 20.0 76 1.2 0 3.8 0.0 40.702 3.316 0.294 42.796 12.892 35.73
7; 6 Aug 19/05 ATR maybe low 20.0 76 1.2 0 3.8 0.0 41.623 3.328 0.311 42.123 12.615 36.33
7: 6 Aug 19/05 ATR maybe low 20.0 76 1.3 0 3.8 0.0 38.751 3.701 0.322 43.127 14.099 34.75
T 6 Aug 19/05 ATR low 20.0 44 1.7 0 2.2 0.0 32.186 5.365 0.231 51.621 10.596 32.03
71 > 6 Aug 19/05 ATR low 20.0 44 1.6 0 2.2 0.0 30.581 5.270 0.291 53.071 10.788 31.18
7( > 6 Aug 19/05 ATR low 20.0 44 1.7 0 2.2 0.0 31.756 5.409 0.304 49.445 13.085 31.83
7
-
' 6 Aug 19/05 ATR low 20.0 | 44 1.7 0 2.2 0.0 29.042 5.686 0.287 52.081 12.905 30.64
255
Table A4.6.4: Summary of Selected ICFBMR Pilot Tests (Sheet 2)
# CH4 conversion Steam InROG [H21wet in ROG Core Pressure (kPa)
Measured Equilibrium from ROG GC from GC predicted by equil temp Reactor Permeate
ROG *lo H2 perm H2 perm SLM [H20] w/ H2 flux no H2 flux (C)
1 19.2% 20.9% 23.5% 93.8 56.30 23.7% 19.2% 19.9% 506 702 101
2 20.8% 21.5% 24.2% 111.2 60.22 23.5% 17.8% 18.5% 496 713 101
3 16.3% 22.4% 25.6% 129.4 68.34 15.9% 14.9% 15.5% 499 1100 101
4 18.0% 18.5% 21.2% 113.5 62.67 18.9% 15.4% 16.1% 499 1124 101
5 25.6% 26.4% 29.5% 113.5 57.03 25.4% 20.2% 20.9% 522 745 101
6 25.2% 25.9% 29.0% 113.8 57.32 25.0% 19.8% 20.6% 519 742 101
7 19.4% 23.1% 26.8% 112.3 61.30 18.7% 18.4% 19.3% 530 1120 101
8 17.3% 23.8% 27.5% 114.1 62.74 16.1% 18.9% 19.8% 533 1096 101
9 22.9% 25.8% 30.1% 109.5 58.52 20.2% 19.8% 20.9% 547 1145 101
10 39.7% 46.9% 49.9% 88.9 37.92 16.6% 21.5% 22.2% 534 662 101
11 39.6% 45.6% 48.6% 89.1 37.71 16.9% 20.6% 21.4% 534 746 101
12 34.8% 41.8% 46.3% 95.9 41.36 12.8% 17.8% 18.8% 534 1109 101
13 34.4% 41.5% 46.1% 96.2 41.65 12.5% 17.6% 18.6% 532 1107 101
14 33.5% 40.0% 44.4% 93.9 41.13 11.9% 16.8% 17.7% 535 1331 101
15 34.0% 40.2% 44.6% 93.5 41.17 12.0% 17.0% 18.0% 537 1328 101
16 29.7% 29.0% 42.9% 36.3 53.91 30.1% 20.6% 24.0% 553 881 101
17 33.1% 32.5% 46.5% 35.4 51.88 31.9% 22.6% 26.2% 574 931 101
16 35.3% 32.5% 48.8% 34.8 52.05 30.3% 21.9% 26.0% 590 1211 101
19 35.5% 32.3% 51.5% 34.7 51.79 30.5% 21.1% 25.9% 589 1214 101
20 35.6% 32.3% 52.3% 34.7 51.82 30.3% 0.209 0.259 589 1209 101
21 35.2% 32.5% 42.6% 34.8 51.43 31.2% 0.233 0.260 590 1213 101
22 36.5% 34.5% 52.9% 34.4 51.67 31.0% 0.226 0.274 591 1047 101
23 34.5% 32.4% 48.0% 48.2 62.92 21.8% 18.6% 21.9% 571.5 1427 101
24 38.2% 25.8% 40.5% 24.1 43.98 21.4% 19.3% 23.2% 569.4 1132 101
25 40.8% 26.3% 40.8% 19.8 37.52 24.9% 20.4% 24.6% 582.8 1149 101
26 48.3% 35.8% 51.6% 32.9 48.87 27.8% 22.3% 26.3% 596.9 1174 101
27 41.1% 35.2% 50.4% 38.6 53.15 26.3% 21.3% 24.9% 592.1 1288 101
28 44.2% 41.9% 53.9% 47.0 55.28 25.5% 22.5% 25.3% 596.4 1165 101
29 39.1% 28.4% 41.1% 21.5 37.56 25.0% 21.3% 25.0% 596.9 1274 101
30 41.5% 33.3% 43.1% 32.8 47.51 26.6% 22.4% 24.9% 588.1 1174 101
31 45.7% 32.6% 47.4% 31.5 47.33 27.9% 21.3% 25.0% 581.3 1089 101
32 36.1% 29.9% 37.9% 45.8 49.27 26.5% 21.0% 23.0% 566.9 1101 101
33 34.6% 27.9% 36.6% 46.4 54.33 26.2% 20.8% 23.0% 558.5 1081 101
34 38.9% 33.3% 42.5% 44.7 48.11 21.9% 19.9% 22.0% 556.25 1137 101
35 43.6% 39.5% 48.3% 42.8 42.20 17.8% 19.2% 21.2% 556.5 1186 101
36 49.4% 46.4% 55.5% 40.5 36.76 16.9% 19.3% 21.3% 555.5 1082 101
37 54.7% 52.2% 60.6% 38.4 32.58 15.6% 19.0% 20.8% 556 1135 101
38 55.0% 52.0% 61.0% 38.2 32.07 16.5% 18.6% 20.6% 553.25 1110 101
39 61.7% 59.9% 68.5% 35.5 28.00 14.9% 19.1% 21.0% 560.75 1132 101
40 61.5% 59.9% 68.7% 35.7 28.05 15.2% 19.1% 21.1% 561 1133 101
41 25.4% 32.2% 37.4% 75.0 57.11 23.7% 24.3% 25.8% 570 901 101
42 28.1% 32.1% 38.9% 73.5 57.85 23.5% 24.1% 26.0% 570 901 101
43 23.5% 28.9% 35.7% 76.2 59.45 20.2% 21.8% 23.6% 570 1201 101
44 23.1% 28.3% 35.1% 76.4 60.16 20.1% 22.0% 23.7% 570 1201 101
45 31.1% 34.1% 40.0% 97.1 64.20 14.8% 21.3% 22.6% 570 1201 101
46 25.5% 33.5% 39.4% 98.9 64.26 23.7% 21.9% 23.3% 570 1201 101
47 25.9% 33.5% 39.7% 98.7 64.53 23.1% 21.8% 23.3% 570 1201 101
48 23.5% 23.8% 31.9% 52.2 50.93 18.5% 21.2% 23.6% 570 1201 101
49 21.7% 23.8% 31.7% 53.2 53.17 15.4% 21.3% 23.7% 570 1201 101
50 20.4% 23.7% 30.7% 54.0 53.00 17.4% 21.7% 23.8% 570 1201 101
51 20.2% 23.7% 30.4% 54.1 53.36 17.5% 21.8% 23.9% 570 1201 101
52 35.6% 37.9% 48.3% 46.1 54.39 24.2% 26.0% 29.0% 615 1201 101
53 37.1% 43.6% 52.1% 92.4 59.23 28.3% 26.3% 28.5% 615 1201 101
54 37.2% 43.7% 50.9% 92.4 59.10 28.0% 26.6% 28.5% 615 1201 101
55 26.3% 31.3% 40.3% 50.8 49.47 20.8% 26.4% 29.4% 615 1201 101
56 27.1% 31.3% 38.9% 50.3 48.94 21.3% 26.9% 29.4% 615 1201 101
57 37.7% 43.6% 52.0% 92.0 59.82 27.1% 26.3% 28.5% 615 1201 101
58 37.5% 43.7% 52.0% 92.2 59.79 27.0% 26.3% 28.5% 615 1201 101
59 32.1% 48.4% 54.6% 95.5 61.01 25.6% 29.1% 30.8% 615 901 101
60 31.7% 48.4% 55.0% 95.7 61.26 25.3% 28.9% 30.8% 615 901 101
61 32.9% 48.3% 56.9% 95.0 62.22 24.1% 28.6% 30.9% 615 901 101
62 33.5% 48.3% 54.9% 94.6 61.63 25.1% 29.0% 30.9% 615 901 101
63 24.9% 32.0% 42.6% 50.2 59.80 23.7% 23.6% 26.4% 568 861 101
64 28.3% 32.4% 44.5% 49.0 57.87 26.1% 23.4% 26.6% 570 861 101
65 29.8% 32.1% 45.2% 48.4 56.88 27.4% 23.0% 26.5% 570 881 101
66 32.4% 31.9% 44.4% 47.4 56.81 26.7% 23.1% 26.3% 569 881 101
67 32.7% 32.4% 44.8% 47.2 56.77 26.7% 23.4% 26.6% 572 891 101
68 24.4% 29.7% 39.2% 50.4 60.62 21.5% 22.2% 24.6% 568 1061 101
6 24.3% 29.7% 39.7% 50.5 60.19 22.2% 22.0% 24.6% 568 1061 101
7C 28.6% 29.1% 40.3% 48.8 58.51 24.0% 21.4% 24.2% 565 1061 101
71 23.6% 35.4% 47.4% 66.7 65.11 24.7% 21.9% 24.6% 572 1062 101
72 23.5% 35.2% 47.7% 66.7 64.74 25.3% 21.7% 24.6% 571 1056 101
73 25.1% 34.6% 45.8% 66.1 65.54 23.4% 21.6% 24.2% 570 1091 101
74 17.3% 25.3% 34.0% 37.1 53.70 20.9% 23.0% 25.7% 573 1041 101
7 17.3% 25.1% 33.2% 37.2 54.39 19.8% 23.1% 25.6% 575 1093 101
7 21.3% 26.2% 34.6% 35.6 52.78 20.8% 23.7% 26.4% 580 1068 101
7" 20.2% 25.8% 33.2% 36.0 54.02 18.9% 23.7% 26.0% 577 1062 101
256
Table A4.6.4: Summary of Selected I CF B MR Pilot Tests (Sheet 3)
# H2 partial P (kPa) 100%H2 (lux
measured
SLM
H2:C
recovery
ratio
Area
from GC
Membrane area
deduced from flux
Predicted
flux(SLM)
Actual / predicted flux
Reactor
avg, model
Permeate
(expfl)
100%H2 (lux
measured
SLM
H2:C
recovery
ratio
Area
from GC
Membrane area
deduced from flux
Predicted
flux(SLM)
Actual / predicted flux
Reactor
avg, model
Permeate
(expfl)
100%H2 (lux
measured
SLM
H2:C
recovery
ratio (m2) no sweep sweep A=0.06 m2 no sweep sweep
1 137 33 6.2 0.15 0.039 0.047 8.02 77%
2 129 33 6.5 0.15 0.041 0.054 7.41 88%
3 167 23 6.4 0.18 0.034 0.036 10.70 60%
4 177 23 6.4 0.15 0.030 0.035 11.19 57%
5 153 30 7.7 0.18 0.041 0.050 9.47 82%
6 150 30 7.7 0.18 0.042 0.051 9.25 84%
7 211 30 9.1 0.21 0.043 0.043 12.74 71%
8 212 30 9.1 0.21 0.049 0.043 12.83 71%
9 233 34 10.5 0.25 0.047 0.048 13.56 78%
10 145 26 7.1 0.17 0.057 0.045 9.74 73%
11 157 26 7.3 0.17 0.051 0.043 10.41 70%
12 203 30 10.3 0.24 0.068 0.051 12.34 84%
13 200 30 10.4 0.25 0.071 0.052 12.17 85%
14 230 30 9.8 0.23 0.059 0.044 13.65 72%
15 233 30 9.8 0.23 0.058 0.044 13.84 71%
16 197 55 12.1 0.81 0.056 0.083 9.61 126%
17 227 55 12.7 0.84 0.052 0.072 11.47 111%
18 290 55 14.6 0.97 0.048 0.064 14.86 98%
19 285 61 17.0 1.13 0.058 0.081 13.94 122%
