Zhang Weiqi

Experimental Investigation on Gas Separation
Using Porous Membranes
vorgelegt von
Master-Ing.
Weiqi ZHANG
von der Fakultt III - Prozesswissenschaften

der Technischen Universitt Berlin
zur Erlangung des akademischen Grades
Doktorin der Ingenieurwissenschaften

Dr.-Ing.
genehmigte Dissertation
Promotionsausschuss:
Vorsitzender:
Prof. Dr.-Ing. Felix Ziegler
Berichter:
Prof. Dr. Frank Behrendt
Berichter:
Prof. Dr.-Ing. Bernd Hillemeier
Tag der wissenschaftlichen Aussprache: 03. December 2010
Berlin 2011
D 83
Ich erklre hiermit, dass ich die vorliegende Arbeit selbstndig verfasst und keine anderen als die angegebenen Quellen und Hilfsmittel verwendet habe.
Berlin, den 03. December 2010
Acknowledgment
I am deeply thankful to colleagues and advisors, who helped me complete for this
project, firstly to Univ.-Prof. Dr. Frank Behrendt, who gave me the opportunity to
do this Ph.D., made this work possible; Prof. Dr.-Ing. Bernd Hillemeier and Prof.
Dr.-Ing. Felix Ziegler, who took over the supervision of my thesis.
Maria Gaggl, who helped me with the practicalities of living in Germany, and even
shared with me her flat for two weeks when I first started my Ph.D.. Gregor Gluth,
for making all the membranes used in this project, but also for his patience. Dr.Ing. York Neubauer and Dr.-Ing. Nico Zobel, for their competence; if you encounter
any problems, either theoretical or experimental status, you can turn to them and
certainly get a reasonable answer. Horst Lochner and Uwe Rhr, who made membrane
cell and many other small parts patiently for me, and helped me with all sorts of
technicalities. Susanne Hoffmann who gave me lots of suggestions over operations with
gas chromatograph (GC ). Fang He, Gregor Drenkelfort, Birgit Packeiser, Renhui sun,
etc., my special thanks also go to for their patience and advice.
I would also like to acknowledge the on going financial support provided by Federal
Ministry of Food, Agriculture and Consumer Protection (BMELV), Agency for Renewable Resources (FNR), and the scholarship from Womens central office to finish my
thesis.
Last but not least, I would like to thank all the helpful persons that I have forgotten
to mention by name. This thesis could not have been written without the support of
my parents, my husband Jingqun Song and my friends.
Contents
Abstract
XIII
Nomenclature
XV
1 Introduction
2 State of the Art
2.1
An introduction to gas separation using membranes . . . . . . . . . . .
2.2
Inorganic membranes . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.2.1
Dense inorganic membranes . . . . . . . . . . . . . . . . . . . .
2.2.2
Porous inorganic membranes . . . . . . . . . . . . . . . . . . . .
2.3
Porous cement membranes . . . . . . . . . . . . . . . . . . . . . . . . .
2.4
Separation and process design . . . . . . . . . . . . . . . . . . . . . . .
10
2.4.1
Possible flow patterns . . . . . . . . . . . . . . . . . . . . . . . .
10
2.4.2
Number of stages . . . . . . . . . . . . . . . . . . . . . . . . . .
11
2.4.3
Known influence of operating parameters . . . . . . . . . . . . .
14
3 Experimental Setup
17
3.1
Flow chart . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
17
3.2
Experimental setup . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
19
3.3
Operating parameters and procedure . . . . . . . . . . . . . . . . . . .
26
Contents
VII
4 Summary of Equations
31
4.1
Basic assumptions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
31
4.2
Gas equations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
32
4.2.1
The fundamental equations for ideal gases . . . . . . . . . . . .
32
4.2.2
Balances . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
32
4.3
Equations for transport mechanisms through porous membranes . . . .
33
4.4
Equations for the experimental setup . . . . . . . . . . . . . . . . . . .
35
4.4.1
LabVIEW . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
35
4.4.2
Soap film flowmeter . . . . . . . . . . . . . . . . . . . . . . . . .
36
4.4.3
Mass flow controller . . . . . . . . . . . . . . . . . . . . . . . . .
36
4.4.4
Gas chromatograph . . . . . . . . . . . . . . . . . . . . . . . . .
36
Efficiency of gas separation through membrane . . . . . . . . . . . . . .
37
4.5
5 Experimental Results and Discussion

5.1
5.2
41
Controlling equipment and corresponding special procedures, calibration
41
5.1.1
Bubble flow-meter . . . . . . . . . . . . . . . . . . . . . . . . .
41
5.1.2
Data correction of mass flow controller . . . . . . . . . . . . . .
42
5.1.3
Calibration of gas chromatograph (GC ) . . . . . . . . . . . . .
43
Experiments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
55
5.2.1
First set of experiments with Gaggls membranes . . . . . . . .
55
5.2.2
Second set of experiments with modified cell . . . . . . . . . . .
62
5.2.3
Third set of experiments with tubular membrane and cell . . . .
83
6 Summary and Outlook
91
6.1
Summary of results . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
91
6.2
Observations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
92
6.3
Future work . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
93
Bibliography
97
Mitteilungen
107
List of Figures
2.1
Schematic representation of membrane separation . . . . . . . . . . . .
2.2
Transport mechanisms in porous membranes [1] . . . . . . . . . . . . .
2.3
Schematics of possible flow patterns [2, 3] . . . . . . . . . . . . . . . . .
10
2.4
Flow pattern in presence of sweep gas [2] . . . . . . . . . . . . . . . . .
11
2.5
Schemes of commercial two-stage separation [2, 3] . . . . . . . . . . . .
12
2.6
Schemes of commercial three-stage separation [2, 3] . . . . . . . . . . .
13
2.7
Novel single-stage separation with recycling [2, 3] . . . . . . . . . . . . .
13
3.1
Process schematic of gas separation . . . . . . . . . . . . . . . . . . . .
17
3.2
Process schematic of reference measurements . . . . . . . . . . . . . . .
18
3.3
Gas chromatographic system . . . . . . . . . . . . . . . . . . . . . . . .
22
3.4
Chromatogram of five-component gas . . . . . . . . . . . . . . . . . . .
23
3.5
LabVIEW controlling system . . . . . . . . . . . . . . . . . . . . . . .
25
4.1
Chromatograms of two-component gas and pure standard-gases . . . .
37
5.1
Flow rate of two-component gas at 2.4 bar . . . . . . . . . . . . . . . .
43
5.2
Flow rate of 2 % to 4 % . . . . . . . . . . . . . . . . . . . . . . . . . .
44
5.3
Flow rate of two-component gas at different pressures . . . . . . . . . .
45
5.4
GC measurements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
46
5.5
Base line of chromatogram . . . . . . . . . . . . . . . . . . . . . . . . .
46
5.6
Area of H2 in two-component gas measurements with different run times 47
5.7
Area of pure H2 measurements at different temperatures . . . . . . . .
48
List of Figures
5.8
GC measurements of different reference-flow rate . . . . . . . . . . . . .
50
5.9
N2 amount and flow rates in automatic injection . . . . . . . . . . . . .
51
5.10 Flow rate calculation of standard-gases . . . . . . . . . . . . . . . . . .
52
5.11 Pure H2 peak area for calibration of 2M measurement . . . . . . . . . .
53
5.12 Calibration curve for H2 of 2M measurement . . . . . . . . . . . . . . .
54
5.13 Schematic of the first idea . . . . . . . . . . . . . . . . . . . . . . . . .
55
5.14 Schematic of the first membrane cell . . . . . . . . . . . . . . . . . . .
56
5.15 The first membrane cell and holders . . . . . . . . . . . . . . . . . . . .
56
5.16 Pore size distribution of the first membranes . . . . . . . . . . . . . . .
57
5.17 Gaskets for the first membrane cell . . . . . . . . . . . . . . . . . . . .
58
5.18 Flow rate influence at different temperatures . . . . . . . . . . . . . . .
58
5.19 Gas separation with different volume flows . . . . . . . . . . . . . . . .
59
5.20 Gas separation with different feed gases . . . . . . . . . . . . . . . . . .
60
5.21 Experimental and theoretic selectivity . . . . . . . . . . . . . . . . . . .
61
5.22 Problem of the first membrane cell . . . . . . . . . . . . . . . . . . . .
62
5.23 First version of the secondary membrane cell . . . . . . . . . . . . . . .
63
5.24 Final design of the modified membrane cell . . . . . . . . . . . . . . . .
63
5.25 Axial section view of the modified membrane cell . . . . . . . . . . . .
64
5.26 Pore distribution of PZ-2 . . . . . . . . . . . . . . . . . . . . . . . . . .
67
5.27 Graphite gaskets around membrane . . . . . . . . . . . . . . . . . . . .
68
5.28 Performance of membrane cells in <H2 ;N2 > . . . . . . . . . . . . . . .
69
5.29 Influence of temperature in <H2 ;N2 > . . . . . . . . . . . . . . . . . . .
70
5.30 Influence of temperature in <2M ;N2 > . . . . . . . . . . . . . . . . . .
70
5.31 Influence of equivalent water to cement ratio in <2M ;N2 > . . . . . . .
71
5.32 Influence of pore size in <2M ;N2 > . . . . . . . . . . . . . . . . . . . .
72
5.33 Effect of different sample thickness on diffusion in <2M ;N2 > . . . . . .
73
5.34 Membranes after heating . . . . . . . . . . . . . . . . . . . . . . . . . .
74
5.35 Comparison of compositions in <5M ;N2 > . . . . . . . . . . . . . . . .
75
List of Figures
XI
5.36 Permeabilities of H2 using different feed gases . . . . . . . . . . . . . .
76
5.37 Influence of pressure difference in <2M ;N2 > . . . . . . . . . . . . . . .
76
5.38 Influence of sweeping gas in <H2 ;N2 > . . . . . . . . . . . . . . . . . . .
77
5.39 Measurements of different sweeping gases in <2M ;N2 > and <2M ;CO>
78
5.40 Influence of adhesives . . . . . . . . . . . . . . . . . . . . . . . . . . . .
79
5.41 SEM images of the PZ-2+MS . . . . . . . . . . . . . . . . . . . . . . .
80
5.42 Knudsen number of H2 and CO2 . . . . . . . . . . . . . . . . . . . . . .
81
5.43 Diffusion coefficients of H2 . . . . . . . . . . . . . . . . . . . . . . . . .
82
5.44 Schematic of transport in tubular membrane cell [1] . . . . . . . . . . .
83
5.45 Tubular membrane cell . . . . . . . . . . . . . . . . . . . . . . . . . . .
84
5.46 Heating system for tubular membrane . . . . . . . . . . . . . . . . . . .
84
5.47 Design of tubular membrane cells . . . . . . . . . . . . . . . . . . . . .
85
5.48 Tubular membrane and gaskets . . . . . . . . . . . . . . . . . . . . . .
86
5.49 Components in permeate-gas in <2M ;N2 > . . . . . . . . . . . . . . . .
87
5.50 Separation factors of H2 to CO2 . . . . . . . . . . . . . . . . . . . . . .
87
5.51 Water from tubular membrane . . . . . . . . . . . . . . . . . . . . . . .
88
5.52 Chromatogram in <5M ;N2 > at 200 C . . . . . . . . . . . . . . . . . .
88
5.53 Large cracks after heating . . . . . . . . . . . . . . . . . . . . . . . . .
89
6.1
Process schematic of using CO2 as sweeping gas . . . . . . . . . . . . .
95
6.2
Process schematic of using steam as sweeping gas . . . . . . . . . . . .
95
List of Tables
2.1
Applications of gas separation using membranes . . . . . . . . . . . . .
2.2
Classification of inorganic materials on pore size [4] . . . . . . . . . . .
2.3
Separation factor of some typical gas mixtures . . . . . . . . . . . . . .
15
3.1
Operating conditions of Gas Chromatograph . . . . . . . . . . . . . . .
23
5.1
Flow rates of two-component gas controlled by MFC . . . . . . . . . .
42
5.2
Gases compositions using N2 as reference . . . . . . . . . . . . . . . . .
48
5.3
Gases compositions using He as reference . . . . . . . . . . . . . . . . .
49
5.4
Volume flows of permeate-gases . . . . . . . . . . . . . . . . . . . . . .
50
5.5
Corresponding points of standard-gases . . . . . . . . . . . . . . . . . .
51
5.6
Characteristic peak area of H2 in permeate-gas and standard gases . . .
52
5.7
H2 concentration in permeate-gases . . . . . . . . . . . . . . . . . . . .
53
5.8
Physical and geometrical data of the first test membranes . . . . . . . .
56
5.9
Cement membranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
65
5.10 Code name of cement membrane . . . . . . . . . . . . . . . . . . . . . .
66
5.11 Porosity of cement membrane . . . . . . . . . . . . . . . . . . . . . . .
66
5.12 Permeation fluxes using PZ-2+MS in <2M ;N2 > . . . . . . . . . . . . .
73
5.13 Separation factors using HOZ+MS in <5M ;N2 > . . . . . . . . . . . . .
75
5.14 Separation factors using 5 mm membranes in <2M ;N2 > . . . . . . . .
80
5.15 Data using PZ-2+MS (5 mm, (w/c)eq 0.25) in <2M ;N2 > . . . . . . .
81
5.16 Permeation ability using PZ-2+MS (5 mm, (w/c)eq 0.25) in <2M ;N2 >
82
5.17 Permeation ability using tubular-PZ-2+MS (5 mm, 0.25) in <2M ;N2 >
89
5.18 Permeation ability using tubular-PZ-2+MS (5 mm, 0.25) in <5M ;N2 >
90
Abstract
Membranes have been long utilized in industry for separation of gas mixtures [5].
Thanks to their chemical, physical, and thermodynamic stability, as well as for their
high durability at elevated temperatures and high permeation flux, ceramic membranes
have become especially popular in the field. Cement is looked at as a valid alternative
for the future, as in addition to being stable, it would bring the advantage of lower costs
and longer lifespan. Research is still necessary to access the performance and reliability
of cement membranes and the present thesis wants to contribute to this topic.
More specifically, purpose of this work was to investigate the influence of gas molecules
properties on material transport, and to explore the influence of operating conditions
and membrane composition on separation efficiency. To this aim, a series of experiments
were performed.
In more detail, an experimental setup was manufactured and tested. Fifty types of
membranes were produced. Several membrane cells were designed into a module with
counter current flow pattern, where gases on two sides of the membrane flow in contrary
directions. Pure H2 , CO2 , CO, CH4 , two-component gas (49.8 % H2 and 50.2 % CO2 ),
and five-component gas (13 % H2 , 16 % CO, 13 % CO2 , 53 % N2 , and 5 % CH4 ) were
used as feed gases, while N2 and CO were used as sweeping gases.
A new method was introduced to calibrate the automatic injection of sample gases
into gas chromatography. Experiments were conducted from high to low temperatures.
Chromatograms obtained by GC could then be used to determine the amount of each
component in both permeate and retentate gas. New calibration formulas, which offer
more accurate quantification methods, are also presented in this work. On this base,
permeation rate and efficiency of gas separation could be calculated and the influence
of operating condition and membrane shape and composition could be studied.
Main results of this work cement are: the influence of all the above parameters is
collected, the best conditions and membrane type are found, cementitious material has
XIV
Abstract
the ability to separate gas mixtures, and new designs considering purification of the
product gases are provided.
Nomenclature
Abbreviations
ngstrm = 1010 m
bar
0.9869 atmosphere or 100 kPa
degrees Celsius, K-273.15
cm
centimeter
gram
GC
gas chromatography
joule
degrees Kelvin
kg
kilogram
meter
mA
milliampere
MF C
mass flow controller
min
minute
ml
milliliter
mm
millimeter
mol
gram-mole
micron
microvolt=106 v
nm
nanometer
second
V ol
volume
VOL
volatile organic liquids
Latin Letters
A
surface area of the membrane
[cm2 ]
molar density of the fluid mixture
[mol/ml]
CH 2
partial molar density of component H2
[mol/ml]
Nomenclature
XVI
CCO2
partial molar density of component CO2
[mol/ml]
diffusion coefficient
[cm2 /min] or [m2 /s]
Di
molecular diffusion coefficient
[m2 /s]
Di,K
Knudsen diffusion coefficient
[m2 /s]
DPI
value of pressure difference meter
[bar]
DS
surface diffusion coefficient
[cm2 /min] or [m2 /s]
transition diffusion coefficient
[m2 /s]
base of the natural log
[-]
ED
activation energy of diffusion
[kJ/mol]
driving force parameters
[-]
Plancks constant
[-]
ampere values
[A]
setpoint of MFC
[-]
permeation rate
[molmin1 cm2 ]
Jn
permeation rate in mole
[mol]
phenomenological coefficient
[-]
kB
Boltzmann constant
[-]
permeability coefficient
[mols1 m1 Pa1 ]
LKn
permeability coefficient of Knudsen diffusion
[mols1 m1 Pa1 ]
permeability coefficient of viscous flow
[kmolm2 s1 Pa1 ]
Mi
molecular weight of component i
[kg/mol]
amount of gas present
[mol]
NKn
Knudsen number
[-]
absolute pressure
[Pa]
PI
value of pressure meter
[bar]
pm
average pressure in the membrane
[Pa]
universal gas constant
8.314472 [Jmol1 K1 ]
rp
pore radius
[m]
Separation factor
[-]
SD
activation entropy of diffusion
[kJmol1 K1 ]
SH2 ,CO2
Separation factor of H2 to CO2
[-]
time
[min]
thermodynamic temperature
[K]
Nomenclature
XVII
volume
[m3 ]
volume flow rate
[m3 /min]
average volume flow rate
[ml/min]
vn
volume flow rate under standard condition
[mln/min]
mole fraction of certain component
[100 %]
compressibility factor
[-]
(average) value of peak area
[25 Vs]
Greek Letters
selectivity
[-]
ideal selectivity
[-]
permeability
[-]
coordinate dimension
[mm]
thickness of the membrane
[mm]
fluid viscosity
[kgm1 s1 ]
mean free path of molecular
[nm]
density of the membrane
[kg/m3 ]
pore tortuosity
[-]
pore tortuosity of the surface
[-]
porosity of the membrane
[-]
Superscripts
2M
two-component gas
5M
five-component gas
feed gas
permeate gas
retentate gas
Subscripts
i
one component
setpoint value
m mass
o
objective component
Chapter
Introduction
Gas separation is any operation that separates a mixture into two or more gases which
differ in composition. This result can be achieved by either removing a single component
from a mixture, as in purification or concentration, or by separating a mixture into
almost pure gases, as in fractionation [6].
Gas separation is a key issue in various industrial fields. For example, hydrogen has
the potential for application in clean fuel technologies and in the fertilizer and refinery
industry [7], hydrogen separation and purification is an important research subject.
Separating CO2 in chemical processes would allow to capture it rather than releasing
it in the atmosphere, where it would contribute to global warming.
A number of membrane materials have already been used for various gaseous separation and membrane process applications. Compared with traditional processes on gas
separation, using membranes enables higher energy efficiency, reduces cost, makes installation, operation and scalability easier [2]. It is already reported that gas mixtures
can be effectively separated by membranes [813]. Recently, research on membranebased gas separation has especially focused on high temperature and low humidity
conditions, low-cost membranes, data collection for membrane transport characterization. Interpretation of the results is still controversial. A large breakthrough in
applications has not yet been realized due to limited reproducibility of prototypes, lack
of fundamental transport data, and cost perspectives. says Mottern [14], implying the
current state of membrane technology.
Membrane materials are classified as organic and inorganic. Nowadays, there is already a wide variety of commercial inorganic membranes. Compared with organic
membranes, inorganic membranes can work at higher pressures up to 10 MPa and can
be cleaned with steam, which is impossible with organic membranes [15]. Inorganic
Chapter 1 Introduction
membranes can be categorized on the base of their pore size, which is usually critical pore diameter. There are porous membrane and non-porous membrane, which
is also referred to dense membrane and is commercially available. Porous membranes
are especially promising for gas separation, as they have the advantage of large gas
permeation which is the penetration of a permeate through a membrane.
Generally four types of transport mechanisms are used to explain gas traveling in
porous membranes: Knudsen diffusion, surface diffusion, capillary condensation flow
and molecular diffusion [2, 1520]. According to T. C. Merkel [21], it has been observed that, when the pressure on the permeation side is low, the diffusion coefficients for both rubbery and glassy polymers manifest in the following sequence:
H2 > O2 > N2 > CO2 > CH4 . That is, the larger the molecule size, the lower the
diffusion coefficient [22]. The size of permeation molecules seems especially important
in determining diffusion coefficients [21]. In the present work, the authors employed
two-gas mixtures which contained H2 and CO2 . In principle, if cementitious materials
themselves have no driving selectivity between H2 and CO2 , for example, if there is
no reaction or solution, the difference between the two gases is just different molecular
sizes, so membrane separation can be presumed size-sieving. The molecular diameter
of H2 and CO2 are 0.74 and 3.87 respectively, H2 molecule is much smaller. Furthermore, the kinetic diameter of H2 is 0.29 nm, smaller than the 0.33 nm of CO2 [23, 24].
Thus, H2 was set as the preferential permeation component for the cement membranes.
If the pore size of the membrane is small enough and driving forces for components are
the same, H2 should be better separated from CO2 .
As introduced above, membranes used for gas separation are better to be cheap porous
inorganic membrane, and membranes should guarantee a maximum discharge of hydrogen. That is because high permeation flux, is another important advantage of porous
membranes, they can then be used as substrates for dense or selective materials during
gas separation. So far, porous ceramic membranes are widely utilized, thanks to their
chemical, physical, and thermodynamic stability. However, cement represents a valid
attraction. It has low thermal expansion coefficients (0.9 to 1.2105 K1 ), relatively
high compressive strengths (thousands pounds per square inch), and can be processed
in various way to meet, for example the desired density or strength. Cement also offers
good thermal resistance properties. Moreover, cement is cheap, has a longer service
life and is recyclable. At present, no report on gas separation using porous cement
membrane exists. The porous cement membranes used in this study were designed
and produced in cooperation with Institut fr Bauingenieurwesen (Institute of Civil
Engineering). Different kinds of membranes with different base materials, additions,
pore-sizes, equivalent water to cement ratios, shapes, areas and thickness were manufactured by Gregor Gluth, a researcher working in the department of Baustoffe und
Baustoffprfung (Building Materials and Construction Materials Testing), Technische
Universitt Berlin.
Typically, membranes are used in gas separation without sweeping gas [25]. In this
study, N2 was used as the sweep gas to carry the permeations away. Next, CO was
used for comparison. To the purpose of reproducibility, experimental setup and procedures will be described in detail in Chapter 2 and 3. A better understanding on the
inherent structures of membranes and their effects on membrane properties is crucial
in improving the predictability of material performance [26]. Main objectives of this
study are: (1) to select a simple but reliable model which is single membrane cell for
detailed study; (2) to determine the influence of ambient parameters, such as pressure, temperature, sweeping gas, and flow rate on the separation process; (3) to study
structure-property (e.g., membrane thickness, equivalent water to cement ratio, pore
size, and additions) influence on permeation transport; (4) to develop a mathematical
model of permeation transport, which incorporates independent constitutive relations
to interpret the mass transfer data; (5) to identify the best conditions and for optimizing gas separation; (6) to collect data for transport characterization and gas separation
through membranes.
This study is organised as follows.
1. The general aspects of membrane technology are discussed in Chapter 2. First,
importance and application of membranes in the field of gas separation are introduced. Then, material and transport mechanisms of dense and porous inorganic
membranes are described, followed by the discussion on the cementitious material,
technology review, and process design.
2. In Chapter 3, the experiments are described. This chapter also details the apparatus, methods for reducing error, operating parameters, and the experimental
procedure.
3. Chapter 4 presents common assumptions and general equations for transport
mechanism, and basic processing methods for the experimental operations. In the
last part of this chapter, parameters in order to assess the ability of separation
are illustrated.
4. Data correction of controlling equipment, calibration of measuring instruments
are firstly introduced in Chapter 5. Then based on the melioration order of the
Chapter 1 Introduction
membrane cells and membrane shapes, Chapter 5 lists the different membrane
stages, membrane cells, gaskets, and corresponding data.
5. Lastly, Chapter 6 presents the results in contrast to the best selection method
for the membrane and its parameters. This chapter also lists the achieved efficiency and problems encountered (e.g., diffusion in the bubble flow meter) during
the study, as well as suggestions for further research, solutions to improve the
technique, and areas for new applications are discussed.
Chapter
State of the Art
2.1 An introduction to gas separation using membranes

Thomas Graham did the first study on gas permeation through polymer in 1829 [2729].
The first membrane for hydrogen recovering was patented in 1980, and the technology of
hydrogen separation and purification by membranes is in constant development [30,31].
Nowadays, membrane processes are effective with unlimited selectivity which is one
parameter to determine efficiency of separation, and play an important role in the
so called green chemistry. As Koltuniewicz and Drioli pointed out, Based on the
recent definition of clean technologies, almost all attributes may be fulfilled by using
membrane processes [5].
Membrane processes have encountered many applications in the field of gas separation.
The processes of applications are usually denominated from the target they can achieve,
such as separation, recovery, enrichment, removal of undesired components, desiccation,
purification, recycling and reuse of specific substances. Most of the applications where
membranes are employed to separate gases are listed in table 2.1 [2, 12, 30, 32]:
The membrane is the central part of the membrane separation, and a schematic representation is given in Figure 2.1. A mixture gas is used as feed gas, and flows along
one side of the membrane surface. During this process, some components permeate
through the membrane, and are carried out of the membrane cell by one sweeping gas.
The residual gas on the feed side is called retentate. The other side of the membrane
is permeate side, and the outgoing gas on this side is permeate gas.
To the purpose of gas separation, the permeability coefficient and separation factor
of membranes are especially relevant. The permeability coefficient measures the gas
permeation volume, while separation factor expresses the membrane performance as
Chapter 2 State of the Art
Table 2.1: Applications of gas separation using membranes
Process
Object
Source
Separation
H2
H2 /N2 [33]
Separation
H2
H2 /CH4 [34]
Recovery
H2
Product streams of ammonia plants [35, 36]
Recovery
H2
In oil refinery processes [37, 38]
Separation
H2
Biogas [39, 40]
Enrichment
O2
Air for medical or metallurgical purposes [41, 42]
Removal
Water vapor
Natural gas [4345]
Removal
CO2
Natural gas [31, 44, 45]
Separation
CO2
Landfill gas (CH4 50 %, CO2 40 %) [30]
Removal
H2 S
Natural gas [44, 45]
Recovery
He
Natural gas [46]
Removal
VOL
Air of exhaust streams [47]
Figure 2.1: Schematic representation of membrane separation
ratio of percentages that components can be permeated [48]. Materials are not yet
available for the separation of all existing gaseous mixtures [49].
2.2 Inorganic membranes

Membrane materials are classified as organic and inorganic. Since 1980s scientists envisioned the possibility of gas separation or purification using ceramic membranes, and
a lot of studies have been done. Nowadays, there is already a wide variety of commercial inorganic membranes. Compared with organic membranes, inorganic membranes
can work at higher pressures (up to 10 MPa) and can be cleaned with steam, which
is impossible with organic membranes [15]. The most common inorganic membrane
2.2 Inorganic membranes
materials are silica [5052], carbon-silica [53], zeolites [5456], glass [57], metal [58, 59],
alumina [8, 5961], and ceramic [62, 63] recently.
As introduced above, inorganic membranes can be categorized on the base of their
critical pore diameters. There are porous membrane, micro-porous membrane and
non-porous membrane, which is also referred as dense membrane and is commercially
available. There are slight differences in the definition and recognition of micro-porous
membrane, e.g. 0.52 nm by M.L. Mottern [14, 15].
Table 2.2: Classification of inorganic materials on pore size [4]
Membrane
Pore diameter
Porous membrane
0.005 - 1 m
Micro-porous membrane
0.001 - 0.005 m
Dense membrane
< 0.001 m
Membranes can also be classified as symmetric or asymmetric. Symmetric membranes,

also called isotropic, have uniform structure and character. In asymmetric membranes, also called anisotropic, chemical and physical features vary along the axial
direction.
Both porous and non-porous inorganic membranes are applicable for gas separations
[48, 64]. However, their transport mechanisms are different [16]. Before discussing
membranes for gas separation, the transport mechanisms through a membrane are
introduced.
2.2.1 Dense inorganic membranes

Dense inorganic membranes are usually made of metals and their alloys, and are especially suitable for separating hydrogen at high temperatures. Gas separation through
dense inorganic membranes is based on different solubility and diffusivity of different
gases through the membrane [31]. Solubility is the ability of a gas to dissolve in a
membrane. Diffusivity is the property of gas molecules to diffuse through a membrane.
In turn, diffusivity is determined by the molecule size.
The transport mechanism is usually described via a solution-diffusion model, in which
components adsorbed by the membrane surface at the feed side, are then diffused
through the membrane and desorption on the permeate side [18, 2729].
Balachandran et al. studied dense ceramic metal composite membranes. These are
thermodynamically and mechanically stable with reasonable flux for hydrogen permeation [64, 65]. Peinemann achieved hydrogen separation from nitrogen with dense
ceramic hydrogen membranes using hydrogen partial pressure gradient as the driving
force [66]. Palladium and its alloys are usually the first choice for dense metal membranes to separate hydrogen [62]. Palladium membrane allows transport of hydrogen
solely, but are very expensive and have low durability.
2.2.2 Porous inorganic membranes

Porous inorganic membranes, such as porous polymeric or ceramic membranes, are
used for ultrafiltration and gas separation. Ultrafiltration is one of the pressure driven
membrane processes, and the pore sizes of the membranes are from 1 to 50 nm [3]. In
these membranes, the pore diameter is smaller than the mean free path of the productgas molecules. Usually the greater the difference between properties of molecules, such
as molecular weights, sizes or shapes, the more effective the separation.
Although dense inorganic membranes can achieve high separation factors, gas fluxes
through porous membranes are much higher. Therefore, many researchers [6771] used
a porous structure material as substrate, and covered it with a thin dense inorganic
membrane layer to increase the separation factor.
Porous membranes are made of microporous media, such as graphite, sintering metal
[72], metal oxide [72], ceramic, polymer and hollow-fiber [73], and might be symmetrical
or asymmetric, charged or uncharged [64]. Cement membranes are also porous.
Gas separation generally results from four types of transport mechanisms: Knudsen
diffusion, surface diffusion, capillary condensation flow and molecular diffusion. As
shown in Figure 2.2a, Knudsen diffusion suits to larger molecular weight ratios. Its
separation is in inverse proportion to molecular weight. surface diffusion in Figure
2.2b is more useful for vapor separation, and usually happens when membrane pore
diameter (dp ) < 10 nm. The surface concentration gradient forces the transport. When
the membrane pores are extremely fine usually dp < 10 nm, and one component in gas
mixture is condensible while others not, it is capillary condensation flow or partial
diffusion as shown in Figure 2.2c. In molecular diffusion or molecular sieving in Figure
2.2d, the pressure difference forces the transport of different-sized molecules, and the
gas molecule larger than the pore diameter is screened [2, 1520].
2.3 Porous cement membranes
Figure 2.2: Transport mechanisms in porous membranes [1]
2.3 Porous cement membranes

The potential applications of a porous inorganic membrane depend on the physical
properties of the membrane, include thermodynamical and mechanical stability which
determine the conditions and duration the membrane can be employed, membrane
thickness which influences the permeation rate and separation factor, pore size and
pore size distribution which relate to the transport mechanisms [1, 64].
Cement is chemically and physically stable. Firstly, it has a very low coefficient of thermal expansion (105 K1 ), so when temperature rises, no distortion happens. Secondly,
cement has relatively high compressive strength (107 Pa). As a result, a cement membrane installed into a membrane cell will not be easily destroyed by rational gaskets
setting for gas-tightness. Thirdly, cementitious material with a tiny porosity can be
obtained. Fourthly, the finished product can cover a wide range of physical properties
and strengths, or chemical, volumetric and thermal resistance properties.
Due to its high compressive strength, cement has been widely applied in the field of
construction. Cementitious material is mainly cement, but also of water, aggregate,
and chemical admixtures. There are many sorts of cements, such as Portland cement,
Natural cement, Pozzolanic and slag cements, Masonry cement and Generic cement
[74]. Different denominations correspond different additivesalso referred as cement
ingredients, such as fly ash and slag cement. Cement can also have different equivalent
water to cement ratios. By varying the proportions of materials and the production
processes, we can get different types of porous cement membranes.
Cementitious material is much cheaper than many other membrane materials, has low
moisture permeability and high durability, and can be recycled. No report on gas
10
separation with porous cement membranes exists to date, which arose the necessity of
the present work.
2.4 Separation and process design

Process design focuses on either recovery or purity of the product, depending on
whether the product of a separation program is the permeate-gas or retentate.
2.4.1 Possible flow patterns

A module is defined as the smallest unit plugged with a membrane. Therefore, in
the single-stage process, membrane cell with the membrane in the center is a module.
Many different flow pattern operations through a module are possible, as shown in
Figure 2.3. The existing flow patterns includes the skew flow, the parallel flow and
cross flow (Figure 2.3D [31, 75]). And the parallel flow could be co-current (Figure
2.3A), counter-current (Figure 2.3B [13]) or both (Figure 2.3C). In dead-end type
(Figure 2.3E), there is no way for retentate outgoing. Gas-mixture enters the module
Figure 2.3: Schematics of possible flow patterns [2, 3]
as feed gas, some of the components permeate through the membrane and exit via the
permeate-pipe, and others will stay in the feed side. As has been pointed out in a
11
host of studies, the type of flow patterns impacts the degree of separation significantly.
Counter-current flow pattern usually performs separation much better. It is the most
efficient type among these flow patterns [2, 76, 77].
Contrary to common practice, sweeping gas was also fetched in the module. Sweeping
gas carries the permeation components away instantly and continuously, which reduces
the permeate partial pressure and enhances the driving force. Furthermore, by adjusting the permeate-side pressure, sweeping gas could also be used to influence two
other factors on permeation, those are permeate pressure and the flow rate of carrying
gas. Knudsen diffusion was expected to be achieved without pressure difference. In
order to obtain better performance, the counter-current flow pattern was adopted in
our experiments, as shown in Figure 2.4. Experiments without sweeping gas were also
performed to confirm the impact of carrying gas on gas separation.
Figure 2.4: Flow pattern in presence of sweep gas [2]
In order to analyze the effects of gas types, N2 and CO have been used as carrying
gases. Since the sweeping gas itself has some permeability through some materials, it
will generally appear in the retentate [2].
2.4.2 Number of stages

In order to enhance operational efficiency, meet process criteria and reduce operating
cost, most commercial applications of gas separation through membranes are designed
as multistage and recycling processes (see Figure 2.5two-stage separation schemes,
and Figure 2.6three-stage separation schemes). Different membrane process designs
exist. If target separation purity is too high, decreasing flow recycling might help
achieve the target. Increase in membrane surface does not always obtain the corresponding progress in separation. However the high economic cost makes huge membrane surface not suitable for commercial applications. In a word, the membrane unit
is necessary to be multistage. Due to economic constraints, the recycling and cascade
12
Figure 2.5: Schemes of commercial two-stage separation [2, 3]
13
Figure 2.6: Schemes of commercial three-stage separation [2, 3]
are essential, and in some design they are used for the final product purification after
membrane separation.
There are also recycling processes for single-stage, as illustrated in Figure 2.7. Since
sometimes increasing membrane area will not improve separation, a single-stage membrane separation is often insufficient to match the separation target in the industry.
Furthermore, the higher product purity results in lower product recovery, which is not
economical. However, single-stage is the basic building block of gas permeation pro-
Figure 2.7: Novel single-stage separation with recycling [2, 3]
14
cesses. A detailed knowledge is required for the development of such processes. Hence,
in order to study the influence from operating conditions and the inherent properties of
membranes on the operation of the permeation stage directly and simply, single-stage
module without recycling is used in this project. If it is proved to be successful, the
multistage-research might be a further topic in this area.
2.4.3 Known influence of operating parameters

Relevant parameters include: temperature, pressure difference between two sides of
a membrane, pressure, feed-flow rate, feed composition, sweep-flow rate, sweep-gas
composition, membrane area, equivalent water to cement ratio, membrane thickness,
pore size, pore distribution, membrane shape, permeabilities and selectivity. So far,
the following relationships have been characterized:
1. T. C. Merkel [21], using size-sieving rubbery polymers without pressure difference
between two sides of the membranes, found out that more soluble penetrants are more
permeable, and that the permeability coefficients increase with increasing pressure.
Penetrants are the permeated components. However, H2 , N2 and O2 are essentially
independent of pressure [22]. Furthermore, at low permeate-pressure, for both rubbery and glassy polymers, permeation components with large molecular size give low
diffusion coefficients.
2. Each model has a maximum operational temperature limit. In the affordable temperature range, the higher the temperature, the better membrane permeability, but
the smaller separation factor and selectivity [2].
3. Permeate to feed-flow pressure ratio, and their difference are both important for
membrane separation [2, 32].
4. Increasing feed-pressure and decreasing permeate-pressure both increase permeation
rate and purity of the retentate. However, the higher the feed pressure, the higher the
costs [2, 32].
5. Larger membrane areas result in higher retentate purities and lower purities of
permeate gas [2, 32].
6. Generally speaking, high product recovery is associated with low product purity
[2, 32].
7. The larger the membrane surface the higher the membrane selectivity, though this
might increase the overall membrane process costs [2].
15
8. Given the membrane, the permeate-flow rate will not be significantly affected by
the feed-flow rate. However, the purity of the retentate will be reversely affected [2].
9. The counter-current flow pattern usually performs separation much better than other
patterns in the parallel flow models. For an asymmetric membrane, the separation will
be better performed by the cross flow rather than the counter-current flow [2].
10. Increasing difference between molecules in molecular weights, sizes or shapes will
raise separation efficiency [2].
11. In the permeation of non-condensible gases in membranes, diffusion coefficients are
independent of permeation concentrations [26].
12. Permeation rate is inversely proportional to membranes thickness [1].
13. Some Knudsen separation factors obtained by Klaas Keizer [15] at room temperature are listed in Table 2.3:
Table 2.3: Separation factor of some typical gas mixtures
Gas mixture
Knudsen separation factor
O2 /N2
0.94
H2 /CH4
2.83
H2 /N2
3.74
CO2 /CH4
0.60
And Renate M. de Vos et. al. obtained the selectivities of H2 /CO2 3.9 at 100 C and
6.8 at 200 C, when the average pressure was 1.5 bar, and pressure difference between
feed-flow and permeate-flow was 1 bar [51]; Koros and Mahajan have experimented with
similar membranes for gas separation and got a separation factor of 6.75 for H2 /CO2
at low temperature [78].
Chapter
Experimental Setup
3.1 Flow chart
Figure 3.1: Process schematic of gas separation
The flow chart of H2 permeation measurement through a cement membrane included

a heating system is shown in Figure 3.1. Separation experiments were performed with
H2 or mixture gas containing H2 as feed gas, and with N2 or CO as sweeping gas. The
sweeping gas also ensured pressure balance between two sides of the membrane. The
18
Chapter 3 Experimental Setup
gases were stored in high pressure cylinders and reducers were used for pressure control
(2.4 bar).
Before gases entered the membrane cell, their flow rate was set at the wanted level
by mass flow controllers (MFC ). Pressure difference between the two membrane exits
was measured as well as the absolute pressure of permeate-gas. Finely regulated valve
could change the pressure difference between the two sides of the membrane. In the
measurements, the membrane cell was heated in a gas chromatography (GC ) oven and
temperatures were measured with type-K thermocouples.
The permeate-gas was detected and analyzed by a GC. The flow rates were measured
by two soap film flow meters located after the GC. The amount of H2 in the effluents of
sweep-side was calculated from the character spectrum peak of the product and pure
H2 as reference gas. The residual gases went directly through the flow meter to the
outside at atmospheric pressure.
Figure 3.2: Process schematic of reference measurements
Qualitative and quantitive analysis of gas separation through porous membranes were
both needed. Therefore, so were the spectrum peaks of the reference gases in order
to calculate their percentage. The process of reference gas measurements is shown in
Figure 3.2. Pure gases of feed-components were usually injected into the front column
3.2 Experimental setup
19
of GC, while sweeping gas was analyzed by the back detector. In addition to hydrogen
and nitrogen, the amount of other gases could be measured by the detectors using He
or N2 as reference gases.