20 283 56 17.6 1.17 0.059 0.082 14.33 123%
21 299 101 9.3 0.62 0.038 0.053 11.16 83%
22 262 49 16.7 1.11 0.059 0.077 14.20 118%
23 289 45 13.6 0.90 0.050 0.057 15.42 88%
24 241 42 12.6 0.84 0.056 0.061 13.47 94%
25 258 42 12.6 0.84 0.048 0.056 14.62 87%
26 286 48 14.5 0.96 0.050 0.060 15.53 93%
27 297 101 13.8 0.92 0.064 0.082 11.11 124%
28 278 101 11.4 0.76 0.061 0.072 10.32 111%
29 295 101 11.3 0.75 0.056 0.068 11.07 102%
30 278 101 9.0 0.60 0.046 0.057 10.16 88%
31 252 54 13.2 0.88 0.052 0.067 12.92 102%
32 242 101 9.6 0.48 0.055 0.076 8.20 118%
33 237 48 10.2 0.51 0.042 0.052 12.42 82%
34 238 48 10.4 0.52 0.049 0.053 12.40 84%
35 240 48 9.9 0.49 0.053 0.050 12.54 79%
36 220 48 10.2 0.51 0.063 0.055 11.58 88%
37 226 46 9.3 0.46 0.058 0.048 12.02 77%
38 218 45 10.0 0.50 0.061 0.054 11.68 86%
39 227 45 9.8 0.49 0.063 0.050 12.36 79%
40 227 48 10.0 0.50 0.065 0.052 12.06 83%
41 226 101 9.69 0.32 0.085 0.082 7.43 130%
42 226 57 12.70 0.42 0.073 0.071 11.20 113%
43 272 101 12.26 0.41 0.089 0.080 9.65 127%
44 274 101 11.19 0.37 0.082 0.072 9.73 115%
45 264 51 10.80 0.36 0.070 0.049 13.65 79%
46 271 101 10.69 0.36 0.063 0.070 9.60 111%
47 271 101 11.35 0.38 0.069 0.074 9.57 119%
48 269 40 14.11 0.47 0.066 0.059 15.09 94%
49 270 44 13.95 0.47 0.081 0.060 14.61 96%
50 273 101 12.34 0.41 0.112 0.081 9.68 127%
51 274 101 11.94 0.40 0.108 0.078 9.73 123%
52 330 101 13.32 0.67 0.072 0.066 12.96 103%
53 329 101 16.71 0.56 0.075 0.081 12.93 129%
54 331 101 14.28 0.48 0.065 0.069 12.99 110%
55 335 101 16.82 0.56 0.110 0.081 13.18 128%
56 338 101 14.40 0.48 0.091 0.068 13.31 108%
57 329 55 16.61 0.55 0.059 0.060 17.13 97%
58 329 55 16.42 0.55 0.058 0.060 17.12 96%
59 270 101 12.92 0.43 0.095 0.079 10.19 127%
60 269 101 13.85 0.46 0.103 0.085 10.15 136%
61 268 57 17.15 0.57 0.090 0.076 14.06 122%
62 270 54 13.85 0.46 0.068 0.059 14.47 96%
63 215 55 12.8 0.64 0.075 0.075 10.80 119%
64 215 57 14.7 0.73 0.079 0.089 10.65 138%
65 218 49 15.8 0.79 0.074 0.087 11.61 136%
66 217 52 15.1 0.75 0.074 0.086 11.30 133%
67 223 52 15.1 0.75 0.073 0.083 11.61 130%
68 248 101 11.3 0.57 0.090 0.086 8.50 133%
69 247 101 11.9 0.59 0.090 0.091 8.46 141%
70 242 52 13.2 0.66 0.061 0.068 12.36 106%
71 247 55 14.5 0.73 0.066 0.074 12.44 117%
72 244 56 15.1 0.76 0.068 0.079 12.18 124%
73 250 38 13.5 0.67 0.055 0.059 14.36 94%
74 253 101 10.3 0.52 0.087 0.076 8.81 117%
75 266 101 9.5 0.4a 0.081 0.065 9.41 101%
76 268 38 10.1 0.51 0.046 0.041 15.42 66%
77 264 38 8.9 0.44 0.044 0.037 15.19 59%
Average 0.075 0.059 117%93%
Std. Deviation 0.009 0.015 0.15 0.21
257
Table A4.6.5: Calculation of solids circulation in pilot reactor from helium tracer tests
(Correlations for solids flux for horizontally and vertically panels presented in Figure 3.20)
Units C H 4 H
2
0 N
2
Total
Reactor feed rate (SLM) SLM 42 126 6.6 175
Reactor feed rate (kg/h) kg/h 1.80 6.08 0.50 7.88
Density of feed at 550C,T 100kPa (p
f
) kg/m
3
2.76 Ideal gas
Particle density (p
p
) kg/m
3
2150 NiO catalyst material
Reactor feed gas flow (Q
core
) m
3
/s 8.41E-4 Assume 100%flows to core
Flow area of reactor core (A
core
) m
2
0.0048
Flow area of reactor annulus (A
ann
) m
2
0.0074
Superficial gas velocity in core (U
core
) m/s 0.175 = Qcore 1 Acore, at core entry
Solids voidage at U
m
/(e
m
f) - 0.5 Assumed value
Fraction of measured [He] in core
compared to annulus
- 0.12
Assume that solids entering
core carry gas with [He]
measured at mid-height
annulus
Solids circulation rate (m
pcore
) kg/s 0.22 = 0.12 (Qcore / e
mf
) (p
p
1 s
mf
)
Average downward velocity in annulus m/s 0.027 = 0.12 (Qcore / s
mf
) 1 A
am
Solids fluxup core (G
pcore
) kg/m
2
s 45 Wlpxore / ACOre
Product of (Ucore Pp)
kg/m
2
s 377 Scaling variable
Predicted solids flux from cold model
experimentation (G
pC0
re)
kg/m
2
s
28
Horizontal slotted panels (eq.
5.2)
Predicted solids flux from cold model
experimentation (G
pC0
re)
kg/m
2
s
42
Vertically slotted panels (eq
5.1)
Table A4.6.6: Data from ATR experiments with 0
2
:C molar ratio varied from 0 to 0.6
# Reacto r temperatures (C) Reacto r Heater duty (kW) Feed flo w (SLM)
Co re Splash Freebo ard pressure Preheater Reacto r CH4 H20 N2 Air
average zo ne (kPa)
1 558.50 559 484 1081 1.794 4.2 20.05 60.15 3.2 0.0
2 556.25 560 487 1137 1.872 3.8 20.05 60.15 3.5 11.4
3 556.50 569 492 1186 1.872 2.6 20.05 60.15 5.6 22.9
4 555.50 565 197 1082 1.872 1.8 20.05 60.15 6.7 33.9
5 556.00 575 499 1135 2.34 1.4 20.05 60.15 6.9 45.6
6 553.25 571 498 1110 2.73 1.8 20.05 60.15 7.3 45.6
7 560.75 583 505 1132 2.574 0 20.05 60.15 7.9 58.2
8 561.00 585 507 1133 1.56 0 20.05 60.15 7.6 58.2
# Permeate Reacto r off gas (GC) Steam to 02 to H2 to
Flo w [H2] H2 flow H2 N2 CO CH4 C02 CH4 carbo n carbo n carbo n
(SLM)
[H2]
(SLM) co nv. ratio ratio ratio
1 21.5 47.49 10.19 40.4301 8.1737 0.3483 33.6113 17.4366 34 . 6% 3.0 0.000 0.508
2 21.8 47.86 10.44 32.4328 26.0142 0.3836 25.392 15.774 38. 9% 3.0 0.119 0.521
3 21.0 47.21 9.92 25.376 40.4261 0.2202 19.2968 14.6809 4 3. 6% 3.0 0.240 0.495
4 21.5 47.21 10.16 23.105 48.1202 0.2161 14.5713 13.9874 4 9. 4 % 3.0 0.355 0.507
5 20.2 45.89 9.27 20.7149 54.0275 0.1667 11.4451 13.6458 54 . 7% 3.0 0.478 0.463
6 22.4 44.86 10.04 21.7646 53.4657 0.1599 11.1439 13.4658 55. 0% 3.0 0.478 0.501
7 22.1 44.10 9.75 19.1315 58.932 0.1628 8.3946 13.3791 61. 7% 3.0 0.610 0.486
8 21.1 47.14 9.97 19.4709 58.6093 0.1663 8.4454 13.3081 61. 5% 3.0 0.610 0.497
258
Table A4.6.7: Temperature profile of the reactor core during high temperature ATR tests
(Run #6, NG feed = 20 SLM, S:C = 3.0, note that catalyst activity was low for these tests)
02 : C ratio 0.15 0.3 0.45
Po int Co re 1 Co re 2 Co re 1 Co re 2 Co re 1 Co re 2
D (to p) 64 7. 0 64 6. 5 648. 0 64 8. 0 653. 0 658. 5
C 64 4 . 5 64 8. 5 642. 5 64 7. 0 674 . 0 652. 0
B - 64 6. 0 - 64 1. 0 - 64 4 . 5
A (bo tto m) 635. 5 64 9. 0 646. 0 - 656. 0 -
50%
40%
c
o
E 30%
CD
>
C
o
o
20%
10%
0%
X equilibrium (no membranes)
sweep
no sweep
550 570 590 610 630 650
Temperature (C)
Figure A4.6.1: Measured and predicted methane conversion as a function of reactor temperature
(1,060 kPa, steam-to-carbon = 3.0, run #6, predicted conversion is equilibrium with no H
2
removal, note that catalyst activity is low for these data)
50%
40%
c
o
'jn 30%
>
c
o
o
rf 20%
I
O
10%
0%
no sweep
sweep
X Equilibrium (no membranes)
2.0 2.5 3.5 4.0 3.0
S:C ratio
Figure A4.6.2: Methane conversion as function of steam-to-carbon ratio, reactor temperature and
sweep gas (1,060 kPa, 570C, run #6, catalyst activity is low in these tests)
259
20
^ 15
_J
W
x 10
X
* *
X s
K
- *
R
X
X
X
I
s
X
\ *
X
10 15 20 25 30 35 40 45
Natural gas f eed rate ( SLM)
Figure A4.6.3: Hydrogen flux as a function of natural gas feed rate for all data in Table A4.6.4
260
Appendix 4.7 - Microreactor Data
Table A4. 7. 1: Microreactor catalyst test data
Catalyst: 0.3 g of catalyst mix (50% crushed NiO, 50% alumina)
Conditions: 550C, 201 kPa
Feeds: 30 Nml/min CH4
105 Nml/min H20 (S:C = 3.5)
30 Nml/min H2
Space Vel: 99,400 1/h (based on feed at operating conditions)