Membranes
Three different membrane main-cells were employed in this project, whose settings
progressively allowed to solve problems of heat-stability, air leak, gas turbulence. In
the experiments, membranes with different mineral composition and additives were
employed. Membranes are classified depending on shape, thickness, base materials,
additives, equivalent water to cement ratio, pore size.
The disc-shaped porous cement membranes from Maria Gaggls Diploma project were
tested in the first part of ours study. These membranes had a 50 mm diameter, 10
mm thickness, and 0.6 equivalent water to cement ratio. Using the method of mercury
intrusion porosimetry (MIP) which is a widely used technique to characterize the distribution of pore sizes in cement-based materials [79], the average pore diameter is 110
nm.
At a second stage, fifty disc-shaped and one tubular cement membranes made by Gregor
Gluth, from the Institut fr Bauingenieurwesen of Technische Universitt Berlin were
used. The disc-shaped membranes had thickness of 5, 10 and 20 mm. There were seven
different kinds of base materials, and two additives. Equivalent water to cement ratio
was 0.25, 0.30, 0.35 or 0.45. Most of the pore diameters in these materials were from
8 to 100 nm. Details will be introduced.
The scientific literature reports about hydrogen purification achieved using large pored
substrate materials coated with a selective surface layer. Accordingly, 7 nm-surfacelayer sample membranes were used in the 3rd part of this study. The membranes
produced by KERAFOL-Keramische Folien GmbH as alpha stage products were made
of ceramic. The substrate had pore diameter of 2 m and thickness of 6.0 mm.
Sealings
For the primary membrane cell, the seal rings between membrane and metal shell were
made of Teflon. However, as Teflon is only suitable for temperatures lower than 250
20
C, graphite gaskets were used to perform experiments of gas separation at higher
temperature.
Gases
In the experiments, at least eight kinds of gases were used. N2 and He were reference
and sweeping gases for the gas chromatography. In the measurements, feed gas could
be H2 , CO, CO2 , CH4 , two-component gas (49.8 % volume percentage H2 and 50.2
% CO2 ), and five-component mixture gas (the volume percentage reported on the
cylinder were 13 % H2 , 16 % CO, 13 % CO2 , 53 % N2 , and 5 % CH4 ). Sweeping gas
were mostly N2 and sometimes CO. All gas cylinders were bought from the company
ALPHAGAZ TM 1Ar .
Oven
Three heaters were employed in this project.
The first one was a drying machine manufactured by Heraeus in Hanau, type T6060.
It was employed to dry the membranes and remove the excess moisture. The dried
membranes were then put into the desiccator.
In Figure 3.1, the oven for membrane cell heating was a HEWLETT PACKARD (hp)
GC, type 5890A, series II, with maximum and minimum temperature of 400 C and
-80 C, respectively.
The GC -oven was not large enough for the cell of the tubular membrane. Therefore,
a Temperature Controller -HT MC1 made by HORST GmbH in Lorsch was employed,
with maximum temperature 800 C and minimum temperature 0 C. Serial interface
was RS-232 ; Series-number was RD1051000000. There was a special heating asbestine
mat designed for tubular-membrane cell. The probes used in the heater to measure
temperature were made of N iCr N i, type K. The heating mat covered the membrane
cell so closely that, the heat loss can be compensated when it is used for heating.
Pipe system
Chromatographic Service GmbH (CS, Artifical number 198004 ) copper pipes were used.
Outside diameter was signed as 1/8 3.2 mm and inside diameter was 2.0 mm. The
maximum pressure it could withstand was 45 bar.
21
In order to avoid the effect caused by pipe loss, the corresponding pipelines of the
primary and secondary side had same length. The enter pipelines were much longer,
almost 2.3 m, to make sure that the gases were heated enough before reaching the
membrane.
The pipes connected with the reducer valves and MFC s were made of Teflon and had
6 mm length.
Mass flow controllers

Both mass flow meters/controllers (MFC ) were Bronkhorstr Select. One was for 750
mln /min (100 % range) N2 , series number: m7211047B; F.201CV-1K0-ABD-33-V ;
the other mass flow controller was for 750 mln /min CO2 (series number: m7211047A;
F.201CV-1K0-ABD-33-Z ). Both working pressure should be between 1 and 4 bar,
which was measured at the normal condition (20 C), with 8 bar He by the company
Bronkhorst Mttig GmbH.
This company also designed a special program for the project, which incorporated the
densities of gases. As a result, the N2 type can be used directly for N2 , He, air, Ar,
and the CO2 one can be used directly for all the feed gas mentioned above.
Gas chromatograph
Our gas chromatograph (GC ) measures parts-per-billion concentrations in gaseous
samples. One of the equipment used was made by Agilent Technologies (type 6890N
and Serial number: US10149120 ).
This GC (Figure 3.3 [26]), plugged with the G2613A injector and G2614A tray, identified gas composite with thermal conductivity detectors (TCD), and had the 7683
automatic liquid sampler. Analysis time was approximately 15 minutes. Two samplesource switching systems (ten-port switching valve) are used in the GC analysis. Upon
switching, the contents of the sample loop (0.6 ml Scott Gas Mix ) are inserted automatically into the inlets. Better reproducibility and time-optimization were realized
by using automatic injection. Column A and column B shown in Figure 3.3 are both
metal tube packed columns (12392U,150 1/800 stainless steel), inside which are the
stationary phase of 60/80 Carboxen-1000. At the end of both columns are the TCD
detectors. The inside covered phase has the ability to adsorb and desorb some gases
in various time periods. Therefore, different components in a sample are separated by
22
Figure 3.3: Gas chromatographic system
the stationary phase inside the columns, expelled from the columns at different times
which is defined as retention time, and detected by the detectors. The chromatograms
with peaks at different time were thus achieved. Each gas has a different, characteristic
peak spectrum. Both flow rate of carrier gas and the temperature can slightly alter the
retention time.
The choice of reference gases is significant. The TCD is a concentration sensitive
detector in that it responds to all solutes and determines by the thermal conductivity of
gases [80]. An inert gas helium and an unreactive gas nitrogen are used as the reference
gases in this project. He is non-flammable and has relatively high thermal conductivity,
that can obtain a large measurable range of gas types. However, employing helium as
the carrier gas in a gas Chromatograph for quantitative determination of hydrogen was
difficult, because the thermal conductivity of hydrogen-helium mixtures with hydrogen
at low concentrations is anomalous [81, 82]. The representative peak of H2 with He as
reference will be very small. In order to avoid large calculation errors, N2 was used as
a carrier gas with a respective channel for H2 . The reference gas flow rate was set at
20 ml/min.
Both permeate-gas and retentate were measured synchronously. The concentrations of
gas components easily change with time, and are sensitive to temperature and pressure.
That is also the reason for using two columns as this allows to have both He and N2
as reference gases for the measurements.
We chose the parameters at fixed values reported in Table 3.1.
A chromatogram represents each component by a diagram of peaks, and corresponding
different retention times. The gas amount can be calculated from the area under its
representative peak through a calibration curve. For instance, the chromatogram of
23
Table 3.1: Operating conditions of Gas Chromatograph
inlet pressure/[kPa]
Columns
outlet pressure
200.0
Ambient
max temperature/[ C]
230
pressure/[kPa]
Reference flow
front (back) gas
200.0
N2 (He)
flow rate/[ml/min]
20
heater/[ C]
Detectors
230
front det.
N2 -Negative Polarity
back det.
He
set point/[ C]
60 (1 min)
maximum/[ C]
225
heating rate/[ C/min]
Oven
target value/[ C]
Runtime
20.00
205 (2.25 min)
whole run time/[min]
10.5
valve1 (front) on/[min]
0.00
valve2 (back) on/[min]
0.01
valve1 (front) off/[min]
0.10
valve2 (back) off/[min]
0.11
Thermal Aux #1
heater/[ C]
80
Signals
data rate/[Hz]
20
minimum peak width/[min]
0.01
the five-component gas is shown in Figure 3.4. Here the x-coordinate is retention
time, where retention time zero means injection time. Thus, gas-1# represents H2
Figure 3.4: Chromatogram of five-component gas
24
with a retention time of 1.316 min, gas-2# is N2 of 3.544 min, gas-3# is CO of 4.437
min, gas-4# is CH4 of 7.318 min, and gas-5# is CO2 with a character peak at 9.495
min. The area of each peak under the curve is the peak area mentioned above. The
chromatograms have good reproducibility.
Thermocouples
Thermocouples were employed to measure the temperature near the surface of the
membrane. One thermocouple was used with the disc-shape membranes. With tubular
membrane, four thermocouples were placed at different positions around the membrane,
to check whether the membrane was heated uniformly. All thermocouples were made
by Electronic Sensor, type K, with diameter of 1.0 mm and length of 1000 mm. Their
measurable range of temperature went from -200 to 1000 C, with tolerances of 0.4
%. The experiments with disc-membranes were run at 350 C, those with the tubular
membrane at 800 C.
Pressure meter
A pressure meter was installed to obtain the absolute pressure of the permeate agent,
at the exit of the sweeping side. The KELLER pressure meter had a precision of 0.05
%F S (0.003 % as linearity error at 25 C). This typePAA-33X/3bar/80794 (Serial
number: 106276 ) a measurement-range of 0 to 3 bar, and can work at temperature
between -10 C and 80 C. Connected with the Binder 723 and multibus NI 9203,
PAA-33X sends the signal to computer. The output signal is converted from the
ampere value (4 20 mA ) to pressure value (0 3 bar ) via a LabVIEW program.
Pressure difference meter

A pressure difference meter is connected directly with both exits of the membrane cell
via two triple-connections. The finely regulated valves, on outgoing pipes of the cell,
adjust the pressure of gases at both sides by screwing. Thus, the pressure difference
between two sides of the membrane could be measured by the pressure difference meter.
This meter was also made by KELLER, type of PD-33X/-0.1. . . 0.1bar/80920 (Serial
number: 102764 ). It worked at the temperature range of -10 C to 80 C and measured
the pressure difference between -0.1 and 0.1 bar with a linearity error of 0.002 %FS.
25
Same as the pressure meter, PD-33X shows us the digital value of pressure difference
with the help of Binder 723, multibus NI 9203 and LabVIEW.
National Instruments Lab View

National Instruments Lab View was the graphical program in the project. It controlled
the running of GC and MFC s and measured most of the operation-parameters synchronously. For instance, the parameters included the absolute pressure of permeategas, pressure difference between the two sides of the membrane (NI 9203 8-channel
20 mA, 16-Bit analog input module), the chromatogram from GC (from which the
amount of certain component in the permeate-gas was possible to be calculated ), the
flow rate (RS232, value of MFC ), and the temperatures at different positions of the
cell or ambient (NI 9211 4-channel thermocouple input module, see Figure 3.5). With
the module box-NI cDAQ-9172, LabVIEW becomes an instrument for various devices
administration and numerous data acquisition. It realizes multi-processing in one program. This multi to one is of easy controlment, fast collection and accurate analysis.
Figure 3.5: LabVIEW controlling system
26
Soap film flowmeters

Soap film flowmeter is a glass tube marked with volume lines. It is suitable for checking
flow rates. Since the flow rate had changed after diffusion and permeation through the
membrane from both sides, two HEWLETT-PACKARD 1-10-100ml 0101-0113 -soap
film flowmeters were used after each GC detector, before the gas going out to ventpipe. In theory, every time GC injects the same amount (0.6 ml) of test gases, and the
loop temperature and pressures are invariable, so the changing of the flow rate should
not affect the GC measurements. In order to make sure the impact of flow rates on
GC measurements as well as verify the accuracy of MFC, it is necessary to measure
the volumetric flow rate again.
Since the soap film flowmeter has four volume marks of 0, 1 ml, 10 ml, 100 ml, six
measuring volumes are available. Those are 1 ml, 10 ml, 100ml, 10 1 = 9 ml,
100 1 = 99 ml, 100 10 = 90 ml depending one bubble speed. After interposed into
the flow path by the pump, a flat soap film moves from one volume mark to another. A
stop watch is used to record the travel time. Then the flow rate can easily be calculated
as ratio of volume to the travel time.
Pipe cooling system

The suitable working environment for pressure meters should be no higher than 80 C;
the temperature of sample-gases injected into GC had to be lower than 60 C and GC
analyses the samples by increasing the gas temperature from 60 to 230 C. In that
way, the gases had to be cooled down enough before reaching the devices.
The gas-pipes were very thin and the flow rates for measurements were lower than 100
ml/min. Therefore, pipes of half meter were chosen. Wet paper ensured safe operation
of instruments and the precision of the results (keeping the samples almost at the same
temperature lower than 60 C). In the pipe cooling system, paper were dewed, then
wrapped over the pipe, and later re-wetted every twenty minutes with distilled water.
3.3 Operating parameters and procedure

Errors control
In this work, each permeate-sample was obtained as average of three stable measurements. The first GC measurements, either as the membrane vessel or pipeline still
27
had residue gases from last measurements, or because of incomplete warm up. Measurements usually became stable after one hour of GC operation. In order to avoid
experimental errors arising from atmosphere, the gas-samples of comparison were done
in a continuous way and at the same conditions.
When using the soap film flowmeters, a flat soap film was made to measure the flow
rate of gases. Actually one film is not enough, we made more bubbles and chose the
sixth or seventh film for calculation. Furthermore, taking the accuracy into account,
measure range should be between 10 to 200 ml/min.
Operational steps
1 . Open N2 and He gas for GC.
2 . Switch on computer and the power of the National Instruments (NI cDAQ-9172);
Write down the time.
3 . Connect the GC machine (6890N (G1530N)) to the computer and open it. When
the GC was ready, run the Instrument 1 Online program on the desktop.
4 . Activate the two FlowDDEs (MFC, V4.58 (MBC)); and change the gas types in
the program of FlowView (V1.15).
5 . When the temperature of the GC reached 80 C at both detectors, change the
Method to FNBHE.M , and record the time. After the temperature rising upto 230
C, run the detectors and choose the Negative for the front detector. Record the
time (Denoted as the time A).

6 . Change the paper on the pipes over the oven to wet paper, then power on the oven
and change the setpoint of temperature to 350 C. Record the time (Denoted as the
time B).
7 . Open the gases for measurements in two minutes of time A (Here take H2 and N2
for example).
8 . Open test LabVIEW Instrument file, which could not only control MFC s but also
display temperatures, pressure and pressure difference. Run it and set the flow rate to
3 %. Record the time.
9 . Thirty minutes later than time A, press Start on GC, reference-gases (See Figure
3.2) were measured. During this period, the membranes were dried fully. The program
was regulated to stop automatically in 10.5 minutes. Wait until the GC interface was
28
ready, that mean GC was well prepared for the next measurement. Then make sure
the active base line are stable, then Start again. Record the values into the form.
10 . When the detectors stop injecting gases at the last reference-value measurement,
set the flow rates of gases in the test LabVIEW Instrument file to 0 first, then change
the pipe-connections to the experimental stateadd the main cell as shown in Figure
3.1.
11 . Set the flow rates of gases in the test LabV Instrument file to 30 %. Use soap
bubble to test the gas-tightness of the connections. If there was no air leak, change the
flow rates in the test LabVIEW Instrument file back to 0 again.
12 . Sixty minutes later than the time B, set the flow rates back to 3 % again, and
record the time.
13 . Ninety minutes later than the time B, begin the experiments.Press the button
Start on GC and begin measurement. The program stopped automatically in 10.5
minutes. Wait for ready and make sure the base-line is stable, then Start again
as above. Measurements of five temperature groups were done: 350 C, 350 C(II)20
minutes later, 200 C, 100 C and ambient temperature. Each group contained four
measures. Generally, the first value could not be used. When a lower temperature
was required, setpoint was better to be 20 C or even 50 C lower than the standard
to save time.
14 . Record all the data into the form.
15 . When all the measurements are finished, switch off the detectors first. Then
change the method of the Instrument 1 Online program to STBY1.M.
16 . Set the flow in the test LabVIEW Instrument file to zero.
17 . Change the connections of the pipes back to the reference way as shown in Figure
3.2.
18 . Set the flow rates in the test LabVIEW Instrument file to 30 %. Use soap
bubbles to test the gas-tightness of the connections. If the tightness was good, close
the gas bottles of H2 and N2 .
19 . Take off the paper over the pipes, and put them together.
20 . When the flow rates in the test LabVIEW Instrument file decreased to zero,
change the setpoints to zero and close the test file.
21 . Press F4 to halt running of DDEs. Power off the National Instruments.
29
22 . When the temperature of GC detectors is below 80 C, turn off the window of

Instrument 1 Online program, shut down the computer and GC machine.
23 . Close the bottles of N2 an He. Shut down the fuming cupboard.
24 . The last task is data processing.
Chapter
Summary of Equations
Cement separation ability and gas transport mechanisms are still object of research.
Corresponding equations are reported in this chapter. The equations used for data
acquisition and processing are also listed. Finally, the expressions are introduced,
which will be used to quantify the membrane performance in gas separation.
4.1 Basic assumptions

The assumptions employed in analysis and design are as follows [2]:
1. No pressure drop and end effects caused by the pipes and connections or GC, hence,
the flow rate is unaltered between the outgoing section of the membrane cell and the
outgoing section of the GC ;
2. No influence on gas viscosities from pressure;
3. Uniform distribution of gas;
4. Steady-going permeation at the same condition;
5. No physical deformation of the membranes;
6. No gas concentration gradients at cross section of the module;
7. No fouling in the pores of the membrane, so the pore sizes are invariable;
8. No pressure drop on the shell side of the membrane cell;
9. Negligible pressure drop on the transverse section of the module.
32
Chapter 4 Summary of Equations
4.2 Gas equations

4.2.1 The fundamental equations for ideal gases
The ideal-gas equation says that [49]:
pV = (z)nRT
(4.1)
where,
p is the absolute pressure of the gas (Pa);
V is the volume of the gas (m3 );
z is the compressibility factor, depending on conditions and phase of the components. For an ideal gas z is constant;
n is the amount of gas present, normally expressed in moles;
R is the universal gas constant (8.314472 Jmol1 K1 );
and T is the thermodynamic temperature (K).
Since gases were flowing all the time in our experiments, we introduced the time into
Equation (4.1). The volumetric flow rate v (m3 /min) is equal to the volume V (m3 )
divided by time t (min):
v=
V
.
t
(4.2)
By replacing V , we get:
pvt = nRT.
(4.3)
That can also be written as :

n
RT.
(4.4)
t
At room temperature, when the MFC controls the gas flow at a fixed value, the mopv =
lar amount of gas flowed per unit time remains unchanged, which means that n/t is
constant. Meanwhile, both ends of two gas channels are opened to the atmosphere,
so p can be considered equal to atmospheric pressure, which is also constant. From
Equation (4.4) v is directly proportional to temperature T . Therefore, when the impact of temperature on gas separation is studied, whether the flow rate affects GC
measurements should also be taken into account.
4.2.2 Balances
At ideal conditions, the total amount of materials stays invariant [49].
4.3 Equations for transport mechanisms through porous membranes
33
Material balances
For counter-current flow in our experiments, the overall material balance is expressed
as follows,
nF + nS = nP + nR
(4.5)
nFi = nPi + nR
i
(4.6)
nF xFi = nP xPi + nR xR
i
(4.7)
For the i component,
where x is the mole fraction of certain component, F is the feed gas, P is the permeate
gas, R is the retentate gas, and S is the sweeping gas.
From Equation 4.3, we get,
n=
P vt
PV
=
RT
RT
(4.8)
Therefore, the Equation (4.7) could be written as:

P vF t F
P vP t P P vRt R
xi =
x +
x
RT
RT i
RT i
(4.9)
v F xFi = v P xPi + v R xR
i
(4.10)
nPi = (Jn )i
(4.11)
nP xPi = (Jn )i
(4.12)
Membrane rate balance

For each component i,
where, (Jn )i (mol) means molar permeation rate of component i.
4.3 Equations for transport mechanisms through porous membranes

As described above, there are generally four gas transport mechanisms in porous
membranes: Knudsen diffusion, viscous flow, surface diffusion and molecular diffusion [5, 14, 17, 83].
34
Knudsen diffusion
When the pore size is much smaller than the mean free path of the molecule ( expressed
in Equation (4.13)) [84] and molecular weight ratios are larger, Knudsen diffusion
occurs. It can be described as Equation (4.14) [83]:
kB T
=
2pm 2
r
4rp 2RT
Di,K =
3
Mi
(4.13)
(4.14)
here, kB is the Boltzmann constant, is collision diameter, Di,K is the Knudsen diffusion coefficient (m2 /s), means the fluid viscosity (kgm1 s1 ), rp is the pore radius
(m), Mi is the molecular weight of component i, and pm is the average pressure in
the membrane (Pa). Usually researchers reckon that the transport is mainly Knudsen
diffusion (Equation (4.43)), if rp is between 530 , and /dp > 1 [5]. The expression
/dp is called the Knudsen number (NKn ). It is also reported that, Knudsen diffusion
predominates when the Knudsen number is far larger than one; when it is far smaller
than one, the transport mechanism is mainly molecular diffusion and when it nears one
the transport is transition diffusion [83]. The diffusivity of the transient region can be
expressed in the following formula [85].
1
1
1
=
+
D
Di,K Di
(4.15)
where D is transition diffusion coefficient, Di is molecular diffusion coefficient, p =