Original NiO NiO after 1st run NiO after 3rd run
Time CH4 Time CH4 Time CH4
(hour) conversion (hour) conversion (hour) conversion
0.92 48.6 0.53 44.90 0.48 44.76
1.42 46.7 1.0 46.31 1.03 44.88
1.92 46.3 1.68 45.25 1.72 43.38
5.9 46.1 3.03 45.06 2.48 44.38
6.57 44.7 4.23 44.19 3.47 44.36
19.09 45 20.10 45.15 4.23 43.91
19.59 44.9 23.72 44.71 20.57 39.70
20.22 44 28.40 44.21 22.52 39.70
21.92 44.9 44.43 43.35 24.52 39.35
30.47 44.3 46.85 43.52 26.52 40.56
30.97 44.3 48.55 43.80 28.12 39.88
43.92 43.1 50.57 42.95 44.47 36.19
44.5 42.8 52.38 42.60 46.55 34.77
45 43.8 68.28 43.53 48.52 35.20
48.92 42.8 50.65 34.36
49.45 42.4 52.28 34.00
53.22 41.6 68.30 31.10
53.92 41.6 70.93 30.85
54.65 42.1 72.65 30.65
65.58 40.3 140.32 20.72
66.08 40.6
66.58 38.9
69.83 39.4
70.45 39.3
72.17 39.2
72.67 39.3
261
Table A4. 7. 2: Data from virgin A T R microreactor tests
to
to
Operating
Mode
Date Time Hour
Bed temp fC) GC analysis Exit flow
(s/60ml)
CH4 Conv
(%)
Carbon
Balance
H2:C
Operating
Mode
Date Time Hour
T1 T2 T3 AvgT H2 CO CH4 C02
Exit flow
(s/60ml)
CH4 Conv
(%)
Carbon
Balance
H2:C
ATR
06/13/05 12:10 0.00
ATR
06/13/05 14:02 1.87 511 557 583 550 57.7 1.43 15.45 25.42 13.53 63.48 94.9 1.29
ATR
06/13/05 15:09 2.98 508 565 583 552 57.96 1.41 15.68 24.95 13.57 62.70 93.8 1.29
ATR
06/13/05 16:28 4.30 508 562 584 551 57.85 1.37 16.18 24.6 13.49 61.61 95.0 1.30
ATR
06/14/05 8:12 20.03 502 536 615 551 56.23 1.26 19 23.46 14.13 56.54 90.4 1.16
ATR
06/14/05 11:59 23.82 503 540 617 553 55.83 1.22 19.33 23.63 13.68 56.25 97.1 1.23
ATR
06/14/05 16:20 28.17 503 539 619 554 55.13 1.31 20.05 23.51 13.62 55.32 99.4 1.22
ATR
06/15/05 9:59 45.82 502 540 604 549 55.3 1.24 20.4 23.05 13.73 54.35 97.5 1.21
SMR
06/15/05 11:05 46.92 517 517 517 517 67.39 1.07 23.82 7.72 15.37 26.95 118.4 2.44
SMR
06/15/05 12:13 48.05 550 550 550 550 72.94 2.11 15.09 9.86 14.88 44.24 101.5 2.73
SMR
06/15/05 13:18 49.13 551 551 551 551 72.53 2.10 15.72 9.65 14.86 42.77 103.2 2.71
SMR
06/15/05 14:56 50.77 551 551 551 551 72.39 2.10 15.94 9.57 14.92 42.27 103.3 2.70
SMR
06/15/05 15:50 51.67 551 551 551 551 72.47 2.08 15.83 9.62 14.92 42.50 103.0 2.70
SMR
06/16/05 9:10 69.00 550 550 550 550 72.49 2.17 15.95 9.38 . 14.92 42.00 102.8 2.70
SMR
06/16/05 11:06 70.93 550 541 557 549 72.30 2.16 16.16 9.37 14.77 41.64 104.6 2.72
SMR
06/16/05 13:00 72.83 551 543 558 551 72.41 2.17 16.04 9.38 14.81 41.86 104.0 2.72
SMR
06/16/05 16:30 76.33 550 542 558 550 72.28 2.18 16.19 9.36 14.68 41.62 105.4 2.74
SMR
06/17/05 9:02 92.87 550 544 560 551 72.13 2.23 16.50 9.14 14.99 40.80 103.7 2.68
SMR
without H2
06/17/05 10:13 94.05 547 537 560 548 67.62 3.03 14.97 14.37 17.58 53.75 102.7 2.14
SMR
without H2
06/17/05 11:07 94.95 548 538 560 549 67.70 3.07 14.85 14.38 17.76 54.02 101.5 2.12
SMR
without H2
06/17/05 12:01 95.85 548 538 560 549 67.71 3.07 14.86 14.36 17.66 53.98 102.0 2.13
SMR
without H2
06/17/05 12:36 96.433 548 538 560 549 67.66 3.07 14.90 14.37 17.67 53.93 102.1 2.13
SMR
without H2
06/17/05 14:10 98 549 538 561 549 67.72 3.05 14.89 14.34 17.62 53.87 102.2 2.13
02 cycling
every one
mintue
06/17/05 14:40 98.5 0 51.85 1.54 29.14 17.47 39.48
02 cycling
every one
mintue
06/17/05 14:55 98.75 0 52.32 1.55 28.99 17.14 39.20
02 cycling
every one
mintue
06/17/05 15:10 99 0 53.28 1.46 28.27 17.00 39.50
02 cycling
every one
mintue
06/17/05 15:25 99.25 0 52.97 1.56 27.80 17.66 40.88
ATR
06/17/05 16:00 99.833 501 546 608 552 50.42 1.49 25.31 22.79 14.33 48.96 99.80 1.95
ATR 06/17/05 16:41 100.52 502 541 605 549 50.02 1.48 25.69 22.81 14.62 48.60 96.72 1.90
ATR
06/17/05 17:28 101.3 501 541 609 550 49.81 1.5 25.91 22.79 14.49 48.39 98.86 1.91
Appendix 4.8 - TGA Analysis of SMR Catalyst
Thermo-grayimetric analysis (TGA) was performed on three S MR catalyst samples (NiO, Siid-
Chemie G-91 5/8" x 1/4" EW, see Table A5.3.1). This work was carried out in a Shimadzu TGA50H.
A sample of crushed catalyst (~18 mg) was heated in a 50 ml/min gas flow of mixed air / nitrogen
from ambient temperature to 800C at a rate of 10C/min (see Figure A5.3.1 for temperature profile).
The normalized weight loss / gain profile of the three samples are presented in Figure A5.3.2
Table A4. 8. 1: T G A S MR catalyst samples
# Description
Alumina
dilution
Sample
weight (mg)
Comments
1 Fresh catalyst None 16.88 Crushed from spoked pellets
2
I CF B MR catalyst after Apri l
20 2004 run
50% 17.72
Grey-black powder. Activity
shown to O Kin microreactor
I CF B MR catalyst after Apri l
20 2004 run
tests
3
I CF B MR catalyst after last
Ni O run
50% 18.75
Grey-black powder. Activity
known to be low
1000
O 800
0)
^ 600
ns
E
* 200 -
0 ^ : , , , , , ,
0 20 4 0 60 80 100 120 140 160
Time (min)
Figure 4.8.1: Temperature profile of T G A tests
The fresh Ni O catalyst showed a steady weight loss over most of the temperature range. The T GA
weight profiles for the two used catalysts were almost identical and showed a slight weight increase,
perhaps due to oxidation of nickel. The time derivative of the weights for sample #1 (fresh catalyst)
and sample #3 (used catalyst) are presented in Figures A4.8.3 and A4.8.4 respectively. The profile for
the other used S MR catalyst sample (#2) is very similar. As can be seen, the fresh sample lost weight
at a fairly consistent weight, where the derivative profile for the used catalyst peaked around 400C.
263
1.02
| 0.96
o
z
0.94
3. After 3rd run
2. After 1st run
1. Fresh NiO
200 300 400 500 600 700 800
Temperature (C)
0 100
Figure A4.8.2: TGA weight profiles of NiO samples, normalized to initial sample weight
0.0010
8ffl0
-0.0010
Temperature (C)
Figure A4.8.3: TGA differential weight profiles of sample #1 (fresh NiO catalyst)
0.0010
8<D0
-0.0010
Temperature (C)
Figure A4.8.4: TGA differential weight profiles of sample #3 (after final ICFBMR run)
264
Appendix 4.9 - XRD Analysis of SMR Catalyst
X-ray diffraction analysis (XRD) was performed on SMR catalyst samples to identify the form of
nickel in the new and spent reforming catalyst in order to better understand the mode of catalyst
deactivation. XRD is a crystallography technique in which the pattern of diffracted x-rays from a
powdered sample are analysed to identify the nature of the crystal lattices. The analyses were carried
out in Siemens Diffraktomer D5000 with a cobalt detector operating at 40 mA / 35 kV. Samples were
ground to a fine slurry in acetone and then deposited as a thin film on a glass slide. After drying, the
slides were placed in the XRD machine and subjected to the x-ray source over an angle of 8 to 80.
The spectrum was analysed using a commercial software package (XRD Commander) and matched
to a spectra database (EVA). The same three samples analysed in the TGA apparatus where analysed
in the XRD machine (samples 1 - 3 in Table A4.9.1).
# Description Alumina dilution Comments
1 Fresh SMR catalyst None Crushed from spoked pellets
2
ICFBMR catalyst after April 20 2004
run
50%
Activity shown to OK in microreactor
tests
3 ICFBMR catalyst after last NiO run 50% Activity known to be low
o
O
l< I
I M l ! I h i t ,
i nAI'MII$fy

r ^f*^ Vu''^A^|>1 M>rr*yfi/w

2-Theta - Scale
rr^1 KiO premn -File: 1NiO premn.raw -Typa: t.odred Orruoied - Start: 3000* -rnd- SO 013 ' -Step: 0037 -Step time: 177 P. 8 -Temp : 25 *c {Room) -Time Started' 9 $-2-Theta: 3 000
a
-Th
Operations: Y ScaleAdd 562 f V Scaie Add 1000: Background 1.000.1.000! import
>^Y + 10.0mm-2 NiO used - File: 3 NiO used.raw -Type: Loosed Coupled -Start 3.000 * - tftc: 80.013 * Step. C.C37 -Step tme: 177.8 s - Temp: 25 "CfRo o mj-Time Started % s -2-Theta:
Operations: V Seals Add 2921Y ScaleAdd -375 \ Y Scats Add 1X0) Background 1.000, 1.000 [ Import
t^UY 20.0 mm-1 NiO preryn - File: t NiO prert.-n.row Type. Locked Coupled -Start 3.000 * End: 80.013 - Step: 0.037 -. step time: 177.8 s Temp.: 25 *C (Room) - Time Started: C- s -2-Trre
Operations: Y Scsle Add ' j Y Scars Add -750| Range Cp A-B | Background i.C0C.1.000| Import
Figure A4.9.1: XRD analysis of fresh SMR catalyst (sample #1, top spectra) and used catalyst
(sample #3, middle spectra). The bottom spectra is sample #1 subtract sample #3.
265
APPE NDI X 5 - Post-Run Membrane Testing Details
Side A
3/16"
tube
^ maybe a leak
\ o n tube weld
Side B Side A
2 leaks, old
creases
still seen
old crease
faintly
present
2 small \
leaks
Side A
Panel #1
3/16"
tube
Side B
no leaks
detected
Panel #5
Side B Side A
no leaks
detected
Side A
Panel #3
3/16"
tube
3/16"
tube
2 small
leaks?