Ap /A the porosity of the membrane, Ap is the pore area, and is the pore tortuosity,
is the thickness of the membrane.
Viscous Flow
Viscous flow (also referred to laminar flow) is one of the transport mechanism in porous
membranesthe capillary condensation flow or partial diffusion as discussed in Chapter
2. According to Professor Koltuniewicz [5],
L =
rp2 p P
8 R T
(4.16)
For gas:
1
i =
N d2m
Mi R T
3
(4.17)
4.4 Equations for the experimental setup
35
Surface diffusion
Surface diffusion can occur in parallel with Knudsen diffusion. Some components can
be adsorbed onto the pore walls and move along the surface. Thus the more adsorbable
components can permeate further using surface diffusion [1].
dC
(4.18)
d
here, is the density of the membrane, S is the tortuosity of the surface, DS is the
JS = S DS (1 p )
surface diffusion coefficient, and C is the molar density (mol/ml). At high temperature,
adsorbability can be restrained, so Knudson diffusion will be more ascendant.
Molecular diffusion
Molecular diffusion (also referred as molecular sieving) dominates the transport mechanism when membrane pores are of similar size to the molecule. It is a highly restrictive
diffusion. The smaller the permeation components, the faster to diffuse.
The molecular diffusion obeys the following relation [17, 86]:
Di = e2
SD
ED
18.58T 3/2 [(Mi + Mj )/Mi Mj ]1/2
kB T
exp( ) exp(
)=
2
h
R
RT
pi,j
(4.19)
where e is the base of the natural log, h is Plancks constant, SD is the activation
entropy of diffusion (kJmol1 K1 ), ED is the activation energy of diffusion (kJ/mol),
and is the collision integral.
4.4 Equations for the experimental setup

4.4.1 LabVIEW
National Instruments Lab View controls the running of GC and MFC s and measures
synchronously most of the operation-parameters such as absolute pressure of permeategas, pressure difference between the two sides of the membrane. MFC and GC can
be controlled directly, but the pressure values must be converted first. The signal
from pressure meters are in the form of ampere values I (A). The outcome range of
the pressure meter is 4 20 mA, and the measurable pressure range is 0 3 bar.
Furthermore, the pressure difference meter should also convert the signal from 4 20
mA to 0.1 0.1 bar. Hence, the conversion Equation (4.20) is shown bellow:
PI = 187.5 I 0.75
DPI = 12.5 I 0.15
(4.20)
36
4.4.2 Soap film flowmeter

The soap film flowmeter has four volume marks of 0, 1 ml, 10 ml, 100 ml, and six
measuring volumes are available. After selecting two mark line, a stop watch is used
to record the travel time t (min). Then the flow rate can be calculated easily, using
the measuring volume divided by the travel time. Equation (4.21) shows the example
of the marks of 10 ml and 100 ml.
v=
100 10
t
(4.21)
4.4.3 Mass flow controller

MFC can be regulated by LabVIEW program. The set value is in the form of percentage. Both MFC s ranges are 750 mln /min (100 %). The setted flow rates are actually
equal to 750 mln /min multiplying by the percentages.
j
(4.22)
100
here, natural number j (0<j<100) is the setpoint value of MFC, vn (mln /min) means
vn = 750
flow rate under standard condition (T0 = 273.5 K). For example, setpoint of 3 % means
the flow rate of 22.5 mln /min and 24.56 ml/min at room temperature.
v = vn
T
j
T
= 750
T0
100 T0
(4.23)
4.4.4 Gas chromatograph

GC can detect and measure gas components by chromatograms, which are diagrams of
characteristic peaks with different retention times. The amount of components can be
calculated from the area under its representative peak and a calibration curve. From
a theoretical point of view, the content of certain component is equal to the ratio of
its peak areas of objective gas and pure standard-gas. The chromatograms of twocomponent gas and pure H2 and pure CO2 are put into one figure. Thus, the principle
is easily to be understood, as shown in Figure 4.1 and Equation (4.24). The green line
shapes into peaks of H2 (left) and CO2 (right) in two-component gas (2M ). The blue
peak is pure H2 , and red peak is pure CO2 .
ZH2 2M
ZCO2 2M
CH2 2M =
CCO2 2M =
ZP ureH2
ZP ureCO2
(4.24)
here, CH2 2M is the molar percentage (100%) of H2 in two-component gas, ZH2 2M

(25Vs) is the characteristic peak area of H2 in chromatogram of 2M . CO2 is expressed
similarly.
4.5 Efficiency of gas separation through membrane
37
Figure 4.1: Chromatograms of two-component gas and pure standard-gases

Factors affecting separation ability of a membrane include: diffusivity of species in the
membrane, group complexity, crystalline, free volume, orientation, fillers, humidity.
There are four parameters to determine the performance of a given membrane, i.e. the
efficiency of gas separation.
Separation factor
One of the parameters to indicate the ability of separation is the separation factor,
which is also referred to as the relative split ratio and the separation power. There
were two key components in the multicomponent feed gas, H2 and CO2 . Separation
factor, S, shows the relatively sharp separation between these two key components. It
is defined in Equation (4.25) [3], by the compositions of the two products in feed and
permeate-gas (or retentate and permeate gas Equation (4.26)) [87]:
SH2 ,CO2 =
P
F
CH
/CH
2
2
P
F
CCO
/C
CO2
2
(4.25)
SH2 ,CO2 =
P
R
CH
/CH
2
2
P
R
/C
CCO
CO2
2
(4.26)
or
38
here, C is the molar density (mol/ml) of the fluid mixture; CH2 and CCO2 is the partial
molar density (mol/ml) of component H2 and CO2 . For a binary system, we have
P
P
R
R
CH
+ CCO
= 1 and CH
+ CCO
= 1, then the separation factor is readily converted
2
2
2
2
into the following forms [15]:

SH2 ,CO2 =
P
R
P
R
CH
CCO
CH
/(1 CCO
)
2
2
2
2
=
P
R
P
R
(1 CH
)/C
(1
C
)(1
CCO
)
CO2
H2
2
2
(4.27)
Using the GC measurements results, it is easy to calculate mole fraction of certain

components. Thus, the Equation (4.25) could also be written as follows:
SH2 ,CO2 =
(C P xPH2 )/(C F xFH2 )

xPH2 /xFH2
=
(C P xPCO2 )/(C F xFCO2 )
xPCO2 /xFCO2
(4.28)
In general, when two key components are selected, S is better to be much larger than
1.0 or far lower than 1.0. In the case of SH2 ,CO2 < 1, we can consider the opposite of
the representation, i.e., SCO2 ,H2 . Then, when the separation factor is in the expression
of greater than 1, the larger value corresponds to the higher separation effectivity, and
a value close to 1.0 spells a low degree of separation [88]. As S the membrane
tends towards super selectivity.
Permeability
The permeability of certain component is also used in several articles. It has already
been formulated in the previous equations. Some researchers named it as selectivity
[89]. Here we use the former-permeability ().
i =
CiP
CiR
(4.29)
Thus, Equation (4.25) could also be written as:

SH2 ,CO2 =
H 2
CO2
(4.30)
Permeation rate
Another parameter that can indicate the ability of separation is the permeation rate [3].
The rate of molar transfer of certain component is usually expressed as the molar
amount of the component passing through unit area of the interface per unit time,
thus,
Ji =
v P CiP
A
(4.31)
39
here, A is the surface area of the membrane (cm2 ), J (molmin1 cm2 ) means permeation rate.
According to Koichis conclusion [90], we have
N
X
Ji 0
(4.32)
i=1
These should also be verified in the experiments.

Separation could take place as a result of the different permeation-ability of a given
membrane for dissimilar gasesone or some components are able to permeate a membrane easier than others. The permeation ability depends on not only the different
properties between the membrane and components but also the driving force between
both sides of the membrane.
The driving force comes from the gradient or difference in some generalized quantity,
such as concentration, pressure, or temperature between both sides of the membrane.
Furthermore, the permeation rate, which sometimes is also called flux or absolute
activity, is proportional to the driving force [49]. The relationship can be expressed by
the following equation:
dF
(4.33)
d
where F represents the driving force that causes the trend of transporting between both
Ji = k
sides of the membrane, k is the phenomenological coefficient, and is the coordinate

dimension in the membrane.
Although there are many different means of expression, the most common expression
is the mass transport recently, which is referred to Ficks law of diffusion in Equation
4.34, and volume flux results from pressure difference, which is depicted as permeation
in Darcys law in Equation (4.35) [3, 5, 90, 91].
Jm = D
dC
d
(4.34)
JV = L
dP
d
(4.35)
where, the diffusion coefficient D is, the diffusivity in dimensions of m2 s1 . As introduced above, it depends on diffusing species, membrane characters, temperature and
sometimes concentration. L is the permeability coefficient (mols1 m1 Pa1 ).
Take Darcys law as an example, after integration the relationship forms the Equation
(4.36) [49, 62]:
(JV )i = JV xPi = L
P P xPi P R xR
i
(4.36)
40
Therefore, Equation (4.12) could also be expressed as:

P P xPi P R xR
i
At
(4.37)
P P xPi P R xR
P P vp P
i
xi = L
A
(4.38)
RT
Using Henrys Law for equilibrium of molecules, Equation (4.35) could be written as:
nP xPi = L
xF +xR
here, Patm
P F i 2 i Patm xPi
P R PiP
Ji = L i
=L
represents the pressure of atmosphere (Pa).
(4.39)
Selectivity
The last parameter is the selectivity of the membrane , defined as the ratio of the
permeabilities between components [26, 62, 92].
H2 ,CO2 =
LH 2
LCO2
(4.40)
Substituting Equations (4.36) into (4.40), we get:

xP
H
H2 ,CO2 =
xP
CO
R R
(P P xP
H P xH )
2
(4.41)
R R
(P P xP
CO P xCO )
2
When P P approaches to zero,

xP
H
H2 ,CO2 '
xP
CO
xR
H
= SH2 ,CO2
(4.42)
xR
CO
Hence, the selectivity of the membrane is approximately equal to the separation factor
of the membrane.
In the transport mechanism of Knudsen diffusion [5],
1
8 rp p
(4.43)
Li,Kn =
3 2RT Mi
where, Li,Kn is the permeability coefficient in Knudsen diffusion. Substituting Equation
(4.43) into Equation (4.40), then we get [1, 15]:
H2 ,CO2 =
DH2 ,K
MCO2 1/2
=(
)
DCO2 ,K
MH2
(4.44)
Therefore, molecular weight ratios should be larger as mention above. Low selectivity
based on Knudsen diffusion will be got with a low weight ratio. The high value of
the permeability is one of the advantages of Knudsen diffusion. Using an extra transport mechanism (surface diffusion, for instance) for one of the components will mostly
increase the separation factor.
Chapter
Experimental Results and Discussion
This chapter includes data correction of controlling equipment, calibration of measuring instruments, and the results of all measurements, which are worked out with
the methods and formulas mentioned in Chapter 4. In the project, the main model
employed was the single-module of counter-current flow pattern with purge gas. The
introductions of membranes, membrane cell, gaskets, detail procedures and results will
be listed according to the order of the melioration.
5.1 Controlling equipment and corresponding special procedures,

calibration
5.1.1 Bubble flow-meter
Measurements using soap film flowmeters are quick and results are reproducible. However, when measuring very low-rate gas flow, diffusion problems of soap-film flowmeter
arise. Especially with hydrogen at low speed, the flat soap bubbles move too slow for
measurement to be reliable. After tens of tests, I found it was not so accurate enough
if just one single soap film was tested in the glass tube, maybe because of the diffusion
problems mentioned by Jia Guo [93]. If six or seven bubbles were interposed regular
at intervals, e.g., every 10 ml, and the penultimate bubble was taken as the measure
target, then the results were reliable and reproducible. With the sixth or seventh soap
film, both sides were the pure sample gas, gases were far away from the air and no
pressure drop occurred, so that no diffusion occurred.
If the gas flow rate was very slow, the bubble wormed in the glass tube, and it became
difficult for the counter to gauge the begin and stop time. When the gas flowed fleetly,
42
Chapter 5 Experimental Results and Discussion
it was too fast to count. Therefore, though it was reported that the 100 ml bubble
flowmeter had a kit range of lower than 300 ml/min, we chose measure the gas flow
between 10 and 200 ml/min, taking the accuracy into account.
5.1.2 Data correction of mass flow controller

As introduced in Chapter 4, both MFC s ranges are 750 mln /min (100 %). The setted
flow rates are equal to the percentages multipying by 750 mln /min. For example,
setpoint of 3 % means the flow rate of 22.5 mln /min. One MFC in this project was
for direct control of nitrogen, air, etc., and the other was for direct control of the feed
gases such as hydrogen, carbon dioxide, methane, and mixed gases. Their allowable
working pressure range was from 1 bar to 4 bar.
In actual operation, the gas pressure was controlled by the reducer at 2.4 bar. The
set flow rates and the actual flow rates of two-component gas are shown in Table 5.1
and Figure 5.1.
In Figure 5.1, dashed line represents the estimative value of MFC,

Table 5.1: Flow rates of two-component gas controlled by MFC
Setpoint [%]
10
20
30
50
100
Ideal estimative value [mln /min]
7.50
75.00
150.00
225.00
375.00
750.00
Estimative value [ml/min]
8.19
81.86
163.71
245.57
409.28
818.56
Actual flow rate [ml/min]
12.84
89.53
173.36
256.90
433.97
855.13
and the real line is the actual volume flow measured by soap film flowmeter at 25 C.
The results from 1 % to 50 % answer for linear-relationship. The whole-range value in
Table 5.1 is deduced from this liner-relationship of measured points. The real outcome
of MFC is a little larger than its setpoints. The flow rate of 55 % or higher was too
fast to be measured by a stop watch.
Other gases were all measured and results were similar to two-component gas. Since
most of the experiments were done with low-velocity gas (22.5 mln /min), the comparison of other gases flow rates is shown in Figure 5.2. For different kinds of gases,
the MFC s operated their flow rates in similar liner-relationship but of different slopes.
Therefore, though feed gas and sweeping gas were both set at 3 % in experiments, the
actual volume flows were sightly different.
In order to ensure the absence of control errors under small gas pressure, the actual flow
rates of two-component gas at 3.0 bar and 4.0 bar were also measured (see Figure 5.3).
The results show that, in the allowable range of work pressure, MFC can control gases
5.1 Controlling equipment and corresponding special procedures, calibration
43
Figure 5.1: Flow rate of two-component gas at 2.4 bar
stably. Different work pressures did not influence the volume flow of MFC. Equipment
error of MFC existed, but the relationship of estimative points and real values were
stable. Therefore, the MFC s could be calibrated and were believable.
However, to ascertain the actual control regulations of MFC s, even more data were
required. They were not the main object of the project, and the duration of project
was restricted, so the regulations were not totally clear. It can be included in the further
research. Thus, the results were calculated only by the linear-relationship of the small
area around the experimental flow rate instantaneously. Details were introduced in the
next section.
5.1.3 Calibration of gas chromatograph (GC )

The basic principle and the theoretic method of calculation were introduced in Chapter
3 and Chapter 4 respectively. For quantification with the 6890N, calibration became
more essential. Since the injection was automatic, it was difficult to use some standardgases or to calibrate with the manual-injection-reference measurements. Though automatic injection was much more convenient and seemed more accurate without operator
errors, lots of parameters can influence the measure of GC. The problems which appeared in the experiments and new methods for calibration are described.
44
Figure 5.2: Flow rate of 2 % to 4 %
Measurements of warming up
When GC started to measure samples, the first two or three data gathered were usually
not stable. As shown in Figure 5.4, the first two data at room-temperature (RT-blue
line) are obviously not normal. That might because the membrane vessel or pipeline
were not swept clean enough, so there were some residue gases from last measurements.
That also might be caused by the incomplete warming up of GC. However, generally
since the fourth or fifth measurement, data become stable and normal. Furthermore,
the first measurements of all the posterior processes are unusual, see data at 100 C in
Figure5.4. This is likely caused by the pipeline-residual gas. Therefore, in the following
processes, three or four measurements were carried out for the average value (except
the first one).
Base line of chromatogram

Program of GC makes the base line and calculates peak height and areas automatically. Usually operators prefer using the automatic data, since there are no man-made
operating errors. However, sometimes the automatic base line is actually obviously
bad, then the base line should be redrew. Figure 5.5 shows one chromatogram with
both automatic and manual base line. The rose line is the base line made by GC automatically that shapes a much larger area than the peak itself; and the orange one made
manually with mouse pointer is necessary to get the right area value. The manual line
45
Figure 5.3: Flow rate of two-component gas at different pressures
should be made in a fixed range for certain gas characteristic peak, as then the data
are comparable with each other.
Influence of run time
In the measurements with GC, one problem appeared, that time duration affects the
area of spectrum peaks. Because of different retention times of different components,
at the beginning of the project, run time was not constant. For example, when H2
was the object to be observed, three minutes were long enough for appearance of its
characteristic peaks. Later when the time duration was set longer for other gases,
the area of H2 peak varied. Then tests of the same gas sample with different time
duration were done. Outcomes revealed that, the run time of GC-Method could affect
the chromatograms slightly. Longer time duration resulted in lower area value. For
instance, H2 in two-component gas is shown in Figure 5.6. Though the differences
were small (just 2.94 %), in order to obtain much more accurate quantification, fixed
run-time in the later experiments was applied. Furthermore, CO2 was the component
of the longest rentention time (9.495 min). Hence, measure method was set to run 10.5
min.
46
Figure 5.4: GC measurements
Figure 5.5: Base line of chromatogram
Influence of gas temperature on automatic-injection

According to the ideal-gas equation (Equation (4.4)), temperature can change the volume flow or density of gas. Measure method of GC used a basic temperature of 60 C to
avoid such influence. Gases at different temperatures were still tested for confirmation.
Figure 5.7 shows the characteristic peak areas of pure H2 at higher temperatures with
pipe cooling system, which has been introduced in Chapter 3. The results show that,
with the pipe cooling system and 60 C basic temperature, GC measurements are not
impacted by temperature. Therefore, compositions of permeate-gases outgoing from
47
Figure 5.6: Area of H2 in two-component gas measurements with different run times
membrane cell at higher temperature can also be calculated with calibration gases at
room temperature.
Influence of reference gases for GC measurements

As has been pointed out in Chapter 3, both N2 and He were required as reference gases
for GC. If just He was used, the representative peak of H2 was very small. Thus, N2
was used as a carrier gas at an individual channel for H2 to avoid large calculation
errors. If just N2 was used, the composition of N2 in mixture was impossible to be
measured, and the measurement of other gases was inaccurate. The feed gases used in
this project were mainly H2 , CO2 , two-component gas (2M contains 49.8 % volume
percentage H2 and 50.2 % CO2 ), and five-component mixture gas (5M 13 % H2 , 16
% CO, 13 % CO2 , 53 % N2 , and 5 % CH4 ). Compositions of feed gases measured by
GC with N2 or He as reference gas are shown respectively in Table 5.2 and Table 5.3.
As can be observed, using N2 as reference gas, content of H2 can be measured accurately
(12.35 % is close to 13 % and 49.88 % is close to 49.8 %). When He is used as reference
gas, CO2 and N2 are in the right range, which are 13.17 %, 50.3 % and 56.20 %
corresponding to 13 %, 50.2 % and 53 %. But the contents of H2 are just 4.97 % in the
five-component gas and 34.57 % in the two-component gas, which are far away from
the right levels. The measurements of CO2 using N2 are also of large errors. Therefore,
48
Figure 5.7: Area of pure H2 measurements at different temperatures

Table 5.2: Gases compositions using N2 as reference
Peak area
H2
CO2
Gas type
[25Vs]
[25Vs]
5M
10289.70
1691.83
2M
41550.75
5297.60
H2
83302.05
CO2
9209.05
Percentage [%] in 5M
12.35 %
18.37 %
49.88 %
57.53 %
the front detector of N2 ought to monitor H2 only. He can be used as reference gas for
all the other gas components in the project.
Influence of flow rate on automatic-injection
Upon switching the gas sampling valve of alternate streams, the contents of sample
loops (0.6 ml) were inserted automatically into the inlets. Since the volumes of the
sample loops and injection-time (0.1 min) were all fixed, the flow rate determined the
injected amount of samples at room temperature and under ambient pressure. The
influence of flow rate (H2 ) on automatic injection is shown in Figure 5.8.
49
Table 5.3: Gases compositions using He as reference
Peak area
H2
CO2
N2
Gas type
[25Vs]
[25Vs]
[25Vs]
5M
93.40
20894.60
52502.9
2M
649.75
79804.00
H2
1879.65
CO2
158648.20
N2
93429.6
4.97 %
13.17 %
56.20 %
34.57 %
50.30 %
This result testifies the influence of flow rate on automatic-injection amount. Higher
volume flow causes larger amount in automatic injection. N2 changes more obviously
(see Figure 5.9). As a result, there are only two ways to realize the believable quantification. One is accurately controlling, and keeping the same for all the sample-flows
rates. Another is promptly measuring the flow rate of sample-gas, and designing a serial
experiments for exact calibrations. Automatic injection is not convenient or accurate
unless the problems of flow rates have been well solved.
New method for calibration