no leaks
detected
Side B Side A
no leaks
detected
Panel #6
leak?
Side B
no leaks
detected
Panel #4
3/16"
tube
Area of no scale, V"""\
flaked off? / * \
^ likely a leak
on tube weld
Side B
Id crease
faintly
seen
no leaks
detected
Panel #8
Figure A5.1: Post-pilot run membrane panel refrigerant leak testing observations
266
Figure A5. 2: S EM of fresh Pd
7 5
Ag
2
5 foil at xlOOOmagnification
268
kCts-f
20H
154
0 2 4 6 8 keV
Line Method Intensity K-ratio ZAF Concentration 2 Sigma Z A F
0KA STOICH 4.36 wt% 0.04 wt%
Al KA PRZ 2308.76 0.031 1.583 4.91wt% 0.02 wt% 0.898 1.763 1.00C
Ca KA PRZ 205.01 0.009 0.959 0.82 wt% 0.01wt% 0.921 1.043 0.99S
FeKAl PRZ 26.81 0.010 0.931 0.94 wt% 0.05wt% 1.032 1.002 0.90C
NiKAl PRZ 669.78 0.864 1.025 88.54 wt% 0.54 wt% 1.025 1.000 1.00C
Rh LA PRZ 0.00 0.000 1.000 0.00wt% 0.00wt% 1.000 1.000 1.00C
Pd LA PRZ 66.80 0.003 1.270 0.42 wt% 0.02 wt% 1.217 1.045 0.999
Far.for
Figure A5. 8: ED X scan #1 of scaled front of membrane
Line Method Intensity K-ratio ZAF Concentration 2 Sigma Z A F
Al KA PRZ 54.29 0.002 1.272 0.25 wt% 0.03 wt% 0.794 1.605 0.998
NiKAl PRZ 106.53 0.378 0.874 33.03 wt% 0.80wt% 0.864 1.011 1.000
Pd LA PRZ 2965.90 0.407 1.087 44.29 wt% 0.23 wt% 1.068 1.018 1.000
AgLA PRZ 1623.73 0.209 1.073 22.42 wt% 0.20wt% 1.063 1.009 1.000
Normalized, Factor : 1
Figure A5. 9: ED X scan #2 of polished front of membrane
270
Li ne Method Intensity K-rati o Z A F Concentration 2 Si gma Z A F
F e K A l PRZ 65.22 0.097 0.859 8.37 wt % 0.26 wt % 0.831 1.034 1.0C
P d L A PRZ 2421.93 0.479 1.022 48.94 wt % 0.23 wt % 1.017 1.005 1.0C
A g L A PRZ 2280.28 0.423 1.010 42.68 wt % 0.21 wt % 1.013 0.998 1.0C
Normalized. Factor : 1
Figure A5. 10: ED X scan #3 of smooth zone of back of membrane (Box 1 in Figure 6.9)
kCtsI ' ~ ~ ~ 1
0 v '2 i f ! 4 jf ! 6 ' 8 keV
Line" -Method Intensity K-ratio ZAF Concentration 2'Sigma Z A F -
Al KA PRZ 86.12 ' ' 0.002 1341 028 \vt% 002 wt% 0.830 1 618 0999
Cr KA PRZ 269.94 0 056 0932 ' 5 24wt% 0.08 wl% 0 933 1.027 0973
Fe KA1 PRZ 603 97 0.416 0942 39.22 wt% 0.27 wt% 0.935 1 015 0.992
Ni KAl . PR/ 87 05 0.205 0 937 19.21 wt% 0.40 wt% 0924 1.014 1.000
PdLA' ' PRZ 3443.03 0314 - 1 137 35.73 wt% 0.13 wt% TU9- 1.017 0.999
AK L A PRZ 32 74 0003 1.122 031 wt% - -0 08 \vt% 1 115 1008 0999
* Mnrmal i wH F>nrtnr f *"* * <
1
_
Figure A5. 11: ED X scan #4 of scaled zone of back of membrane (Box 2 in Figure 6.9)
271
Table A5. 1: Flux data for I CF B MR panel #6 and #8 after service in pilot plant
(Conditions when permeate flow measured = 25 C, 101 kPa)
E
Test Vessel Permeate Average permeation values
Temp (C) Pressure Flux Flux Flux Std. Dev. Flux 95%confidence
(kPa) (ALM) (SLM) (SLM) (SLM) (mol/s) interval (mol/s)
1 560 308 1.50 1.38 1.37 0.010 0.00102 1.05E-05
561 314 1.50 1.38
563 310 1.49 1.36
562 308 1.48 1.36
562 308 1.48 1.36
2 561 376 1.87 1.71 1.72 0.015 0.00128 1.47E-05
561 371 1.86 1.70
564 368 1.86 1.71
565 373 1.90 1.74
565 373 1.87 1.71
3 563 439 2.27 2.08 2.06 0.014 0.00153 1.45E-05
563 438 2.25 2.06
563 436 2.23 2.04
563 436 2.25 2.06
563 435 2.24 2.05
4 563 509 2.54 2.33 2.35 0.017 0.00175 1.75E-05
563 511 2.57 2.35
563 512 2.59 2.37
563 512 2.57 2.36
563 513 2.54 2.33
5 563 581 2.82 2.58 2.62 0.031 0.00195 1.75E-05
563 585 2.83 2.59
563 588 2.88 2.63
563 591 2.88 2.63
563 597 2.90 2.66
6 567 236 1.06 0.97 0.99 0.012 0.00074 1.75E-05
567 238 1.09 1.00
567 240 1.10 1.00
567 239 1.08 0.99
567 239 1.08 0.99
7A 565 239 2.24 2.05 2.10 0.027 0.00156 1.75E-05
565 242 2.28 2.09
565 243 2.29 2.10
565 245 2.31 2.12
565 247 2.31 2.12
8A 563 303 3.08 2.82 2.88 0.038 0.00215 1.75E-05
563 306 3.15 2.88
563 308 3.15 2.89
563 310 3.17 2.90
563 311 3.19 2.93
7B 563 246 2.35 2.16 2.16 0.011 0.00161 1.75E-05
563 248 2.35 2.15
563 248 2.34 2.15
563 248 2.36 2.16
563 249 2.37 2.17
8B 561 310 3.15 2.89 2.87 0.019 0.00213 1.75E-05
561 309 3.12 2.86
561 308 3.13 2.86
561 308 3.10 2.84
561 308 3.15 2.88
9 560 382 3.94 3.61 3.59 0.024 0.00267 1.75E-05
560 381 3.91 3.58
560 379 3.94 3.61
560 378 3.88 3.55
560 377 3.92 3.59
10 558 445 4.57 4.18 4.21 0.036 0.00313 1.75E-05
558 445 4.55 4.17
558 447 4.59 4.20
558 448 4.65 4.26
558 449 4.62 4.23
11 554 508 5.30 4.85 4.82 0.047 0.00359 1.75E-05
554 508 5.33 4.88
554 508 5.22 4.78
554 509 5.21 4.77
554 509 5.25 4.81
12 568 164 1.13 1.03 1.03 0.005 0.00076 1.75E-05
568 164 1.13 1.03
568 164 1.12 1.03
568 164 1.11 1.02
568 164 1.12 1.03
272
Appendix 6.1 - Simulation Details
Table A6.1.1: HYSYS simulation details
1 Program HYSYS, Aspen Technology Inc., v3.4 (2004)
2. Physical properties package PRSV, default settings
3 Enthalpy method Equation of state
4 Chemical components C
2
H
6
, C H 4 , CO, C0
2
, H
2
, H
2
0, N
2
, 0
2
, Ca
273
Figure A6. 1. 1: HYSI S reactor simulation flowsheet (Sheet 1: Left hand side)
Figure A6.1.1 (cont.): HYSI S reactor simulation flowsheet (Sheet 2: Right hand side)
Table A6. 1. 2: Stream table for 30 Nm
3
/h base case reactor simulation
Name 1_hot feed 2_Cat recycle 2_recycle 3 gas recycle 3 gas recycle-2 4_gas gibbsl 5solids 6 1 retentate 6 2 retentate 6 3 retenate 6 4 retentate 6 5retentate 6 6 retentate 6 7retentate
Mass flow[kg/h] 37.55 1558.98 1558.98 5.33 5.33 42.88 1558.98 42.61 42.34 42.07 41.80 41.53 41.26 40.99
Volume flow[m3/h] 6.18 1.14 1.14 0.65 0.65 7.61 1.14 7.21 6.93 6.65 6.37 6.10 5.83 5.57
Molar flow[kmolm] 2.14 38.90 38.90 0.22 0.22 2.62 38.90 2.49 2.40 2.31 2.22 2.14 2.05 1.97
Temperature [C| 600 618 618 618 618 600 600 600 597 594 592 588 585 582
Pressure [kPal 2500 2500 2500 2500 2500 2500 2500 2500 2500 2500 2500 2500 2500 2500
Vapour Fraction 1 0 0 1 1 1 0 1 1 1 1 1 1 1
Molecular Weight 17.52 40.08 40.08 24.52 24.52 16.34 40.08 17.11 17.65 18.22 18.81 19.45 20.12 20.83
Density [kg/m3] 6.07 1368 1368 8.26 8.26 5.64 1368 5.91 6.11 6.33 6.56 6.81 7.07 7.35
Viscosity [cP] 2.66E-02 3.27E-02 3.27E-02 2.71E-02 2.75E-02 2.77E-02 2.79E-02 2.81E-02 2.83E-02 2.86E-02 2.88E-02
Thermal cond. [W/m-K) 9.24E-02 8.02E-02 8.02E-02 1.17E-01 1.10E-01 1.06E-01 1.03E-01 9.96E-02 9.63E-02 9.30E-02 8.97E-02
Heat capacity [kJ/kg-C] 270 0.90 0.90 1.61 1.61 2.62 . 0.89 2.55 2.48 2.41 2.34 2.27 2.20 2.13
Heat flow[kJ/h] -378515 7634481 7634276 -32686 -32688 -386065 7609344 -388346 -38S871 -385226 -383426 -381496 -379421 -377189
Mole fraction-CH4 0.25 0 0 0.0131 0.0131 0.1551 0 0.1634 0.1607 0.1572 0.1530 0.1480 0.1421 0.1352
Mole fraction - CO 0 0 0 0.0154 0.0154 0.0084 0 0.0088 0.0096 0.0103 0.0110 0.0116 0.0122 0.0128
Mole fraction -C02 0 0 0 0.1778 0.1778 0.0578 0 0.0609 0.0718 0.0839 0.0973 0.1122 0.1288 0.1471
Mole fraction - H20 0.75 0 0 0.4095 0.4095 0.5532 0 0.5830 0.5877 0.5913 0.5940 0.5959 0.5968 0.5961
Mole fraction - N2 0 0 0 0.3040 0.3040 0.0252 0 0.0266 0.0276 0.0286 0.0298 0.0310 0.0323 0.0336
Mole fraction - 02 0 0 0 0 0 0 0 0 0 0 0 0 0 0
Mole fraction - H2 0 0 0 0.0802 0.0802 0.2003 0 0.1572 0.1428 0.1287 0.1150 0.1013 0.0878 0.0751
Mole fraction - Ca 0 0 0 0 0 0 1 0 0 0 0 0 0 0
Name 6 8 retenate 6 9retentate 6 10retentate 8 1 H2 8_10H2 8 2H2 8 3H2 8 4H2 8 5H2 8 6H2 8 7H2 8 8H2 8_9H2 9_1 gas
Mass flow[kq/h] 40.72 40.45 40.18 0.27 0.27 0.27 0.27 0.27 0.27 0.27 0.27 0.27 0.27 42.61
Volume flowfm3/h] 5.32 5.07 4.82 8.16 7.86 8.13 8.10 8.07 8.08 8.08 7.99 7.94 7.96 7.32
Molar flowfkmol/h] 1.89 1.80 1.72 0.13 0.13 0.13 0.13 0.13 0.13 0.13 0.13 0.13 0.13 2.53
Temperature [CI 579 575 572 606 579 603 601 598 595 592 589 586 583 597
Pressure [kPa) 2500 2500 2500 120 120 120 120 120 120 120 120 120 120 2500
Vapour Fraction 1 1 1 1 1 1 1 1 1 1 1 1 1 1
Molecular Weight 21.60 22.43 23.30 2.02 2.02 2.02 2.02 2.02 2.02 2.02 2.02 202 2.02 16.82
Density [kg/rn31 7.65 7.98 8.33 0.033 0.034 0.033 0.033 0.033 0.034 0.034 0.034 0.034 0.034 5.82
Viscosity [cPJ 2.91E-02 2.93E-02 2.95E-02 1.98E-02 1.94E-02 1.98E-02 1.97E-02 1.97E-02 1.97E-02 1.96E-02 1.96E-02 1.95E-02 1.95E-02 2.72E-02
Thermal cond. |W/m-Kl 8.65E-02 8.32E-02 7.99E-02 3.81E-01 3.73E-01 3.80E-O1 3.79E-01 3.79E-01 3.78E-01 3.77E-01 3.76E-01 3.75E-01 3.74E-01 1.14E-01
Heat capacity[kJ'kg-C] 2.06 1.99 1.92 14.74 14.70 14.73 14.73 1472 14.72 14.72 14.71 14.71 14.70 2.56
Heat flowfkJ/h] -374877 -372489 -369957 2281 2160 2269 2257 2244 2244 2240 2209 2191 2193 -384602
Mole fraction - CH4 0.1274 0.1187 0.1086 0 0 0 0 0 0 0 0 0 0 0.1522
Mole fraction-CO 0.0133 0.0137 0.0141 0 0 0 0 0 0 0 0 0 0 0.0091
Mole fraction -C02 0.1672 0.1895 0.2140 0 0 0 0 0 0 0 0 0 0 0.0650
Mole fraction -H20 0.5947 0.5925 0.5885 0 0 0 0 0 0 0 0 0 0 0.5566
Mole fraction - N2 0.0351 0.0367 0.0384 0 0 0 0 0 0 0 0 0 0 0.0261
Mole fraction - 02 0 0 0 0 0 0 0 0 0 0 0 0 0 0
Mole fraction - H2 0.0623 0.0489 0.0365 1 1 1 1 1 1 1 1 1 1 0.1881
Mole fraction - Ca 0 0 0 0 0 0 0 0 0 0 0 0 0 0
Table A6.1.2 (cont.): Stream table for 30 NmVh base case reactor simulation
Name 9_2 gas 9_3 gas 9_4 gas 9_5 gas 9_6 gas 9_7 gas 9_8 gas 9_9 gas 9_10gas 10 1 so lids 10 2 so lids 10 3 so lids 10 4 so lids 10 5 so lids
Mass flo w[kg/h] 42.34 42.07 41.80 41.53 41.26 40.99 40.72 40.45 40.18 1558.98 1558.98 1558.98 1558.98 1558.98
Vo lume flo w [m3/h] 7.04 6.76 6.49 6.22 5.96 5.70 5.45 5.20 4.96 1.14 1.14 1.14 1.14 1.14
Mo lar f lo w[kmo^h] 2.44 2.36 2.27 2.19 2.10 2.02 1.94 1.86 1.78 38.90 38.90 38.90 38.90 38.90
Temperature |C] 594 592 588 585 582 579 575 572 569 597 594 592 588 585
Pressure fkPa] 2500 2500 2500 2500 2500 2500 2500 2500 2500 2500 2500 2500 2500 2500
Vapo ur Fractio n 1 1 1 1 1 1 1 1 1 0 0 0 0 0
Mo lecular Weight 17.33 17.86 18.41 19.01 19.64 20.30 21.01 21.78 22.60 40.08 40.08 40.08 40.08 40.08
Density [kg/m31 6.02 6.22 6.44 6.67 6.92 7.19 7.47 7.77 8.10 1367.91 1368 1368 1368 1368
Visco sity |cP] 2.74E-02 2.77E-02 2.79E-02 2.81E-02 2.83E-02 2.86E-02 2.89E-02 2.91E-02 2.95E-02
Thermal co nd. [W/m-Kl 1.11E-01 1.08E-01 1.05E-01 1.02E-01 9.86E-02 9.57E-02 9.27E-02 8.98E-02 8.68E-02
Heat capacity fkJ/kq-Cl 2.49 2.42 2.35 2.28 2.21 2.15 2.08 2.01 1.93 0.89 0.88 0.88 0.88 0.88
Heat flow [kJ/h) -382969 -381181 -379252 -377181 -374980 -372686 -370296 -367797 -365237 7605601 7601699 7597654 7593481 7589166
Mo le fractio n -CH4 0.1486 0.1443 0.1392 0.1333 0.1266 0.1190 0.1105 0.1008 0.0902 0 0 0 0 0
Mo le fractio n -CO 0.0097 0.0103 0.0109 0.0115 0.0120 0.0124 0.0128 0.0131 0.0133 0 0 0 0 0
Mo le fractio n -C02 0.0793 0.0918 0.1056 0.1209 0.1378 0.1562 0.1763 0.1987 0.2230 0 0 0 0 0
Mo le fractio n -H20 0.5589 0.5603 0.5606 0.5600 0.5582 0.5554 0.5515 0.5463 0.5400 0 0 0 0 0
Mo le fractio n - N2 0.0271 0.0281 0.0291 0.0303 0.0315 0.0328 0.0341 0.0356 0.0372 0 0 0 0 0
Mo le fractio n -02 0 0 0 0 0 0 0 0 0 0 0 0 0 0
Mo le fractio n - H2 0.1764 0.1652 0.1545 0.1441 0.1340 0.1243 0.1148 0.1055 0.0963 0 0 0 0 0
Mo le fractio n -Ca 0 0 0 0 0 0 0 0 0 1 1 1 1 1
Name 10 6 so lids 10 7 so lids 10 8so lids 10_9 so lids 10 10So lids 11 Air 13 o xidized 14 ROG 15 H2 pro duct H2 per stage . NG Set Tmax SetP Steam
Mass flo w(kg/hi 1558.98 1558.98 1558.98 1558.98 1558.98 28.84 69.02 63.69 2.70 0.27 8.59 28.95
Vo lume f lo w |m3/hl 1.14 1.14 1.14 1.14 1.14 2.92 8.35 771 80.37
Mo lar.flo w fkmol/hl 38.90 38.90 38.90 38.90 38.90 1.00 2.81 2.60 1.34 0.13 0.54 1.61
Temperature [C| 582 579 575 572 569 600 618 618 593 600
Pressure (kPa) 25O0 2500 2500 2500 2500 2500 2500 2500 120 2500
Vapo ur Fractio n 0 0 0 0 0 1 1 1 1
Mo lecular Weight 40.08 40.08 40.08 40.08 40.08 28.85 24.52 24.52 2.02 2.02 16.04 18.02
Density Ikg/m31 1368 1368 1368 1368 1368 9.86 8.26 8.26 0.03
Visco sity [cP] 4.29E-02 3.27E-02 3.27E-02 1.96E-02
Thermal co nd. [W/m-K] 6.05E-02 8.02E-02 8.02E-02 3.77E-01
Heat capacity fkJ/kg-Cl 0.88 0.87 0.87 0.87 0.87 1.13 1.61 1.61 14,72
Heat flo w [kJ/h] 7584724 7580221 7575640 7570948 7566228 17582 -422902 -390216 22289
Mo le fractio n - CH4 0 0 0 0 0 0 0.0131 0.0131 0 0 1 0
Mo le fractio n -CO 0 0 0 0 0 0 O.0154 0.0154 0 0 0 0
Mo le fractio n -C02 0 0 0 0 0 0 0.1778 0.1778 0 0 0 0
Mo le fractio n -H20 0 0 0 0 0 0 0.4095 0.4095 0 0 0 1
Mo le fractio n - N2 0 0 0 0 0 0.79 0.3040 0.3040 0 0 0 0
Mo le fractio n - 02 0 0 0 0 0 0.21 0 0 0 0 0 0
Mo le fractio n - H2 0 0 0 0 0 0 0.0802 0.0802 1 1 0 0
Mo le fractio n -Ca 1 1 1 1 1 0 0 0 0 0 0 0 0
Heat Streams
Name H heatlo ss
Heat Flo w [kJ/h] -7200
Spreadsheet inputs:
-H2 production
-S:C molar ratio
-H2:C recovery
-Reactor pressure
-Max membrane temp
Spreadsheet input:
-Core gas velocity
Spreadsheet input:
-Reactor heat loss
Spreadsheet input:
-Volumetric flow of
recycled gas
Spreadsheet inputs:
-Membrane thickness
-Permeate pressure
Set reactor feeds <1>
-CH4 / H20 flow
-Pressure
-Temperature = membrane temp
Calculate volumetric flow of
reactor feed <1>
-Calculate core flow area from
Ucore and feed volumetric flow
-Set solids circulation (kg/s) using
Equation 7.1
Distributor reactor
Compute temperature and stream
outputs from Gibbs reactor (A)
Membrane (B11
Adjust H2 split in 1
st
membrane
until permeate <8.1> is 10%of
total H2 production
Core reactor (CU
Compute temperature and stream
outputs from Gibbs reactor (C1)
9 Membrane/reactor pairs
Solve subsequent membranes
(B2-10) & Gibbs reactors (C2-10)
Oxidation reactor (D)
Adjust air flow < 11> until Gibbs
temperature matches returning
solids <2>
Set air feed <11 >
initial flow guess
Pressure
Temperature = membrane temp
NO, Iterate
Set gas recycle
Adjust split of ROG (E) to achieve
desired volumetric flow of gas
recycle <3>
Calculate membranes
7
-H2 core partial pressure &
temperature profile known
-Calculate membrane area per
stage and sum to find total
-H2 core partial pressure &
temperature profile known
-Calculate membrane area per
stage and sum to find total
YES
Figure A6. 1. 2: HYSI S reactor algorithm schematic
(Refer to Figure 6.1 for nomenclature)
Table A6. 1. 3: 30 Nm
3
/h process inputs
Feed Supply
pressure (kPa)
Base case cost ($CAD) Notes
1 Natural gas 120 $0.285/Nm
3
15 mg S/m
J
sulfur (as S)
2 Water 300 $0.34/1,000 m
3
City supply, trace chlorine
3 Ai r 101 Free Atmospheric
4 Electricity - $0.080/kWh
278
Table A6.1.4: Pinch analysis summary
Temperature (C) Heat flow (kW)
TI T2 T3 T4 Q12 Q23 Q34 Total
cn
Reactor off-gas 618 178 100 11.98 12.84 24.82
4)
O
l_<
Hydrogen 600 40 6.09 6.09
3
O
Burner gas 980 178 26.3 26.30
t/1
Total sources 57.21
Oxidation air 160 600 3.82 3.82
CO SMR water 68 226 226 600 5.56 15.1 6.64 27.30
_ C
SMRNG 160 600 3.64 3.64
Burner air 21 200 2.20 2.20
Total sinks 36.95
1000 -
800
O
2 600 -
k-
0)
Q. 400 -
E
H
200 -
0 -'
0 10 20 30 40 50 60
Heat (kW)
Figure A6.1.3: Pinch analysis diagram for 30 Nm
3
/h design
Table A6.1.5: System losses for 30 Nm
3
/h design
Description Power loss (kW) Comments
Air compressor 5.9 Rejected to ambient air
Natural gas compressor 1.3 Rejected to ambient air
H
2
compressor 10.9 Rejected to ambient air
Ambient heat losses 4.0 Rejected to ambient air
Hi cooling 2.8 Rejected to ambient air or cooling water
Reactor off-gas cooling 12.5 Rejected to ambient air or cooling water
Burner vent 9.4 Duty to cool burner gases from 250C to 25C
27 9
to
oo
o
H-H2
Hiterchanger
H2 E-H2
thru [nterchanger
mem
co mp 16*co mp
E-H2 H2
Co mp
. Intercooler
H H2
co mp
NG
Internal E-NG
interco o ler
rHP
methane E-NG
prehlat
K-NQ
Co mpresso r
steam
/ CH4
ratio
10'Co W
Feed E-Feed
preheater
H-Air
Co mp
co o ler
Hllluf
gisi
ADJ-Bumer
Temp
der3 H-ROG
39'Burned
o f f gqs
heatlo ss
26'LP
reacto r
vent
-4XJ-
28ROG
Co ndy
27ROQ
Co ndy
Figure A6.1.4: HYSI S 30 Nm /h process simulation flowsheet
Stop/ pBs^] Cgjgl pg] pT^j
to
o o
3
*
OS
IN)
o
3
o
n
as
sr
3
to ri*
Figure A6. 2. 1: Simplified P&I D for 30 NmVh - sheet 1
to
00
to
Fl ue gas ^( /.--SS-HC y
Stop/ pBS^
start
Air
>
F-1
Air fan
-IXK 2--CS-XX >
ICFBMR V-
r-ss-pp ~y-
Bumer controls
(not shown)
V
Natural gas s^>f, y.--cs-xx j-
_ J
Preheat N G )( /. --SS-HC )-
NG FIC >-
B-3
Dei oni zer
P ackage
T-1
Water tank
L - ^ T 6$) X Ira] ( ^ 0 >
p-1
Water Pump
Figure A6.2.2: Simplified P&I D for 30 Nm
3
/h - sheet 2
Table A6. 2. 1: Equipment list for 30 Nm
3
/h I CF BMR design
Tag Name Description Nominal size Pressure rating Materials of Estimated capital Source / Notes
Tag
construction ($CAD)
R-1 ICFBMR Reactor shell and distributor 2.6mx0.2md> 3000 kPa SS $40,000 estimate
Catalyst 60 L N/A
-
$5,300 MRT estimate
Membranes 2.3 m2 N/A Pd/SS $23,400
Off-gas filters (4) 5 um N/A Hastaloy $1,200 Noram quote
Start-up tubular heaters 2 x5k W N/A Inconel tube $1,200 UBC quote
T-1 Water tank Made from piping components 20 L atmospheric SS $1,000 non-ASME
T-2 Separator Made from piping components 10 L 3000 kPa SS $500
B-1 Burner Open chamber combustor with pilot 30 kW 10 kPag SS / ceramic $35,000 scaled from Noram purchase
B-2 Desulfurizers 2 columns, from piping components 2 x30L atmospheric CS $1,000 non-ASME
Adsorbent 60 L N/A - $1,400
B-3 Deionizer package Mixed bed system 3x2 5L atmospheric Fibreglas - rental