The membranes employed were made of porous material and gas separation depended
mainly on the sizes of molecules. There was no special selectivity over the gas types.
Thus, gas components in both feed gas and sweeping gas, can permeate through membrane. Though the flow rates of feed gas and sweeping gas can be controlled by the
MFC, those of permeate-gas and retentate actually depended on the membrane and
conditions. The controlling of the fluxes can not be easily realized. Thus, the method
of prompt measuring and reference-design was the best choice in this situation. Actual
flow rate and characteristic peak areas were supposed to be linear in the smallest setting area of volume flow (each 1 % of MFC ). Take H2 as an example, this project had
three H2 contained gas cylinderspure H2 , two-component gas, five-component gas.
They were feed gases for experiments as mentioned above, but they could also be used
as standerd-gased for H2 calibration.
For instance, in the experiments of gas separation using porous cement membrane
at 200 C, feed gases and sweeping gas (N2 ) were set to 3 % (22.5 mln /min). Fivecomponent gas, two-component gas and H2 were used as feed gases respectively, and
50
Figure 5.8: GC measurements of different reference-flow rate
the three kinds of measurements can be expressed as <5M ;N2 >, <2M ;N2 >, <H2 ;N2 >
in short. During the experiments, volume flows of permeate-gases and retentates were
obtained with the help of soap film flowmeter. Flow rates of permeate-gases for the
last three feed gases are listed in Table 5.4.
Table 5.4: Volume flows of permeate-gases
Measurement
<5M ;N2 >
<2M ;N2 >
<H2 ;N2 >
Volume flow
[ml/min]
[ml/min]
[ml/min]
Permeate-gas
33.18
34.14
35.16
After measurements with membrane, standard-gases were connected directly to GC,

and measured orderly with the flow rates around the small setting area of permeate-gas
volume flow (3 % and 4 %). Then all the chromatograms and flow rates of permeategas, retentate and standard-gases were gathered. The deductive process of calculation
is depicted as follows.
Figure 5.10 shows the actual flow rates of standard-gases with the setpoint of MFC
between 3 % and 4 %, and this range covers the volume flows of permeate-gases.
Because of the linear relationships, corresponding points are easily found in this figure.
For example, a, b and c are the corresponding points in sequence of standard fivecomponent gas, two-component gas and pure H2 in <2M ;N2 > measurement. All the
corresponding relationships are listed in Table 5.5.
51
Figure 5.9: N2 amount and flow rates in automatic injection

Table 5.5: Corresponding points of standard-gases
Measurement
<5M ;N2 >
<2M ;N2 >
<H2 ;N2 >
Standard gas
[%]
[%]
[%]
5M
3.22
3.33
3.45
2M
3.29
3.40
3.52
H2
3.20
3.31
3.42
Peak areas of chromatograms were also collected at 3 % and 4 % by GC. Figure 5.11
illustrates area values for pure H2 standard-gas. In the assumptive linear setting area,
the standard value can be found through the corresponding point. The area point
marked with C is the standard area value of 100 % H2 in <2M ;N2 > measurement
metioned in Figure 5.10 and Table 5.5. Other standard values for calibration are
figured out likewise (see Table 5.6).
The volume-content of H2 in five-component gas, two-component gas and pure H2 are
13 %, 49.8 % and 100 % respectively. Then the calibration curves are achievable. The
calibration curve for <2M ;N2 > measurement is shown in Figure 5.12-A.
Though there are just three points, curve obeys linear relationship quite well. Extending the line, and low concentration range is zoomed in to figure B in Figure 5.12.
There is a small error here, so three points are far not enough for the calibration curve.
All the concentration range should be covered for a more believable calibration, from
zero to 100 %. However, the project was lack of standard-gases for automatic injection
52
Figure 5.10: Flow rate calculation of standard-gases
Table 5.6: Characteristic peak area of H2 in permeate-gas and standard gases
Measurement
<5M ;N2 >
<2M ;N2 >
<H2 ;N2 >
Peak area of H2
[25Vs]
[25Vs]
[25Vs]
Permeate-gas
6152.900
21240.800
43383.750
5M
10802.42
10829.70
10858.48
2M
43513.98
43668.43
43831.37
H2
84381.87
84409.17
84437.96
and calibration curve was not stable. When GC was restarted or its detectors began
to work, the calibration curve should be drawn again. There was not so much time
for the detail calibration curve. Acctually, every experiment took thirteen to fourteen
hours daily already, just with these three standard-gases. Therefore, I added another
standard point into the calibration curve, that is (0, 0). When there is no hydrogen,
chromatogram contains no characteristic peak for H2 . Using the linear relationship in
small ranges, the contents of H2 were calculated more reasonable (Permeate-gas from
experiment of <5M ;N2 > used the range of 0-13 %; <2M ;N2 > used 13 %-50 %; and
<H2 ;N2 > used 13 %-50 % or 13 %-100 % range). Results for the permeate-gases are
shown in Table 5.7.
53
Figure 5.11: Pure H2 peak area for calibration of 2M measurement
Table 5.7: H2 concentration in permeate-gases
Permeate-gas
<5M ;N2 >
<2M ;N2 >
<H2 ;N2 >
Content of H2
7.40 %
25.50 %
51.94 %
Use natural number j (0<j<100) to represent setpoint value. o represents objective

component. Value of j is chose to make vj < vo < vj+1 . Then in the range of 0-13 %,
data processing can be summarized into the following equations:
CoP =
Zo
5M
(Zj+1
Zj5M )
vo vj5M
5M v 5M
vj+1
j
13%
(5.1)
+ Zj5M
here Z is the average value of peak area (25Vs), v is the average value of volume flow
(ml/min). Superscript 5M means standard five-component gas. So vj5M is the average
value of actual flow rates of five-component gas, when the MFC is set to be j %. The
Equation (5.1) can be reduced to Equation (5.2) as follows.
CoP
5M
Zo (vj+1
vj5M )
= 5M
13%
5M
Zj+1 (vo vj5M ) + Zj5M (vj+1
vo )
(5.2)
54
Figure 5.12: Calibration curve for H2 of 2M measurement
Similarly, in the range of 13 % to 50 %, the molar percentage of objective component

is presented in Equation (5.3). And the mole fraction larger than 50 % is formulated
in Equation (5.4).
CoP
5M
Zj5M )
Zo [(Zj+1
=
2M
[(Zj+1
Zj2M )
vo vj2M
2M v 2M
vj+1
j
vo vj5M
5M
vj+1 vj5M
+ Zj5M ]
5M
+ Zj2M ] [(Zj+1
Zj5M )
36.8%+13%
vo vj5M
5M v 5M
vj+1
j
+ Zj5M ]
(5.3)
CoP
2M
Zo [(Zj+1
Zj2M )
=
H2
[(Zj+1
ZjH2 )
H2
vo vj
H
H2
2 v
vj+1
j
ZjH2 ]
vo vj2M
2M
vj+1 vj2M
2M
[(Zj+1
+ Zj2M ]
Zj2M )
vo vj2M
2M v 2M
vj+1
j
49.8%+49.8%
+
Zj2M ]
(5.4)
When calculating CO2 percentage-concentration in permeate-gas, the balance equations in Chapter 4 can be used, as shown in Equation (5.5):
P
CCO
=
2
F
F
R
R
CCO
vCO
CCO
vCO
2
2
2
2
P
vCO
2
(5.5)
Other gas components and experiments were also calculated in the same way. The
calibration methods were found during the long period of experiments, so some early
data were just calculated in the original theoretic way.
5.2 Experiments
55
5.2 Experiments
5.2.1 First set of experiments with Gaggls membranes
Maria Gaggl did her diploma thesis over gas separation with dead-end membrane module, and designed the first membrane cell for the project at the early beginning. The
membranes used for testing were from her diploma project. Maria suggested WickeKallenbach cell with a co-current flow pattern (see Figure 5.13).
Figure 5.13: Schematic of the first idea
As mentioned in Chapter 2 the counter-current flow pattern usually performs separation much better. Hence, the whole experiments were actually operated with the
counter-current flow pattern in my proposal. The thermal couple was also added on
the secondary side (sweeping gas side) to monitor the instantaneous temperature of
permeate-gas. Although the membrane cell had changed greatly after several improvements, the primal idea still played an important role in model design as reference.
First membrane cell

The first membrane cell is shown in Figure 5.14 and Figure 5.15. In Figure 5.14, the
center part marked with M is the cement membrane. The white T parts, made
of Teflon, is holders for membrane. Besides Teflon, there are also two metal holders
covered Teflon parts (see details in the right picture of Figure 5.15). Other parts,
including module shell and side covers, are all made of stainless steel. The cavum of
this membrane cell is a columniform space of 8 cm length and 4 cm diameter. Then,
spaces on two sides of membrane are 43.98 cm3 for 10 mm membrane, 47.12 cm3 for 5
mm membrane, and 37.70 cm3 for 20 mm membrane.
56
Figure 5.14: Schematic of the first membrane cell
Figure 5.15: The first membrane cell and holders
First membranes
The specimens were one type of the micro-porous cement slices in Marias experiments.
In Table 5.8 are the physical and geometric data of the specimens. Pore size distribution
of this membranes is shown in Figure 5.16.
Table 5.8: Physical and geometrical data of the first test membranes
Water
Total
Total
Pellet
Solid
cement
pore
pore
density/
density/
ratio
volume
volume
Density
True density
[-]
[mm3 /g]
[V ol. %]
[g/cm3 ]
[g/cm3 ]
0.6
65.97
19.81
2.10
2.43
Total
Average
Thickness
Surface
Water
Specific
porosity
pore
of the
area
absorption
surface
diameter
specimen
[nm]
[mm]
[mm2 ]
[mol- %]
[m2 /g]
110
10
1963
10.5
3.77
13.8343 %
5.2 Experiments
57
Figure 5.16: Pore size distribution of the first membranes
Teflon materials for gas-tightness

The Teflon holders introduced above, played the role of not only fixation and protection
of samples, but also gas-tightness between the slices and metal parts. This Teflon was
hard enough and was virtually chemically inert, so it was good at supporting and
protecting membranes. Furthermore, Teflon was flexible. Teflon holders contacted
tightly with the membrane surface. Therefore, gases were not easy to leak, and there
was no damage to the membrane.
It is also reported that Teflon has non-contaminating, non-adhesive and thermal properties, thus it can be used at higher temperatures. However, actually, in this project,
Teflon turned into yellow and became harder after being heated. Because of flexibility
loss, Teflon holders were not easy to be detached with the membrane. If they were
forced to be dismantled, the membrane would be damaged. Membrane might be difficult to insert back into the Teflon holders, and joints of the reassembled system could
hardly be airtight.
Four different materials (see Figure 5.17) were compared as gaskets between the main
shell and the side covers. In Figure 5.17, the top left one is made of copper, top right
one stainless gasket, lower left one Teflon and lower right one rubber ring. Testing
results show that, the first two annular gaskets were of no effect, regardless of the
smooth surface and the identical thickness. Airtightness of the latter two were much
58
better, especially at low temperature. However, the heating problems existed with
Teflon, as mentioned above. Furthermore, rubber materials can not withstand higher
temperature (more than 300 C) either. Therefore, searching for new gasket materials
which can work at higher temperature was imperative.
Figure 5.17: Gaskets for the first membrane cell
Figure 5.18: Flow rate influence at different temperatures
5.2 Experiments
59
Results
When this membrane cell was working, just one detector was active. H2 in permeategas is the important study object, so N2 is used as the reference gas of GC. At the
beginning, the influence of volume flow was studied. In order to minimize the effect
from pressure difference, sweeping gas was controlled at the same setpoint as feed gas.
As shown in Figure 5.18, volume flow (pure H2 as feed gas and pure N2 as sweeping
gas) of 112.5 mln /min (setpoint of 15 %), 150 mln /min (20 %) and 225 mln /min (30
%) were measured for comparison. When the volume flow is larger than 150 mln /min,
the air will leak from the joints of the membrane-cell. The experiments were executed
at room temperature and 100 C, respectively.
Figure 5.19: Gas separation with different volume flows
The permeability decreases as flow rate increases. Hence, lower flow rate is preferred for
the higher permeation efficiency. Figure 5.19 shows the contents of H2 in permeate-gas
with even lower flow rates, which were 22.5 mln /min (setpoint of 3 %), 75 mln /min
(10 %) and 112.5 mln /min (15 %). Gas permeation at higher temperature was also
studied. For all the temperature conditions, the permeation rate of 22.5 mln /min was
obviously better than larger volume flows. Considering the measurable range of the
soap film flowmeters, 3 % was the lowest setpoint of MFC s. Hence, both feed gas and
sweeping gas were controlled basically at 22.5 mln /min.
60
Then four pure gases were used as feed gas with flow rate of 22.5 mln /min. They were
all swept by 22.5 mln /min N2 , and the results are shown in Figure 5.20. It can be
observed that, that molar percentage of hydrogen, methane, carbon monoxide, carbon
dioxide are inverse to their molecular weight. As the smallest molecule among all the
components, H2 permeates best. Therefore, we concluded that the larger the molecule
is, the less the gas can permeate through membranes.
Figure 5.20: Gas separation with different feed gases
According to Equation 4.44, the selectivity of two gases is inversely proportional to the
square root of their molecular weight. Figure 5.21 lists out the theoretical value (dashed
line) and experimental results (solid line) together. The experimental selectivity of H2
from CO2 matches the theoretic value quite well. The other two gases performed the
same trend. Since just one detector was employed, measurements of permeate-gas and
retentate can not be done at the same time. Thus, temperature and pressure might
influence the permeation process and results, and mall difference between experimental
results and theoretic value was reasonable. Figure 5.20 and Figure 5.21 verify the theory
in Chapter 4 very well, where the porous materials can separate gases with different
molecular sizes. The increasing difference between molecular weights, sizes or shapes
will raise the efficiency of separation. Therefore, H2 and CO2 mixture gas is used as
feed gas for comparison of other factors.
5.2 Experiments
61
Figure 5.21: Experimental and theoretic selectivity
In summary, the first module was an important prototype of this project. Larger
flow rates resulted in lower permeation rate and less content of object in the product.
Henceforth, most of the experiments were carried on with volume flow of 22.5 mln /min
(setpoint). The permeation component with smaller molecular size resulted in the
higher permeation flux and then higher diffusion coefficient, theoretically supported
by T. C. Merkel [21]. The experimental selectivity was close to the theoryinversely
proportional to the square root of the ratio of molecular weights, which was derived
from Knudsen diffusion. Teflon holders and gaskets were flexible and airtight, but
became harder at temperature higher than 200 C. Hence, the material of gaskets
should be replaced.
Furthermore, this membrane cell had large spaces on both side. With long distance,
gases may stay longer but the problem of turbulent flow appeared. Some gases flowed
out of the reactor directly, and the gas in the corner may stay in the dead angle (see
Figure 5.22-A). In theory, gases should flow along the membrane in the permeation process, as shown in Figure 5.22-B. That is, the vertical length of the spaces of membrane
should be much shorter than its diameter. Then to facilitate the refitting operation,
the membrane was first designed as plan C in Figure 5.22. In this way, it is convenient
to add two steel plate on both sides of the membrane cell, and all the gas molecules
would have the chance to touch the membrane, and then to permeate freely.
62
Figure 5.22: Problem of the first membrane cell
5.2.2 Second set of experiments with modified cell
After consulting machinists for profession suggestions, and considering the gas-tightness
and soundness of the added parts, some cylinders made of stainless steel and more
graphite paper were installed into the membrane cell. The initial model of the secondary
membrane cell was produced for testing. And the axial section diagram of this initial
model is shown in Figure 5.23. Membrane is placed firmly in the center of the module.
Right blue part is the space on the primary side with a cubage of 9.94 cm3 , and left
sweeping volume is 5.03 cm3 . Black parts are the seals made of graphite. However, left
cylinders are not so well pressed closely with each other, so the cylinder A is not fixed,
which is bad for experiments. As a result, membrane cell was modified again in 2009.
Membrane cell
The design of the membrane cell was finalized as shown in Figure 5.24 (for 10 mm
membranes). The spaces on the two sides of membrane are both 5.03 cm3 (with a
diameter of 4 cm and thickness of 4 mm). Both axial section view of the center
membrane (5 mm) subassembly (left) and the whole module (right) are exhibited in
Figure 5.25.
5.2 Experiments
63
Figure 5.23: First version of the secondary membrane cell
Figure 5.24: Final design of the modified membrane cell
Membranes
Cement membrane
Old membranes used for the first membrane cell were also tested to prove the advantage of new membrane cell. As introduced above, microporous cementitious slice of
made in Institut fr Bauingenieurwesen of Technische Universitt Berlin were the main
objective material in the project. Usually the thinner the membrane is, the larger permeation rate is, but the membrane must be thick enough to endure mechanical stresses
64
Figure 5.25: Axial section view of the modified membrane cell
and prevent rupture. Thus, the thickness of the membrane should be no less than 5
mm. Membranes employed had thicknesses of 5, 10 and 20 mm.
Cementitious materials is mainly cement, but also water, aggregate, and chemical admixtures. The detail basic materials, additives and equivalent ratios of water to cement
((w/c)eq) of the membranes, are listed in Table 5.9.
There are short code names defined for these membranes shown in Table 5.10. Here, PZ
is Portland cement, SFA is additive Coal fly ash-EFA-building mineral filler KM/C ,
MS is additive micro silica-Elkem Micro silica 971-U , HOZ is Blast furnace cement,
TZ is Alumina cement, F-PZ is Micro-adhensive based on Portland cement, F-HS is
Micro-adhensive based on slag, and number 1 and 2 are used to distinguish different
types of the same cement.
5.2 Experiments
65
Table 5.9: Cement membranes
Cement and adhesive
Adhesive
(w/c)eq
Aalborg White I CEM 52.5 R-HS/EA/2
none
0.45
none
0.35
none
0.25
Cemex Rdersdorf CEMI 32.5R
none
0.45
none
0.35
none
0.25
Zementwerk Berlin CEM III/B 32.5N-LH/HS/NA
none
0.45
none
0.35
none
0.25
Fly ash
0.45
Fly ash
0.35
Fly ash
0.25
Micro silica
0.45
Micro silica
0.35
Micro silica
0.25
Fly ash
0.45
Fly ash
0.35
Fly ash
0.25
Micro silica
0.45
Micro silica
0.35
Micro silica
0.25
Aalborg White CEM I 52.5 R-HS/EA/2
Micro silica
0.25
Calucem Istra 40
none
0.35
Calucem Istra 40
none
0.25
Kerneos Ciment Fondu EN 14647 CAC
none
0.35
none
0.25
Dyckerhoff MIKRODUR P-U
none
0.30
Dyckerhoff MIKRODUR R-U
none
0.30
Table 5.11 gives the porosity informations of these membranes.
66
Table 5.10: Code name of cement membrane
Cement and adhesive
Additive
Code name
none
PZ-2
Aalborg White CEM I 52.5 R-HS/EA/2
Micro silica
PZ-2+MS
none
PZ-1
none
HOZ
Fly ash
HOZ+SFA
Micro silica
HOZ+MS
Fly ash
PZ-1+SFA
Micro silica
PZ-1+MS
Calucem Istra 40
none
TZ-2
none
TZ-1
Dyckerhoff MIKRODUR P-U
none
F-PZ
Dyckerhoff MIKRODUR R-U
none
F-HS
Table 5.11: Porosity of cement membrane
Code name
(w/z)eq
Average
Critical
Mercury-
Total
pore diameter
pore diameter
porosity
porosity
[nm]
[nm]
[V ol. %]
[V ol. %]
PZ-2
0.45
98
138
25.3
28.1
PZ-2
0.25
66
80
16.3
18.6
PZ-1
0.25
86
96
20.5
24.1
HOZ
0.25
63
100
13.8
21.7
HOZ+SFA
0.45
58
90
22.9
37.6
HOZ+SFA
0.25
18
15.4
21.4
HOZ+MS
0.25
12
11.6
23.0
PZ-1+SFA
0.25
53
59
16.6
23.7
PZ-1+MS
0.45
66
110
24.0
33.0
PZ-1+MS
0.25
37
16
14.0
21.4
PZ-2+MS
0.25
32
6.5
17.5
TZ-2
0.35
1189
1734
26.0
29.5
F-PZ
0.30
30
28
18.0
23.9
F-HS
0.30
19
2.6
19.7
To be more in detail, the pore size distributions of membrane PZ-2 with equivalent
water to cement ratio of 0.25 and 0.45 are shown in Figure 5.26.
5.2 Experiments
67
Figure 5.26: Pore distribution of PZ-2
S938H
One kind of multi-layer membrane named S938H was also used for comparison. Samples of the multi-layer membrane were made by KERAFOL -Ceramic Films GmbH.
The membrane (plate-diameter 50.5 mm) had a ceramic substrate (pore diameter of 2
m and thickness of 6.0 mm) and a 7 nm-thickness coating (pore diameter of 30 nm)
on one side.
Gaskets
Graphite has lots of advantages. First of all, the graphite seals used in the modified
membrane cell had self-lubricating properties and low friction coefficient. They were
much softer than Teflon. Graphite paper can be pressed thinner, so the small surface
defect can be remedied in this way. Thus, the joints were well airtight. The smooth
material could even protect membrane against excessive press rather than destroying
it. Secondly, graphite paper was cheap and the gaskets were shaped easily. When
the membrane cell was installed again, new graphite gaskets were used to keep the
air-tightness. The last but not least, other advantages of graphite were high thermal conductivity, high chemical stability, low thermal expansion coefficient, and high
thermal stability (thousands degree), which were much better than Teflon (250 C).
Black colored parts in Figure 5.25 are the graphite seals. The detail placements of
graphite gaskets around membrane (take the 5 mm as an example) are shown in Figure
5.27. The two parts marked with S are the holders for 5 mm membranes. They are
made of stainless steel. The numbered dark rings are gaskets used in the center of the
membrane cell. Gaskets 2 and 4 are placed between the plate surface and membrane
holders. Gasket 3 is set to cover side surface of the membrane, thus, the permeated gas
68
Figure 5.27: Graphite gaskets around membrane
components does not leak here. Gaskets 1 and 5 are used to maintain the airtightness
between membrane holders and their neighboring stainless steel cylinders.
Results
The experiments with the old membrane were repeated for comparison. Then tens of
the membranes mentioned above were measured with different gas-pairs, to investigate
the influence of different parameters. Performance of the modified membrane cell
Since membrane cell was modified, the comparison of the old and modified membrane
cells was the primal task. In the experiments with first membrane cell, pure gas measurements using earlier membrane type (thickness 10 mm, (w/c)eq 0.6) were carried
out. Among those, results of measurement with H2 as feed gas and N2 as purge gas
(<H2 ;N2 >) are shown in Figure 5.28.
Here, blue points represent the value of H2 molar content in permeate-gas obtained at
different temperatures with modified membrane cell. Points colored with rosiness shows
H2 molar percentage of permeate gas using the old membrane cell. The membrane cell
spaces were changed from 43.98 cm3 to 5.03 cm3 on both sides. The change of internal
volume leads to an alteration of residence time and improvement of the flow conditions.
It is obvious that using the new cell, permeation rates are much higher, and smooth
curve can be got instead of 100 C maximum point with old cell.
5.2 Experiments
69
Figure 5.28: Performance of membrane cells in <H2 ;N2 >
Influence of temperature
At the beginning of each daily experiment, in order to drive vapor and residual gases
out of membrane cell, the membrane was heated at 350 C for 90 min. Flow rates were
both set on the setpoint of 22.5 mln /min, almost the minimum flow rate controlled
by MFC. Furthermore, gases ran 30 min before measurements. This was aimed to
drive residual gases away from the pipelines and pores in the membrane, as well as to
achieve the equilibrium state of the gases diffusion on both sides. Experiments were
conducted from high to low temperatures, in which each temperature group (350 C,
200 C, 100 C and room temperature) were carried out four times. Since the first value
was always inaccurate, the other values were used to obtain the average value. The
results for different membranes are shown in Figure 5.29. The curves of different color
refer to different membrane type. Membranes in this figure all have the thickness of 5
mm. The equivalent ratio of water to cement ((w/c)eq) is 0.45 for PZ-2 and 0.25 for
others. For all of them, when temperature raised up, the permeation rates of H2 will
also increase. Separation factors of H2 /CO2 achieved at different temperature using
these membranes are shown in Figure 5.30. Results reveal that in experiments using
two-component mixture as feed gas, separation factor of H2 /CO2 decreases with the
rising temperature.
When the operating temperature raises up, the diffusion rates of isolated permeating
molecules and associated permeating molecules are high, and as a result, the total
70
Figure 5.29: Influence of temperature in <H2 ;N2 >
Figure 5.30: Influence of temperature in <2M ;N2 >
permeation rate is high and the separation factor is low [94,95]. Therefore, using membranes without selectivity, the increase in temperature leads to better the permeability
of H2 but the separation factor and selectivity will become smaller accordingly. At
room temperature, we can get much higher separation factors of H2 from CO2 .
5.2 Experiments
71
Influence of equivalent water to cement ratio