F-1 Air fan Centrifugal fan 50 m3/h 10 kPag Aluminum
-
cost included in burner
K-1 Air compressor 2 stage compressor (oil-free, air cooled) 30 Nm3/h 3000 kPa C S / S S $30,000 MRT estimate
K-2 NG compressor 2 stage compressor (oil-free, air cooled) 15 Nm3/h 3000 kPa C S / S S $22,000 scaled from Noram purchase
K-3 H2 compressor multistage compressor (oil-free, air cooled) 30 Nm3/h 3000 kPa C S / S S $50,000 $4500/kW
P-1 Water pump Positive displacement diaphragm 40 LPH 3000 kPa SS $2,300 includes pulsation dampner
E-1 Oxidation air preheater Shell & tube exchanger 0.30 m2 3000 kPa SS $590 $2000/m2
E-2 Water preheater Shell & tube exchanger 0.14 m2 3000 kPa SS $270 $2000/m2
E-3 Burner air preheater Shell & tube exchanger 0.26 m2 3000 kPa tube SS $520 $2000/m2
E-4 ROG cooler Shell & tube exchanger 0.50 m2 3000 kPa tube SS tube/CS shell $1,000 $2000/m2
E-5 NG preheater Finned tube exchanger 0.47 m2 3000 kPa SS $930 $2000/m2
E-6 H2 cooler Finned tube exchanger 0.29 m2 atmospheric S S tube/CS shell $590 $2000/m2
E-7 Steam generator Shell & tube exchanger 0.46 m2 3000 kPa tube SS $920 $2000/m2
E-8 Feed preheater Shell & tube exchanger 0.61 m2 3000 kPa tube ss
$1,220 $2000/m2
Total: $220,340
Table A6. 2. 2: Assumptions for Net Present Value analysis
Description Value Units
Economic assumptions
US D / CA D exchange rate 1.18
Cost of capital 10.0%
Inflation rate 2.0%
Marginal tax rate 38.0%
Natural gas cost $6.50 $USD/thousand scf
Natural gas cost
$0,285 $/Nm
j
Natural gas cost
$0,301 $/ G J H H V
Natural gas cost
$6.50 $ US D / MM Btu H H V
Electricity cost $0,080 /kWh
Cost of water $0.34 /1000 m
3
Service life 10 years
Investments
Bare equipment cost $220,000
Initial capital $770,000 Lang factor of 3.5
Cost of 1 membrane changeout $5,000 Labour only
Design Basis
H
2
design production rate 30 Nm
3
/h
H
2
/ CH4 production ratio 2.48 mol/mol
Operating hours per year 8,000 hours
Average operating rate 85%
Annual H
2
production 204,000 N m
3
Water consumption rate 0.07 m
3
/Nm
3
H2
Electrical usage 21 kW/ 30N m
3
of H
2
28 4
Table A6. 2. 3: Net Present Value calculations for 30 NmVh I CF BMR design
Cost over life
Operating Expanses Year 1 2 3 4 5 6 7 8 9 10 11 Life totals $/kqH2 yNm3 H2
Natural Qas cost
$23,952 $24,431 $24,920 $25,418 $25,927 $26,445 $26,974 $27,514 $28,064 $28,625 $262,272 1.428 0.129
Water cost
$5 $5 $5 $5 $5 $5 $5 $5 $5 $5 $46 0.000 0.000
Electricity cost $/batch batch/year $11,652 $11,886 $12,123 $12,366 $12,613 $12,865 $13,123 $13,385 $13,653 $13,926 $127,591 0.695 0.063
Desulfur replacement $1,400
1
$1,428 $1,457 $1,486 $1,515 $1,546 $1,577 $1,608 $1,640 $1,673 $1,707 $15,636 0.085 0.008
Catalyst replacement $5,300
1
$5,406 $5,514 $5,624 $5,737 $5,852 $5,969 $6,088 $6,210 $6,334 $6,461 $59,194 0.322 - 0.029
Dl bed replacement $1,200 $1,224 $1,248 $1,273 $1,299 $1,325 $1,351 $1,378 $1,406 $1,434 $1,463 $13,402 0.073 0.007
Membrane replacement $23,400
1 $23,868 $24,345 $24,832 $25,329 $25,635 $26,352 $26,879 $27,417 $27,965 $28,524 $261,348 1.423 0.128
Membrane chanqeout (labour, etc.) $5,000 $5,100 $5,202 $5,306 $5,412 $5,520 $5,631 $5,743 $5,858 $5,975 $6,095 $55,844 0.304 0.027
Operating &maintenance c/wbare equip cost $11,000 5.0% $11,220 $11,444 $11,673 $11,907 $12,145 $12,388 $12,636 $12,888 $13,146 $13,409 $122,856 0.669 0.060
Misc. (insurance, taxes..)c/wbare equip cost 5.0% $11,220 $11,444 $11,673 $11,907 $12,145 $12,388 $12,636 $12,888 $13,146 $13,409 $122,856 0.669 0:060
Revenues/Cost Savings
HydrogenProduction(kg/year)
18,360 18,360 18,360 18,360 18,360 18,360 18,360 18,360 18.360 18,360 183,600
Hydrogen Sales
$237,274 $242,019 $246,859 $251,797 $256,833 $261,969 $267,209 $272,553 $278,004 $283,564
Pre-taxcash flow -$770,005 $142,198 $145,042 $147,943 $150,902 $153,920 $156,999 $160,139 $163,342 $166,609 $169,941
Depreciation $0 $154,000 $123,200 $98,560 $78,848 $63,078 $50,463 $40,370 $32,296 $25,837 $20,670
Income tax $0 -$4,485 $8,300 $18,766 $27,381 $34,520 $40,484 $45,512 $49,797 $53,493 $56,723
After-taxcash flow -$770,005 $146,683 $136,742 $129,178 $123,522 $119,400 $116,515 $114,627 $113,544 $113,115 $113,218
Cumulative Net Cash Flow -$770,005 -$623,322 -$486,580 -$357,403 -$233,881 -$114,481 $2,034 $116,661 $230,205 $343,321 $456,538
Discounted Cash Flow
-$770,005 $133,348 $113,010 $97,053 $84,367 $74,138 $65,770 $58,822 $52,969 $47,972 $43,650
Cumulative DCF -$770,005 -$636,657 -$523,647 -$426,594 -$342,227j -$268,089 -$202,319 -$143,498 -$90,528 -$42,557 $1,094
Calculated Values
Inflation multiplier 1.00 1.02 1.04 1.06 1.08 1.10 1.13 1.15 1.17 1.20 1.22
Natural gas price ($/Nm3), inflationadjusted $0,285 $0,291 $0,297 $0,303 $0,309 $0,315 $0,321 $0,328 $0,334 $0,341 $0,348
Hydrogen sales price ($/kg), inflationadjusted $12.67 $12.92 $13.18 $13.45 $13.71 $13.99 $14.27 $14.55 $14.84 $15.14 $15.44
Electricity cost (S/kWh), inflationadjusted $0,080 $0,082 $0,083 $0,085 $0,087 $0,088 $0,090 $0,092 $0,094 $0,096 $0,098
Depreciation schedule (double declininq) 0.2 0.0% 20.0% 16.0% 12.8% 10.2% 8.2% 6.6% 5.2% 4.2% 3.4% 2.7% 89.3%
Annual Utilities and Chemicals
Annual H2 production (Nm3) 0 204,000 204,000 204,000 204,000 204,000 204,000 204,000 204,000 204,000 204,000
Annual CH4 consumption(Nm3) 0 82,258 82,258 82,258 82,258 82,258 82,258 82,258 82,258 82,258 82,258
Annual water consumption(m3) 0 13,600 13,600 13,600 13,600 13,600 13,600 13,600 13,600 13,600 13,600
Annual electrical consumption (kWh) 0 142,800 142,800 142,800 142,800 142,800 142,800 142,800 142,800 142,600 142,800
Table A6. 2. 4: Summary of Net Present Val ue analysis for 30 N m
3
/ h I CF B M R desig
Hydrogen Price $12.67 /kg H2
NPV
$994
Payback (years)
6
NG Cost $1.43 /kg H2
Electricity cost $0.69
Desulfurizer replacement $0.09 /kg H2
Catalyst replacement $0.32 /kg H2
Deionizer replacement $0.07 /kg H2
Membrane replacement $1.73 /kg H2
Operating & maintenance $0.67 /kg H2
Operating costs (total) $2.88
Misc. (insurance, taxes...) $0.67 /kg H2
P&l total $0.67
Capital recovery $7.00
286
Appendix 6.3
Alternate 30 Nm
3
/h ICFBMR Cost Analysis
This appendix presents a simple economic analysis for the 30 Nm
3
/h ICFBMR design using the same
assumptions as in Table E-36 ("Distributed size onsite hydrogen via steam reforming of natural gas
with current technology") in "The Hydrogen Economy: Opportunities, Costs, Barriers, and R&D
Needs"(NAE, 2004). Estimated costs are compared to a conventional SMR case of capacity 222
Nm
3
/h. Tables A6.3.1 and A6.3.2 summarizes the cost and process design basis respectively. Unless
otherwise noted, currency values are in $CAD.
Table A6.3.1: Cost basis
USD to CAD exchange rate $1. 18
Average load factor 9 0%
Cost of natural gas $6. 50 US/MM Btu HHV
$0,285 CAD/Nm3
Cost of electricity $0,070 US/kWh
$0,082 CAD/kWh
Table A6. 3. 2: Process basis
Conventional
SMR
ICFBMR Units
H2 capacity 222 30 Nm3/h H2 capacity
20.0 2.7 kg/d
H2 production 1,752,000 236,520 Nm3/year H2 production
157,680 21,287 kg/year
H2 recovery 1.91 2.48 mol H2/mol CH4
NG consumption 917,277 95,371 Nm3/year
655,198 68,122 kg/year
Electricity 346,896 165,564 kWh
Several points are worth noting from the performance data presented in Table A6.3.2:
The small-scale conventional SMR capacity is over seven times larger than the ICFBMR
capacity.
Methane utilization is significantly higher for the ICFBMR process compared to the
conventional SMR system (2.48 vs. 1.91 moles H
2
/mol CH
4
). This is not unexpected, as
conventional SMR relies on steam exports to reach high thermal efficiencies, impractical for
small-scale distributed H
2
production.
Electrical consumption is relatively higher for the ICFBMR process, due to:
o An oxidation air compressor is required in the ICFBMR process, but is not used in
conventional SMR.
28 7
o Product H
2
in the I CF B M R process must be compressed from near-ambient pressure,
while H
2
produced in conventional S M R is at higher pressure (-1,000 kPa).
Table A6. 3. 3 reproduces data for conventional S M R from Table E-36 ( N A E, 2004) in $ CA D . The
same scaling factors used to develop costs for the conventional S M R system are also used for the 30
Nm3/h I CF B M R design, wi th the exception of engineering, whi c h was assumed to be 20% of bare
capital, rather than 10%.
Table A6. 3. 3: Conventional S M R vs. I CF B M R cost comparison
Description Conv . SMR ICFBMR Notes
C
a
p
i
t
a
l

(
x
$
1
,
0
0
0
)

Ref ormer $1, 059 $170
C
a
p
i
t
a
l

(
x
$
1
,
0
0
0
)

H2 compressor $165 $50
C
a
p
i
t
a
l

(
x
$
1
,
0
0
0
)

HP H2 storage $129 $26 f actored by 0. 8 exponent
C
a
p
i
t
a
l

(
x
$
1
,
0
0
0
)

HP H2 dispenser $18 $18 assumed equal
C
a
p
i
t
a
l

(
x
$
1
,
0
0
0
)

Total capital $1, 371 $264
C
a
p
i
t
a
l

(
x
$
1
,
0
0
0
)

Facil ities $274 $53 20 % of capital
C
a
p
i
t
a
l

(
x
$
1
,
0
0
0
)

Engineering $137 $53 1 0 % /2 0 % of capital
C
a
p
i
t
a
l

(
x
$
1
,
0
0
0
)

Contingencies $137 $26 1 0% of capital
C
a
p
i
t
a
l

(
x
$
1
,
0
0
0
)

Working capital $69 $13 5% of capital C
a
p
i
t
a
l

(
x
$
1
,
0
0
0
)

Gul f Coast total $1, 919 $396
C
a
p
i
t
a
l

(
x
$
1
,
0
0
0
)

Site factor 1 1 0% 1 1 0% above Gul f Coast
C
a
p
i
t
a
l

(
x
$
1
,
0
0
0
)

Total capital costs $2, 111 $435
V
a
r
i
a
b
l
e

(
x
$
1
0
0
0
)

Operating & maint. $21 $4 1 % /yr of capital
V
a
r
i
a
b
l
e

(
x
$
1
0
0
0
)

Membranes $28 repl ace annual l y
V
a
r
i
a
b
l
e

(
x
$
1
0
0
0
)

Natural gas $262 $27 /year
V
a
r
i
a
b
l
e

(
x
$
1
0
0
0
)

Electricity $29 $14 /year
N
e
t

(
x
$
1
0
0
0
)

Total variabl e costs $312 $74 /year
N
e
t

(
x
$
1
0
0
0
)

Fixed operating cost $42 $9 2%/yr of capital
N
e
t

(
x
$
1
0
0
0
)

Capital charges $295 $61 14% /yr of capital
N
e
t

(
x
$
1
0
0
0
)

Total H2 costs $649 $143 /year
S
u
m
m
a
r
y

(
$
/
k
g

H
2
)

Total variabl e costs $1. 98 $3. 46 /kg H2
S
u
m
m
a
r
y

(
$
/
k
g

H
2
)

Fixed operating cost $0. 27 $0. 41 /kg H2
S
u
m
m
a
r
y

(
$
/
k
g

H
2
)

Capital charges $1. 87 $2. 86 /kg H2
S
u
m
m
a
r
y

(
$
/
k
g

H
2
)

H2 sel l ing price $4.12 . $6.73 /kg H2
288