In Table 5.9, all kinds of membranes produced for the project are listed. There are
seven basic cements, and membranes can be classified into twelve types with different
adhesives. Each type has also different specimens with a variety of equivalent water
to cement ratios. Figure 5.31 shows the influence of equivalent water to cement ratio
on gas separation. PZ-2 samples with (w/c)eq of 0.45 (sky blue) and 0.25 (dark blue)
are compared here. Thicknesses of both membranes are 5 mm. Since the sample with
(w/c)eq of 0.35 is 10 mm thick, 0.35 comparison is not considered. Samples of 0.45 and
0.25 were measured in the experiment using two-component mixture as feed gas and N2
as purge gas. Separation factors of H2 to CO2 were proved by experiments to decrease
with an increase in temperature. Furthermore, membrane of lower equivalent water to
cement ratio got higher separation of H2 from CO2 . Hence, the 0.25 equivalent water
to cement ratio membranes attracted more attention later.
Figure 5.31: Influence of equivalent water to cement ratio in <2M ;N2 >
Influence of pore size

From Figure 5.26 we learn that most of the pore diameter of cement PZ-2 with equivalent water to cement ratio 0.25 is smaller than that of the cement PZ-2 with equivalent
water to cement ratio 0.45. Table 5.11 also shows that material of lower equivalent water to cement ratio also has a little lower pore sizes. The advantage of lower equivalent
water to cement ratio might be caused by the variation of pore size. Therefore, another
material of maximum pore diameter (8 nm) was brought into comparison. PZ-2 (thickness of 5 mm, (w/c)eq 0.25) has the average pore diameter of 66 nm, and most of pore
72
diameter is 80 nm. The average and maximum-quantity pore diameters of PZ-2+MS

(thickness of 5 mm, (w/c)eq 0.25) are 32 nm and 8 nm respectively. The permeate-gas
components are shown in Figure 5.32-A, and the PZ-2 (dark blue line) achieved larger
permeation flux of CO2 and slightly more H2 than PZ-2+MS. However, Figure 5.32-B
reveals that the latter obtains much better separation factor of H2 /CO2 . When the
pore diameter becomes smaller, molecules with small size can still permeate but not
for the large molecules. Therefore, in particular, the pore size distribution influences
the separation properties of the membrane. A relative small pore size of the membrane
resulted in better separation ability.
Figure 5.32: Influence of pore size in <2M ;N2 >
Influence of thickness
The cylinder products of cement were cut into disc-shaped specimens with the thickness
of 5, 10 and 20 mm. Since the products were friable, not all membrane types had these
three thicknesses. Basically, most of the membranes had the thickness of 5 mm, so the
membranes with the thickness of 5 mm were mainly used in comparative experiments.
Both permeation and separation factor using 5 mm membrane were much better than
those using 10 and 20 mm. Figure 5.33 shows the separation factor of H2 to CO2 in the
measurements <2M ;N2 > with specimens PZ-2+MS ((w/c)eq 0.25) of 5 mm, 10 mm,
and 20 mm. Using 5 mm thick specimen performs much higher separation of H2 from
CO2 . It verify the theory that, permeation rate is inversely proportional to thickness
of membranes [1, 96]. The membranes employed were not thinner than 5 mm, since
5.2 Experiments
73
thinner membrane can not endure mechanical stresses. Thus, the thickness of 5 mm is
a good choice for other comparisons.
Figure 5.33: Effect of different sample thickness on diffusion in <2M ;N2 >
One problem came out in the experiments of 20 mm specimen. In general, the thinner
the membrane is, the larger permeation rate is. However, as shown in Table 5.12
(examples at 350 C and room temperature), permeation fluxes using 20 mm specimen
are unreasonable. Values of 20 mm are larger than those of 10 mm, and the permeation
fluxes of CO2 are even larger than those of 5 mm.
Table 5.12: Permeation fluxes using PZ-2+MS in <2M ;N2 >
350 C
RT
Thickness of membrane
5 mm
10 mm
20 mm
5 mm
10 mm
20 mm
H2 in permeate-gas
13.24 %
4.84 %
10.02 %
16.49 %
6.37 %
11.42 %
CO2 in permeate-gas
3.90 %
3.45 %
7.24 %
9.45 %
3.45 %
5.27 %
Figure 5.34 shows those membranes after heating. 20 mm specimen-PZ-2+MS (top

right) was already broken after the heating. Lots of deep cracks appeared on this
membrane. The surface of 5 mm-PZ-2+MS (top left) looks better with a bit of minor
cracks which are not obvious. There is another membrane-TZ-2 (10 mm, (w/c)eq 0.25)
with additive iron shown at the bottom of Figure 5.34. The surface layer became darker
because of heating, and fall off after the experiments.
74
Figure 5.34: Membranes after heating
The cracks might be caused by water loss while heating or reaction between CO2 and
cement. When Gregor produced the tube membrane, he also found that the last drying
step of making membrane was hard to finish. Water lost might lead to the unuseful
membranes, which had several cracks on their surfaces. Thus, the usable membranes
should be dried slowly for 6 weeks. Among them 20 mm was the thickest one, so water
loss must be more obvious than others. That might also be the reason for the large
permeation fluxes.
Influence of different feed concentration
Besides pure gases and two-component mixture, five-component mixture (13 % H2
and 13 % CO2 included) was also measured as feed gas. One sample with specimenHOZ+MS (thickness of 5 mm, (w/c)eq=0.25) is shown in Table 5.13. It lists the
separation factors of H2 from other components. Compared with the other three gases,
hydrogen has much better degree of separation, which reveals the possibility to separate
hydrogen from the mixtures. Figure 5.35 shows the situation more intuitionisticly. A
and B are the compositions of feed gas and permeate-gas respectively without purge
5.2 Experiments
75
gas N2 . H2 can permeate more through a cement membrane, so concentration of H2

increases in this way. This result is just from the single stage. If the mixture was
separated with cement membranes using multiple stages, recycle design or both, results
will be much better and purification of H2 can be realized then.
Table 5.13: Separation factors using HOZ+MS in <5M ;N2 >
Temperature
Separation factor
H2 /CO
H2 /CH4
H2 /CO2
RT
3.365
2.081
2.180
3.104
1.912
1.950
200 C
3.006
1.760
1.705
350 C
2.782
1.639
1.548
100 C
Figure 5.35: Comparison of compositions in <5M ;N2 >
Permeabilities of different feed gases using specimen-PZ-2+MS (5 mm, (w/c)eq 0.25)

are summarized in Figure 5.36. When pure H2 , two-component mixture and fivecomponent mixture are used as feed gases, and the concentrations of H2 component
are 100 %, 49.8 % and 13 %, respectively. Lower concentration of feed gas (<5M ;N2 >)
corresponds to higher permeability. Therefore, when using real gas from a biomass
gasified, even very low concentrations of target components, this technology is still
operational. Furthermore, the application of cement membranes and circulatory system
will be helpful to reduce costs.
Influence of pressure difference
Pressure on both side of the membrane can affect separation. Pressure difference is
one of the driving forces that determine permeation ability. Membrane-PZ-2+MS (5
mm, (w/c)eq 0.25) was measured in experiment <2M ;N2 > with variational pressure
difference, while flow rates and temperature kept constant (see Figure 5.37).
The value of abscissa is the pressure difference of retentate to permeate side of the
membrane. The results prove that, larger pressure difference leads to higher permeation
76
Figure 5.36: Permeabilities of H2 using different feed gases
Figure 5.37: Influence of pressure difference in <2M ;N2 >
rate. Moreover, larger pressure difference corresponds to lower separation ability of H2

from CO2 . When the pressure difference is larger than 0.005 bar, the separation factor
will keep constant of 1; thus, membrane could not separate H2 from CO2 . The lower
pressure in the feed side of the membrane is, the larger separation factor is. However,
when the pressure is too low, just little gas could permeate, and slow separation is of
poor usability. Thus, the range of 0.002 to 0 bar is the optimal pressure difference in
the experiments.
5.2 Experiments
77
Influence of sweeping gas

Figure 5.38 shows data in experiments of <2M ;N2 > with the decreasing flow rate of
N2 . The setpoint of feed gas was fixed at 75 mln /min, and that of sweeping gas was
conducted from 75 mln /min to zero. Membrane-HOZ+SFA (5 mm, (w/c)eq 0.25) are
used here. Both permeation ability and separation factor became larger as flow rate of
sweeping gas decreases. Sweeping the permeation components away instantly reduced
the permeate partial pressure and enhanced the driving force. Hence, sweeping gas
was necessary. Moreover, sweeping gas could also be used to adjust the permeate-side
pressure and then to obtain another factor on permeation permeate pressure.
Figure 5.38: Influence of sweeping gas in <H2 ;N2 >
The majority of the measurements were performed with nitrogen as purge gas. Alternatively, carbon monoxide was also used. Figure 5.39 shows the mole fraction of H2
in permeate-gas in six experiments. Membranes used here are PZ-2 (5 mm, (w/c)eq
0.45), HOZ+SFA (5 mm, (w/c)eq 0.25), and HZ-2+MS (5 mm, (w/c)eq 0.25). Lines
with foursquare points are data from the measurements <H2 ;CO>, and points round
in shape are results from <H2 ;N2 >. Values of the same membrane are of slight difference between the experiments using different sweeping gas. Especially for HZ-2+MS,
results from <H2 ;N2 > and <H2 ;CO> are much more similar. Therefore, different kind
of sweeping gas did not influence the process of gas separation. The choice of optimal
sweeping gas is determined by the different application. In most cases, the product gas
is required to be with a good separability. There is no theorem to select the purge gas
until now, so the sweeping gas is usually determined by the actual requirement.
In further research, CO can be studied more, since there are already lots of relatively
mature technologies in pre-combustion field to separate CO. Researches can also be
78
Figure 5.39: Measurements of different sweeping gases in <2M ;N2 > and <2M ;CO>
done on CO2 and steam. CO2 can be adsorbed easily by water or lime water, and it is
easy to be released and recycled. Advantages of steam are well-known. Product gas can
be simply purified by a drying system. There are three disadvantages. First it requires
higher temperature. Second, product gas must be dried enough before cooling down,
otherwise water contained will block the pipes. Third, water may react with some
components in cement and change the membrane structure, which should be totally
avoided.
Influence of adhesives
Influence of material with different adhesives were also considered. Usually membranes
containing Microsilica displays better separation factor. As shown in Figure 5.40 with
base cement PZ-2 and PZ-1. However, take PZ-2 as example, with Microsilica corresponding a small critical pore diameter. The critical pore diameter of PZ-2 0.25 is 80
nm. The critical pore diameter of PZ-2+MS 0.25 is 8 nm, the latter obtains much better separation factor of H2 to CO2 . Therefore, advantages of the separation ability of
PZ-2+MS might also be caused by pore size distribution. This can be studied further.
5.2 Experiments
79
Figure 5.40: Influence of adhesives
Separation factor
Figure 5.29 and Figure 5.30 show that higher separation factors and lower permeation
rates at low temperatures are obtained than those at higher temperature regardless of
the feed composition. At higher temperature, the diffusion rates of isolated permeating
molecules and associated permeating molecules are higher, so that total permeation rate
is higher and the separation factor low. Thus, separation factors are more comparable
at room temperature. Table 5.14 shows the separation factors for all 5 mms membranes
that have been measured.
Membranes are in descending order according to separation factor. The separation

factor of S938H is near 1, which means S938H can not separate H2 from CO2 effectively
[88]. Other cement membranes are better than this multilayer ceramic membrane. PZ2+MS ((w/c)eq 0.25) in the first row performs the best separation ability. Therefore,
it is selected as the material for tubular membrane in further research. Images of
PZ-2+MS made by Center for Electron Microscopy of Technische Universitt Berlin
(ZELMI) is shown in 5.41.
80
Table 5.14: Separation factors using 5 mm membranes in <2M ;N2 >
Membranes
(w/c)eq
code name
Mole fraction
in permeate-gas
Separation factor
H2 [%]
CO2 [%]
of H2 /CO2
PZ-2+MS
0.25
13.24
3.9
3.425
HOZ+SFA
0.25
14.20
5.64
2.537
HOZ
0.25
13.08
5.20
2.535
F-HS
0.25
10.30
4.16
2.496
PZ-1+MS
0.25
14.73
5.98
2.483
PZ-1+SFA
0.25
9.60
4.09
2.367
PZ-2
0.25
13.84
5.95
2.346
HOZ+MS
0.25
11.98
5.34
2.260
PZ-1+MS
0.45
12.92
6.39
2.036
F-PZ
0.25
13.45
7.15
1.895
PZ-1
0.25
16.69
9.40
1.790
PZ-2
0.45
18.29
11.43
1.613
HOZ+SFA
0.45
14.24
9.87
1.454
S938H
unknown
27.18
30.84
0.942
Figure 5.41: SEM images of the PZ-2+MS
Permeation ability and diffusion coefficient

Membranes we used are mostly with pore size between 8 to 100 nm. The Knudsen
numbers of H2 and CO2 using membranes with pore diameter 8 nm and 100 nm are
shown in Figure 5.42. We can see that the Knudsen numbers are around one, and
those of membrane with pore diameter 8 nm are larger but the differences are small.
Therefore, according to the theory above the transport mechanism using these porous
cement membranes should be transition diffusion.
5.2 Experiments
81
Figure 5.42: Knudsen number of H2 and CO2
Among the membranes, PZ-2+MS (5 mm, (w/c)eq 0.25) was the best observed object.
The data from experiment <2M ;N2 > using this specimen are listed in Table 5.15.
According to Equation(4.29), Equation(4.34) and Equation(4.31) in Chapter 4, the
Table 5.15: Data using PZ-2+MS (5 mm, (w/c)eq 0.25) in <2M ;N2 >
Temperature [ C]
27.65
101.08
199.79
349.68
Flow rate of feed gas [ml/min]
31.41
31.41
31.41
31.41
Mole fraction of H2 in feed [%]
49.8
49.8
49.8
49.8
Mole fraction of CO2 in feed [%]
50.2
50.2
50.2
50.2
Flow rate of purge gas [ml/min]
30.34
30.34
30.34
30.34
Flow rate of permeate gas [ml/min]
32.02
32.30
32.57
32.30
Mole fraction of H2 in permeate-gas [%]
13.24
14.31
15.26
16.49
Mole fraction of CO2 in permeate-gas [%]
3.90
5.75
7.42
9.45
Flow rate retentate [ml/min]
26.56
27.07
27.43
27.40
Mole fraction of H2 in retentate [%]
31.48
30.10
28.48
26.48
Mole fraction of N2 in retentate [%]
19.5
21.44
23.21
25.12
Mole fraction of CO2 in retentate [%]
45.50
45.06
44.18
42.66
82
permeability, diffusion coefficients (Equation(5.6)) and permeation rate at different

temperature are carried out in Table 5.16.
Table 5.16: Permeation ability using PZ-2+MS (5 mm, (w/c)eq 0.25) in <2M ;N2 >
Temperature
27.65 C
101.08 C
199.79 C
349.68 C
SH2 ,CO2
3.425
2.510
2.072
1.759
H2
42.05 %
47.55 %
53.58 %
62.26 %
DH2 [cm2 /s]
7.42 103
8.34 103
9.21 103
1.02 102
DCO2 [cm2 /s]
1.72 103
2.67 103
3.62 103
4.80 103
H2 ,CO2
4.30
3.12
2.55
2.13
JH2 [molmin1 cm2 ]
1.37 105
1.20 105
1.02 105
8.30 106
Di =
Ji
273.5 R CiP V P
3
10
CiF CiP
60 22.41 A (PiF PiP )
(5.6)
Moreover, as mentioned in chapter 2, the transport is reckoned mainly as Knudsen

diffusion, if the rp is between 530 [5]. Most pore diameters of the membranes
employed in the project were between 8 to 100 nm, so the gas transport mechanism
might not be dominated by Knudsen diffusion. Furthermore, the theoretic values of the
Knudsen diffusion coefficient according to Equation(4.14) and the molecular diffusion
coefficient (Equation(4.19)) with an increase in temperature from room temperature
to 350 C are shown in Figure 5.43. We find actual diffusion coefficients are not
Figure 5.43: Diffusion coefficients of H2
the same with molecular diffusion theory, not with the Knudsen diffusion theory, but
5.2 Experiments
83
between their theoretic ranges. Therefore, the gas transport mechanism using the
cement membranes in the project should combine Knudsen diffusion with molecular
diffusion. The diffusion coefficient should be express as in Equation(5.7). Details can
be studied further.
1
a
b
=
+
D
Di,K Di
(5.7)
where, a and b are two constants.
5.2.3 Third set of experiments with tubular membrane and cell

As the performance of specimen-PZ-2+MS (5 mm, (w/c)eq 0.25) was excellent, it was
chosen as the material for columnar membranes. Using tubular membrane, the gases
can stay a longer time for permeation, larger area can be created for gas diffusion, and
a larger extract rate is hopefully achieved. Falconer illustrated the transport of gases
in a tubular membrane cell [1]. Since counter-current flow pattern performs better
than co-current, it is mainly employed in the project and the co-current flow pattern in
Falconers schematic diagram has been replaced with counter-current here (see Figure
5.44).
Figure 5.44: Schematic of transport in tubular membrane cell [1]
Membrane cell
Figure 5.45 shows an axial cut-away section of the new reactor. The blue-gray circularity cylinder is the tubular porous membrane-PZ-2+MS (5 mm, (w/c)eq 0.25),
and the dark-gray parts are made of non-permeable stainless steel. The spaces beside
membrane are routes for gases. Feed gas flows from left to right inside membrane-tube.
Some components permeate through the porous membrane meanwhile. Sweeping gas
84
enters membrane cell from right, and carries the permeation components out along the
outside-route. The center nonpermeable stainless steel cylinder reduces the space inside membrane, so gases will travel along membrane surface. Furthermore, this center
cylinder can protect membrane from pressing of side covers. However, the length of
the center cylinder must be controlled fitly. If it is too long, then gases will leak from
the spacing between membrane and side covers; on the other hand, center cylinder can
not work as protection, and it will move or even crush the fragile wall of the membrane
from inside. The tubular membrane cell with the special designed asbestine heater is
shown in Figure 5.46.
Figure 5.45: Tubular membrane cell
Figure 5.46: Heating system for tubular membrane
The two side covers were much more complicated. In Figure 5.47, top left picture is
the left view of the whole part. Eight screws fix the left side cover onto the middle
metal shell. The center hole-A (permeate-gas exit) will be separated to four (top
5.2 Experiments
85
middle), connected with the outside space of the membrane. The other large holeB (entrance of feed gas) on the left view, will be oriented to the center-C (bottom
left) then separated to three (bottom middle), and lead to the inside space of the
membrane. Two other holes marked with T1 and T2 in the above four diagrams are
designed for thermocouples. They are located at the same radial position but two
sides of membrane. Right picture in Figure 5.47 is the left view of the inside structure
(without left side cover). Spaces inside and outside membranes are clearer to observe.
T3 and T4 are thermocouple holes settled on the right side cover, in the opposite
direction with T2 and T1, which are planed on measuring temperature roundly. The
length of the tubular-shaped membrane is 18 cm, and diameters of two cirques are 1.72
cm, 2.00 cm, 2.50 cm and 2.70 cm in sequence from inside to outside. Hence, volumes
of inside and outside membrane are 58.90 and 58.81 cm3 respectively.
Figure 5.47: Design of tubular membrane cells
Tubular membrane and gaskets

Photos of tubular membrane and one side cover are shown in Figure 5.48. Membrane
is 18 cm long and 5 mm thick. This was the only measurable tubular membrane,
since membranes were easily destroyed, sometimes cracks came out from fast water
loss, or even holes were present on the surface in the drying process. One of the
plane is not smooth (Figure 5.48-left), which should be avoided in the further research.
86
This membrane is just a tentative step, more membranes and measurements should be
carried out for a universal study. Figure 5.48 shows graphite gaskets in a side cover.
1, 2, 3 are marked at the position for graphite ring-plates. 1 is between the side cover
and metal shell; 2 is between side cover and membrane; and 3 is between side cover
and the center metal cylinder. Those of the other side of the membrane cell are same.
An nonpermeable copper tubular membrane, was used to measure the gas-tightness of
the joints. All the connections were verified to be well airtight.
Figure 5.48: Tubular membrane and gaskets
Results and comparison

One test tubular membrane was heated at 350 C for three hours before measurements,
and a longitudinal crack appeared. In order to avoid the errors from large cracks that
might be caused by heating, the experiment procedures were modified. It was proved
to be feasible to make measurements of all the gas groups at temperature from low
to high. All the gas groups were done at room temperature first; then 100 C; later
membrane was blew with N2 for 16 hours at 200 C and measurements were finished
at 200 C and 350 C, respectively. Standard-gases of 2M , 5M , H2 , CO2 and N2 were
measured each day as references. Each group was conducted three times for a average
value.
Mole fractions of H2 and CO2 using tubular and plate membranes in <2M ;N2 > are
compared in Figure 5.49. Separation factors of H2 to CO2 in <2M ;N2 > and <5M ;N2 >
are shown in Figure 5.50. The results are not so positive. There are more permeations
5.2 Experiments
87
Figure 5.49: Components in permeate-gas in <2M ;N2 >
Figure 5.50: Separation factors of H2 to CO2
for both H2 and CO2 using tubular membrane than plate one (the other gas pairs show
the same trend), but the separation factors are a little smaller. As discussed above,
there was just one tubular membrane, one of whose planes was not smooth. Therefore,
this membrane was just a tentative step, and more membranes should be produced and
investigated to obtain representative values for tubular-shaped cement membrane.
88
When the temperature increased from 100 C to 200 C for the first time, the experiments stopped, as something blocked the pipes and gases could not move further.
When the connections were opened 10 cm away from the outlet of permeate-gas, clear
liquid was observed (see Figure 5.51).
Figure 5.51: Water from tubular membrane
The liquid was smelly and it might be water mixed with the solvent (adhesives in the
cements). That was the reason for 16 hours heating with N2 at 200 Cto drive all
the liquid out of the membrane cell. After that measurements at 200 C went well.
When the membrane was heated from 200 C to 350 C, same phenomena came out.
Thus, the standard-gases were measured first for seven hours, and experiments at 350
C was measured successfully.
One block-chromatograms is shown in Figure 5.52. One more peak appears (gray) at 7.5
Figure 5.52: Chromatogram in <5M ;N2 > at 200 C
min, which can be steam (up to parked materials in columns). The water-loss problem
might also happen at 100 C. A small amount of water can not easily be found. Under
normal circumstances, the water vaporizes at 100 C. In the experiments, vaporizing
also occurred at 200 C. That may because that, water in micropores gasified at higher
5.2 Experiments
89
temperature, when the pore pressure increased large enough, vapors can be pressed
out. In much smaller pores, water loss did not happen at 200 C, but it was achieved
by 350 C. At last, large crack occurred on the tubular membrane (Figure 5.53).
Figure 5.53: Large cracks after heating
Vapors flowed out of the heating membrane cell, into the pipes at room temperature.
Then they were cooled, condense and accumulated until the pipelines were blocked.
Inner diameter of the pipes was small, only 2 mm, as long as a drop of water came
into being, the problem became obvious. Pipe blocking baffled drawing gases for
chromatograph-measurements, while also changed pressures on both sides of membrane, which then influenced the gas separation. As mentioned above, water loss can
result in larger holes and cracks, which changed the characteristics of membrane itself,
and also influenced its gas separation performance. Hence, the methods of manufacture
and experiments need to be improved.
Diffusion coefficients and other parameters calculated are listed in Table 5.17 and Table
5.18.
Table 5.17: Permeation ability using tubular-PZ-2+MS (5 mm, 0.25) in <2M ;N2 >
Temperature
23.2 C
101.5 C
190.6 C
358.65 C
SH2 ,CO2
1.465
1.844
1.747
1.842
H2
81.89 %
82.27 %
60.37 %
47.75 %
DH2 [cm2 /s]
7.59 104
8.00 104
1.27 103
1.69 103
DCO2 [cm2 /s]
4.42 104
3.43 104
5.03 104
5.63 104
H2 ,CO2
1.72
2.33
2.53
2.99
JH2 [molmin1 cm2 ]
1.25 106
1.02 106
1.01 106
8.50 107
90
Table 5.18: Permeation ability using tubular-PZ-2+MS (5 mm, 0.25) in <5M ;N2 >
Temperature
23.2 C
101.5 C
190.6 C
358.65 C
SH2 ,CO2
1.140
1.406
1.724
2.302
H2
81.99%
4
81.01 %
8.91 10
1.56 10
2.14 103
DCO2 [cm2 /s]
6.95 104
5.32 104
5.82 104
4.78 104
1.22
1.67
2.68
4.47
JH2 [molmin cm ]
3.53 10
2.83 10
39.45 %
8.51 10
H2 ,CO2
54.32 %
DH2 [cm /s]
2.86 10
2.50 107
Chapter
Summary and Outlook
6.1 Summary of results

Three membrane cells were designed to form a the single-stage module with the countercurrent flow pattern. 25 cement membranes were tested. Furthermore, experiments
were conducted in order to characterized the following points: 1. gas molecules properties related to their transport in materials; 2. impact of operating conditions on the
separation process; 3. influence of membrane properties of the membrane structure
on gas permeation; 4. the relative parameters necessary to determine the membrane
performance.
1. Gas molecules properties related to their transport in materials.
Permeation component with a relatively small molecular size corresponded to a
relatively high permeation flux and diffusion coefficient. Compared with the other
three gases, hydrogen had a considerably good separation factor. The experimental selectivity of H2 to CO2 matched well the theoretical value. The selectivity of
the two components was with good approximation inversely proportional to the
square root of their molecular weight. Use of CO as a sweeping gas instead of N2
did not affect the results. In most cases, good separability of the permeated gas
determined the choice of the optimal sweeping gas. A lower feed concentration
value led to a higher value of permeability.
2. Impact of operating conditions on the separation process.
Permeation fluxes increased, while the separation factors of H2 to CO2 decreased
with increasing temperature. A large pressure difference resulted in a high permeation rate and a low separation ability of H2 from CO2 . The permeability
92
Chapter 6 Summary and Outlook
decreased with an increase in the flow rate of feed gas. Both the permeation
ability and the separation factor increased with a decrease in the flow rate of the
sweeping gas. Sweeping the permeation components away instantly reduced the
permeate partial pressure and enhanced the driving force. Thus, the sweeping
gas was necessary.
3. Influence of membrane properties of the membrane structure on gas permeation.
Membranes with a thickness of 5 mm show a considerably higher separation of H2
from CO2 , than membranes with thicknesses of 10 mm and 20 mm. A membrane
with low equivalent water to cement ratio could achieve a high separation of
H2 from CO2 . In particular, the pore size distribution influenced the separation
properties of the membrane. A relative small pore size of the membrane resulted
in better separation ability. Relatively large permeation fluxes of both H2 and
CO2 were obtained when a tubular membrane was used than when a plate one was
used, but the separation factors were slightly smaller. More membranes should be
produced and investigated to obtain representative values for the tubular-shaped
membranes.
4. The relative parameters necessary to determine the membrane performance.
The separation factors of all the disk-shaped membranes at room temperature
were calculated. The multilayer ceramic membrane S938H was the worst with
an H2 /CO2 separation factor of almost 1.0. Furthermore, PZ-2+MS (5 mm
(w/c)eq 0.25) has the best separation ability. The permeation ability and diffusion
coefficients of a disc-shaped membrane were successfully estimated, as shown
in Table 5.16. These values were slightly lower than those of other inorganic
membranes (e.g., a separation factor of 6.75 for H2 /CO2 at low temperature
obtained by Koros and Mahajan [78]). However, as a cheap new material, PZ2+MS has potential, and the relevant researches are in progress.
6.2 Observations
Provided below are the observations pertaining to the sealing materials and the operating apparatus:
1. Teflon could not withstand a higher than 250 C. It became darker and harder
when it was heated. Furthermore, the airtightness became poor, especially at
6.3 Future work
93
the connections between the side covers and the metal shell. Graphite showed an
excellent capability as an optional gasket.
2. The measurement of the volumetric flow rate using soap film flowmeters was a
quick process and the results were reproducible. However, a large quantity of
flat soap was required during the measurements because of the diffusion problem.
Furthermore, the range of measurement improved from 10 to 200 ml/min.
3. The flow rates controlled by the mass flow controllers (MFC s) were generally
larger than the set values. Fortunately, the actual flow rates and setpoints had
a linear relationship. Therefore, the observed linear relationship of a small range
around the experimental flow rate was considered data processing.
4. The front detector of a gas chromatograph (GC ) using N2 as a reference, should
be used to monitor only H2 . He could be used as a reference gas for all the
other gas components used in the project. A high volumetric flow rate led to the
automatic injection of a large amount of the sample. However, the use of new
methods of data processing helped overcome such problems during calibration.
Reliable measurements were taken by using a manual base line with a fixed run
time of 10.5 min. The ambient temperature did not affect the chromatograph.
6.3 Future work

More membranes in different shapes should be produced and investigated. The following are the suggestions for further researches, and some ideas over purification of
product-gas.
1. Incongruous flow rates caused by MFC can easily be solved by the linear - relationship for laboratory experiments. However, when the measurements are extended to a larger range of flow rates, more standard-gases measurements would
be required. Therefore, new equipments or methods are necessary to control the
flow rates strictly for further measuring. Experiments on real gas from a biomass
gasified are necessary, since they are fundamental for practical applications.
2. Influence of flow rates on GC measurements can also be amplified in further
experiments, the same as that of MFC. Therefore, standard-gases with more
different mole fractions of target components are required to calibrate GC more
accurately, which is the most essential for quantification. A new method for faster
measuring can also be considered, e.g., laser.
94
Chapter 6 Summary and Outlook
3. Graphite has high thermal stability. The material is soft, so it can protect membranes and remedy the small surface defect. However, graphite is also fragile.
When the membrane cell is installed, graphite gaskets pasted on the membrane
cell should be cleared and new gaskets are required. Handling the thicknesses of
graphite around the columnar surface of membranes is also difficult. Gaskets of
new material which should be much harder, airtight and reusable, e.g., Carbon
graphite, are demanded to replace graphite paper.
4. Water dissolved with adhesives was lost from membrane, which brought new
components into product gas, changed the structure of membrane, embarrassed
measurements with GC, and influenced gas separation. Moreover, water loss
stunted cement membranes using at higher temperature, which was the notable
advantage of inorganic membranes. Better methods or bind to produce membrane is required to avoid this problem. In addition, because the effectivity of
membrane with a equivalent ratio of water to cement ((w/c)eq) of 0.25 is better
than that of 0.45, we can search for new methods to reduce the equivalent water
to cement ratio further. Hence, the membrane itself can be more refined and
more stable, and better separation ability can be achieved. With good results,
more membranes can be manufactured, and different shapes membranes can then
be studied at even higher temperatures.
5. Provided below are the ideas to use a different sweeping gas for the maneuverable
purification of permeation-gas.
As pointed out above, there are already lots of relatively mature technologies
in pre-combustion field to separate CO, so using CO as feed gas can be studied
further. Other possibilities of feed gas are CO2 and steam. Firstly, CO2 can be
adsorbed by water or lime water easily, and it is also easy to be released and
recycled. Possible schematic process is shown in Figure 6.1.
Secondly, using steam as sweeping gas, product gas can be simply purified by
a drying system (Figure 6.2). The precondition is that water should not react
with some components in the material, otherwise it will change the membrane
structure.
6. The investigation of relationship among diffusion coefficient and all the other
parameters, such as temperature, pressure difference, thickness of membranes is
necessary. An expression can be built on the investigation.
6.3 Future work
95
Figure 6.1: Process schematic of using CO2 as sweeping gas
Figure 6.2: Process schematic of using steam as sweeping gas
7. More experiments on using cement membranes to separate gases from a biomass

gasified are required. With good result, this material can be applied on gas
separation or purification in the industrial field.
Bibliography
[1] Falconer, John L. ; Noble, Richard D. ; Sperry, David P.: Catalytic membrane reactors. In: Noble, Richard D. (Hrsg.) ; Stern, S. A. (Hrsg.): Membrane Separations Technology-Principles and Applications. (Membrane Science
and Technology Series, Volume 2). Amsterdam, Netherlands : Elsevier Science
B.V., 1995, Kapitel Chapter 14, S. 669712
[2] Sengupta, Amitava ; Sirkar, Kamalesh K.: Analysis and design of membrane
permeatiors for gas separation. In: Noble, Richard D. (Hrsg.) ; Stern, S. A.
(Hrsg.): Membrane Separations Technology-Principles and Applications. (Membrane Science and Technology Series, Volume 2). Amsterdam, Netherlands : Elsevier Science B.V., 1995, Kapitel Chapter 11, S. 499552
[3] Mulder, Marcel: Basic Principles of Membrane Technology. 2nd ed. The Netherlands : Kluwer Academic Publishers, 2000
[4] Sutherland, Ken: Filters and filtration handbook.
Heinemann, 2008. 68 S
5th ed.
Butterworth-
[5] Koltuniewicz, Andrzej B. ; Drioli, Enrico: Membranes in Clean Technologies:

Volume 1 - Theory and Practice. Weinheim, Germany : WILEY-VCH Verlag
GmbH & Co. KGaA, 2008
[6] Noble, Richard D. ; Terry, Patricia A. ; Varma, Arvind (Hrsg.): Principles of Chemical Separations with Environmental Applications. United Kingdom :
Cambridge University Press, 2004
[7] Service, Robert F.: HYDROGEN POWER: Bringing Fuel Cells Down to Earth.
In: Science 285 (1999), July, Nr. 5428, S. 682 685
[8] Sea, Bongkuk ; Lee, Kew-Ho: Modification of Mesoporous -Alumina with Silica
and Application for Hydrogen Separation at Elevated TemperSea2001ature. In:
Journal Industrial & Engineering Chemistry Research 7 (2001), September, Nr.
6, S. 417423
[9] Ismail, Ahmad F. ; Ridzuan, Norida ; Rahman, Sunariti A.: Latest development on the membrane formation for gas separation. In: Songklanakarin Journal
of Science and Technology 24 (2002), April, S. 10251043
98
Bibliography
[10] Gavalas, George R.: Diffusion in Microporous Membranes: Measurements and

Modeling. In: Industrial & Engineering Chemistry Research 47 (2008), July, Nr.
16, S. 57975811
[11] Meinema, Harry A. ; Dirrix, Ruud. W. ; Brinkman, H.w. ; Terpstra, R.A. ;
Jekerle, Jiri ; Ksters, P.H.: Ceramic Membranes for Gas Separation - Recent
Developments and State of the Art. In: Interceram 54 (2005), Nr. 2, S. 8691
[12] Bernardo, P. ; Drioli, E. ; Golemme, G.: Membrane Gas Separation: A
Review/State of the Art. In: Industrial & Engineering Chemistry Research 48
(2009), April, Nr. 10, S. 46384663
[13] Al-Rabiah, A.A.: Membrane Technology for Hydrogen Separation in Ethylene
Plants. In: 4th Ibero-American Congress on Membrane Science and Technology
(CITEM), 2003
[14] Mottern, M. L. ; Shi, J. Y. ; Shqau, K. ; Yu, D. ; Verweij, Henk: Microstructural Optimization of Thin Supported Inorganic Membranes for Gas and
Water Purification. In: Li, Norman N. (Hrsg.) ; Fane, Anthony G. (Hrsg.) ; Ho,
W. S. W. (Hrsg.) ; Matsuura, T. (Hrsg.): Advanced Membrane Technology and
Applications. New Jersey, the United states of America : John Wiley & Sons, Inc.,
2008. 903, Kapitel Chapter 34, S. 899928
[15] Keizer, Klaas ; Uhlhorn, Robert J. ; Burggraaf, Ton J.: Gas separation using inorganic membranes. In: Noble, Richard D. (Hrsg.) ; Stern, S. A. (Hrsg.):
Membrane Separations Technology-Principles and Applications. (Membrane Science and Technology Series, Volume 2). Amsterdam, Netherlands : Elsevier Science B.V., 1995, Kapitel Chapter 12, S. 553588
[16] Cen, Y. ; Lichtenthaler, R.N.: Vapor permeation. In: Noble, Richard D.
(Hrsg.) ; Stern, S. A. (Hrsg.): Membrane Separations Technology-Principles and
Applications. (Membrane Science and Technology Series, Volume 2). Amsterdam,
Netherlands : Elsevier Science B.V., 1995, Kapitel Chapter 3, S. 85112
[17] Williams, P. J. ; Koros, William J.: Gas Separation by Carbon Membranes.
In: Li, Norman N. (Hrsg.) ; Fane, Anthony G. (Hrsg.) ; Ho, W. S. W. (Hrsg.) ;
Matsuura, T. (Hrsg.): Advanced Membrane Technology and Applications. New
Jersey, the United states of America : John Wiley & Sons, Inc., 2008. 601,
Kapitel Chapter 23, S. 599631
[18] Javaid, Asad: Membranes for solubility-based gas separation applications. In:
Chemical Engineering Journal 112 (2005), September, Nr. 1-3, S. 219226
[19] Adhikari, Sushil ; Fernando, Sandun: Hydrogen Membrane Separation Techniques. In: Industrial & Engineering Chemistry Research 45 (2006), January, Nr.
3, S. 875881
Bibliography
99
[20] Wu, Jeffrey Chi-Sheng: Feasibility of Manufacturing Hydrogen and Styrene

through the Use of Porous Ceramic Membranes. In: Industrial & Engineering
Chemistry Research 38 (1999), September, Nr. 11, S. 44914495
[21] Merkel, T. C. ; Bondar, V. I. ; Nagai, K. ; Freeman, B. D. ; Pinnau, I.:
Gas Sorption, Diffusion, and Permeation in Poly(dimethylsiloxane). In: Journal
of Polymer Science: Part B: Polymer Physics 38 (2000), S. 415434
[22] Kusuma, Victor A. ; Freeman, Benny D. ; Jose-Yacaman, Miguel: Structure/Property Characteristics of Polar Rubbery Membrane for Carbon Dioxide
Removal. In: Li, Norman N. (Hrsg.) ; Fane, Anthony G. (Hrsg.) ; Ho, W. S. W.
(Hrsg.) ; Matsuura, T. (Hrsg.): Advanced Membrane Technology and Applications. New Jersey, the United states of America : John Wiley & Sons, Inc., 2008.
934, Kapitel Chapter 35, S. 929953
[23] Li, Yan-Shuo ; Liang, Fang-Yi ; Bux, Helge ; Feldhoff, Armin ; Yang, WeiShen ; Caro, Jrgen: Molecular Sieve Membrane: Supported Metal-Organic
Framework with High Hydrogen Selectivity. In: Angewandte Chemie International
Edition 49 (2010), S. 548 551
[24] Itta, Arun K. ; Tseng, Hui-Hsin ; Weya, Ming-Yen: Effect of dry/wet-phase
inversion method on fabricating polyetherimide-derived CMS membrane for H2 /N2
separation. In: international journal of hydrogen energy 35 (2010), S. 16501658
[25] Krantz, William B.: Membrane Characterization by Ultrasonic Time-Domain
Reflectometry. In: Li, Norman N. (Hrsg.) ; Fane, Anthony G. (Hrsg.) ; Ho,
W. S. W. (Hrsg.) ; Matsuura, T. (Hrsg.): Advanced Membrane Technology and
Applications. New Jersey, the United states of America : John Wiley & Sons, Inc.,
2008. 889, Kapitel Chapter 33, S. 879897
[26] Vieth, Wolf R.: Diffusion in and through polymers: principles and applications.
Munich : Hanser, 1991
[27] Suloff, Eric C.: Sorption Behavior of an Aliphatic Series of Aldehydes in the
Presence of Poly (ethylene terephthalate) Blends Containing Aldehyde Scavenging
Agents, Food Science and Technology, Diss., 2002
[28] Dhingra, Sukhtej S.: Mixed Gas Transport Study Through Polymeric Membranes: a Novel Technique, Virginia Polytechnic Institute, Diss., 1997
[29] Pandey, Pratibha ; Chauhan, R. S.: Membranes for gas separation. In: Progress
in Polymer Science 26 (2001), S. 853893
[30] Kase, Yoji: Gas Separation by Polyimide Membranes. In: Li, Norman N. (Hrsg.)
; Fane, Anthony G. (Hrsg.) ; Ho, W. S. W. (Hrsg.) ; Matsuura, T. (Hrsg.):
Advanced Membrane Technology and Applications. New Jersey, the United states
of America : John Wiley & Sons, Inc., 2008, Kapitel Chapter 22, S. 581598
100
Bibliography
[31] Baker, Richard W.: Membrane Technology and Applications. 2nd ed. Wiley,
New York : John Wiley & Sons, Ltd., 2004
[32] Spillman, Robert: Economics of gas separation membrane processes. In: Noble,
Richard D. (Hrsg.) ; Stern, S. A. (Hrsg.): Membrane Separations TechnologyPrinciples and Applications. (Membrane Science and Technology Series, Volume
2). Amsterdam, Netherlands : Elsevier Science B.V., 1995, Kapitel Chapter 13,
S. 589667
[33] Sebastin, Vctor ; Lin, Zhi ; Rocha, Joao ; Tllez, Carlos ; Santamara,
Jess ; Coronas, Joaqun: A new titanosilicate umbite membrane for the separation of H2 . In: Chemical Communications 24 (2005), April, S. 30363037
[34] Hayes, Richard A.: Polyimide Gas Separation Membrne. Nov. 1989. Appl. No.:
136846
[35] Graham, Tommy E. ; MacLean, Donald L. Process for Hydrogen Recovery from
Ammonla Purge Gases. Dec. 1979
[36] Thomas, George ; Parks, George: Potential Roles of Ammonia in a Hydrogen
Economy-A Study of Issues Related to the Use Ammonia for On-Board Vehicular
Hydrogen Storage / U.S. Department of Energy. 2006. Forschungsbericht
[37] Whysall, Michael ; Picioccio, Kathy W. Selection and Revamp of Hydrogen
Purification Processes. March 1999
[38] Yamashiro, H. ; Hirajo, M. ; Maitland, C.F. ; Schell, W.J.: Plant uses
membrane separation. In: Hydrocarbon Process 64 (1985), Feb., Nr. 2, S. 8789
[39] Olsson, David: Comparisson of Reforming Process Between Different Types of
Biogas Reforming Reactors / Dept. of Energy Sciences, Faculty of Engineering,
Lund University,. Sweden, May 2008. Forschungsbericht
[40] Hedstrm, L. ; Wallmark, C. ; Alvfors, P. ; Rissanen, M. ; Stridh, B.
; Ekman, J.: Description and modelling of the solar-hydrogen-biogas-fuel cell
system in GlashusEtt / Royal Institute of Technology, KTH Chemical Engineering
and Technology. 2003. Forschungsbericht
[41] Bisio, Giacomo ; Bosio, Alessandro ; Rubatto, Giuseppe: Thermodynamics
applied to oxygen enrichment of combustion air. In: Energy Conversion and
Management 43 (2002), November, S. 25892600
[42] Clark, G.A. ; Rowan, M.J.: A Feasibility Study of Using Oxygen Enrichment
for Fuel Cell Air Independent Propulsion / Aeronautical and Maritime Research
Laboratory. Melbourne, August 1996. Forschungsbericht
[43] Metz, S.J. ; van de Ven, W.J.C. ; Potreck, J. ; Mulder, M.H.V. ;
Wessling, M.: Transport of water vapor and inert gas mixtures through highly
Bibliography
101
selective and highly permeable polymer membranes. In: Journal of Membrane

Science 251 (2005), April, S. 2941
[44] TABE-MOHAMMADI, ABDULREZA: A Review of the Applications of Membrane Separation Technology in Natural Gas Treatment. In: SEPARATION SCIENCE AND TECHNOLOGY 34 (1999), Nov., Nr. 10, S. 20952111
[45] Baker, Richard W. ; Lokhandwala, Kaaeid: Natural Gas Processing with
Membranes: An Overview. In: Industrial & Engineering Chemistry Research 47
(2008), Nr. 7, S. 21092121
[46] Pan, C. Y.: Gas separation by permeators with high-flux asymmetric membranes.
In: AIChE Journal 29 (1982), August, Nr. 4, S. 545 552
[47] Majumdar, S. ; Bhaumik, D. ; Sirkar, K. K. ; Simes, G.: A pilot-scale
demonstration of a membrane-based absorption- stripping process for removal and
recovery of volatile organic compounds. In: Environmental Progress 20 (2004),
April, Nr. 1, S. 2735
[48] Dickenson, T. C.: Filters and Filtration Handbook. 4th ed. United Kingdom :
Elsevier A.T., 1997
[49] Hoffman, E. J.: Membrane Separations Technology: Single-Stage, Multistage,
and Differential Permeation. United States of America : Gulf Professional Publishing, 2003
[50] Kim, Young-Seok ; Kusakabe, Katsuki ; Morooka, Shigeharu ; Yang, SeungMan: Preparation of Microporous Silica Membranes for Gas Separation. In:
Korean Journal of Chemical Engineering 18 (2001), Nr. 1, S. 106112
[51] de Vos, Renate M. ; Verweij, Henk: High-Selectivity, High-Flux Silica Membranes for Gas Separation. In: Science 279 (1998), Nr. 5357, S. 17101711
[52] Petersa, T.A. ; Fontalvoa, J. ; Vorstmana, M.A.G. ; Benesa, N.E. ; van
Damb, R.A. ; Vroonb, Z.A.E.P. ; van Soest-Vercammenc, E.L.J. ; Keurentjesa, J.T.F.: Hollow fibre microporous silica membranes for gas separation and
pervaporation: Synthesis, performance and stability. In: Journal of Membrane
Science 248 (2005), S. 7380
[53] Park, Ho B. ; Lee, Young M.: Pyrolytic carbon-silica membrane: a promising
membrane material for improved gas separation. In: Journal of Membrane Science
213 (2003), March, Nr. 1-2, S. 263272
[54] Casanave, D. ; Ciavarella, P. ; Fiaty, K. ; Dalmon, J.-A.: Zeolite membrane reactor for isobutane dehydrogenation: Experimental results and theoretical
modelling. In: Chemical Engineering Science 54 (1999), S. 28072815
102
Bibliography
[55] Vankelecom, I. F. J. ; Dotremont, C. ; Morobe, M. ; Uytterhoeven,

J.-B. ; ; Vandecasteele, C.: Zeolite-Filled PDMS Membranes: 1. Sorption of
Halogenated Hydrocarbons. In: The Journal of Physical Chemistry B 101 (1997),
Nr. 12, S. 21542159
[56] Vankelecom, Ivo F. J. ; Merckx, Edouard ; Luts, Mark ; Uytterhoeven,
Jan B.: Incorporation of zeolites in polyimide membranes. In: The Journal of
Physical Chemistry 99 (1995), Nr. 35, S. 1318713192
[57] Yang, Jianhua ; ermkov, Jiina ; Uchytil, Petr ; Hamel, Christof ;
Seidel-Morgenstern, Andreas: Gas phase transport, adsorption and surface
diffusion in a porous glass membrane. In: Catalysis Today 104 (2005), S. 344351
[58] Jirage, Kshama B. ; Martin, Charles R.: New developments in membrane-based
separations. In: TIBTECH 17 (1999), May, S. 197200
[59] Mottern, M.L. ; Shqau, K. ; Shi, J.Y. ; Yu, D. ; Verweij, Henk: Thin
supported inorganic membranes for energy-related gas and water purification. In:
International Journal of Hydrogen Energy 32 (2007), S. 37133723
[60] Miller, James R. ; Koros, William J.: The formation of chemically modified
-alumina microporous membranes. In: SEPARATION SCIENCE AND TECHNOLOGY 25 (1990), Nr. 13-15, S. 12571280
[61] Wei, Qi ; Wang, Fei ; Nie, Zuo-Ren ; Song, Chun-Lin ; Wang, Yan-Li ; QunYan: Highly Hydrothermally Stable Microporous Silica Membranes for Hydrogen
Separation. In: The Journal of Physical Chemistry B 112 (2008), July, Nr. 31, S.
93549359
[62] Li, Kang: Ceramic Membranes for Separation and Reaction. West Sussex, England
: John Wiley & Sons, Ltd., 2007
[63] Zhang, Yuwen ; Li, Qian ; Shen, Peijun ; Liu, Yong ; Yang, Zhibin ; Ding,
Weizhong ; Lu, Xionggang: Hydrogen amplification of coke oven gas by reforming
of methane in a ceramic membrane reactor. In: INTERNATIONAL JOURNAL
OF HYDROGEN ENERGY 33 (2008), S. 33113319
[64] Ma, Yi H.: Hydrogen Separation Membranes. In: Li, Norman N. (Hrsg.) ; Fane,
Anthony G. (Hrsg.) ; Ho, W. S. W. (Hrsg.) ; Matsuura, T. (Hrsg.): Advanced
Membrane Technology and Applications. New Jersey, the United states of America
: John Wiley & Sons, Inc., 2008, Kapitel Chapter 25, S. 671684
[65] Balachandran, U. ; Lee, T.H. ; Chen, S.J.and Picciolo J. ; Dorris, S.E.:
Hydrogen permeation and chemical stability of dense hydrogen separation membranes. In: Proceedings of the 22nd Annual International Pittsburgh Coal Conference. PA, Pittsburgh, Sept. 2005
Bibliography
103
[66] Peinemann, Klaus-Viktor ; Numes, Suzana P.: Membrane Technology: Volume

2 - Membranes for Energy Conversion. Weinheim : Wiley-VCH Verlag GmbH &
C. KGaA, 2008
[67] Ayturk, M. E. ; Engwall, Erik E. ; Ma, Y. H.: Microstructure Analysis of the
Intermetallic Diffusion Induced Alloy Phases in Composite P d/Ag/Porous Stainless Steel (PSS) Membranes. In: Industrial & Engineering Chemistry Research
(ACS Publications) 46 (2007), Nr. 12, S. 42954306
[68] Li, Anwu ; Liang, Weiqiang ; Hughes, Ronald: Fabrication of Defect-free P d/Al2 O3 composite membranes for hydrogen separation. In: Thin Solid Films 350
(1999), March, S. 106112
[69] Zhao, H.-B. ; Xiong, G.-X. ; Baron, G.V.: Preparation and Characterization
of Palladium-based Composite Membranes by Electroless Plating and Magnetron
Sputtering. In: Catalysis Today 56 (2000), S. 8996
[70] Wang, Li ; Bao, Shiguo ; Yi, Jianhua ; He, Fei ; Mi, Zhentao: Preparation
and Properties of P d/Ag Composite Membrane for Direct Synthesis of Hydrogen
Peroxide from Hydrogen and Oxygen. In: Applied Catalysis B: Environmental 79
(2008), S. 157162
[71] Wang, Dan ; Tong, Jianhua ; Xub, Hengyong ; Matsumura, Yasuyuki: Preparation of Palladium Membrane over Porous Stainless Steel Tube Modified with
Zirconium Oxide. In: Catalysis Today 93-95 (2004), S. 689693
[72] Kleinlogel, C. ; Gauckler, L.J.: Sintering and properties of nanosized ceria
solid solutions. In: Solid State Ionics 135 (2000), S. 567573
[73] Cao, Chun ; Chung, Tai-Shung ; Chen, Shing B. ; Dong, ZhengJun: The study
of elongation and shear rates in spinning process and its effect on gas separation
performance of Poly(ether sulfone) (PES) hollow fiber membranes. In: Chemical
Engineering Science 59 (2004), S. 10531062
[74] van Oss, Hendrik G.: Background Facts and Issues Concerning Cement and
Cement Data / U.S. Department of the Interior and U.S. Geological Survey. 2005
( 2005-1152). Forschungsbericht
[75] Baker, Richard W.: Future Directions of Membrane Gas Separation Technology.
In: Industrial & Engineering Chemistry Research 41 (2002), February, Nr. 6, S.
13931411
[76] Walawender, W. P. ; Stern, S. A.: Analysis of Membrane Separation Parameters. II. Countercurrent and Cocurrent Flow in a Single Permeation Stage. In:
Separation Science and Technology 7(5) (1972), S. 553584
[77] Gallucci, Fausto ; Basile, Angelo: Co-current and counter-current modes for
Methanol Steam Reforming Membrane Reactor. In: Proceedings International
Hydrogen Energy Congress and Exhibition. Istanbul, Turkey, July 2005
104
Bibliography
[78] Koros, W. J. ; Mahajan, R.: Pushing the Limits on Possibilities for Large Scale
gas Separation: Which Strategies? In: Journal of Membrane Science 175 (2000),
Nr. 2, S. 181196
[79] Abell, A. B. ; Willis, K. L. ; Lange, D. A.: Mercury Intrusion Porosimetry and
Image Analysis of Cement-Based Materials. In: Journal of Colloid and Interface
Science 211 (1999), S. 3944
[80] Gupta, Pardeep K. ; Troy, David B. (Hrsg.): Remington: the science and
practice of pharmacy. 21st ed. Lippincott Williams & Wilkins, 2005. 608 S
[81] Minter, Clarke C.: Thermal Conductivity of Binary Mixtures of Gases. In: The
Journal of Physical Chemietry 72 (1968), S. 19241926
[82] Mukhopadhyay, P. ; Barua, A. K.: Thermal conductivity of hydrogen-helium
gas mixtures. In: British Journal of Applied Physics 18 (1967), S. 635
[83] Reinecke, Stefan A.: The Effect of Water Content on Knudsen Diffusion in
Unconsolidated Porous Media, Applied Science Graduate Department of Civil Engineering University of Toronto, Diplomarbeit, 2000
[84] Khayet, Mohamed: Membrane Distillation. In: Li, Norman N. (Hrsg.) ; Fane,
Anthony G. (Hrsg.) ; Ho, W. S. W. (Hrsg.) ; Matsuura, T. (Hrsg.): Advanced
Membrane Technology and Applications. New Jersey, the United states of America
: John Wiley & Sons, Inc., 2008, Kapitel Chapter 12, S. 297370
[85] Chiang, Hung-Lung ; Tsai, Jiun-Horng ; Chang, Dai-Huang ; Jeng, Fu-Teng:
Diffusion of hydrogen sulfide and methyl mercaptan onto microporous alkaline
activated carbon. In: Chemosphere 41 (2000), S. 12271232
[86] Pavlin, Tina: Hyperpolarized Gas Polarimetry and Imaging at Low Magnetic
Field, California Institute of Technology, Diss., 2003
[87] Bernal, M. P. ; Coronas, J. ; Menndez, M. ; Santamara, J.: Separation
of CO2 /N2 Mixtures Using MFI-Type Zeolite Membranes. In: American Institute
of Chemical Engineers 50 (2004), S. 127135
[88] Seader, J. D. ; Henley, Ernest J. ; Welter, Jennifer (Hrsg.) ; McFadden,
Patricia (Hrsg.): Separation Process Principles. 2nd ed. Hoboken, United States
of America : John Wiley & Sons, Inc., 2006
[89] Nel, J.: Pervaporation. In: Noble, Richard D. (Hrsg.) ; Stern, S. A. (Hrsg.):
Membrane Separations Technology-Principles and Applications. (Membrane Science and Technology Series, Volume 2). Amsterdam, Netherlands : Elsevier Science B.V., 1995, Kapitel Chapter 5, S. 143211
[90] Asano, Koichi: Mass TransferFrom Fundamentals to Modern Industrial Applications. Weinheim, Germany : WILEY-VCH Verlag GmbH & Co. KGaA, 2006
Bibliography
105
[91] Nelson, Philip: Biological Physics: Energy, Information, Life. New York : W.
H. Freeman and Company, 2008
[92] Baker, Richard W.: Vapor and Gas Separation by Membranes. In: Li, Norman N. (Hrsg.) ; Fane, Anthony G. (Hrsg.) ; Ho, W. S. W. (Hrsg.) ; Matsuura,
T. (Hrsg.): Advanced Membrane Technology and Applications. New Jersey, the
United states of America : John Wiley & Sons, Inc., 2008, Kapitel Chapter 21, S.
559580
[93] Guo, Jia ; Heslop, Mark J.: Diffusion Problems of Soap-Film Flowmeter When
Measuring Very Low-Rate Gas Flow. In: Flow Measurement and Instrumentation
15 (2004), S. 331334
[94] Huang, R. Y. M. ; Yeom, C. K.: Pervaporation separation of aqueous mixtures
using crosslinked polyvinyl alcohol membranes. III. Permeation of acetic acid-water
mixtures. In: Journal of Membrane Science 58 (1991), S. 3347
[95] Kim, Sang-Gyun ; Lee, Ki-Sub ; Lee, Kew-Ho: Pervaporation Separation of
Sodium Alginate/Chitosan Polyelectrolyte Complex Composite Membranes for
the Separation of Water/Alcohol Mixtures: Characterization of the Permeation
Behavior with Molecular Modeling Techniques. In: Journal of Applied Polymer
Science 103 (2007), S. 26342641
[96] Lin, Jerry Y. ; Cheng, Scott ; Gupta, Vineet: Proton-Conducting Dense Ceramic Membranes for Hydrogen Separation / Department of Chemical Engineering, University of Cincinnati. 2003. Forschungsbericht
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Experimental Investigation on Gas Separation

Using Porous Membranes

von der Fakultt III - Prozesswissenschaften

Doktorin der Ingenieurwissenschaften

Prof. Dr.-Ing. Felix Ziegler

Prof. Dr. Frank Behrendt

Prof. Dr.-Ing. Bernd Hillemeier

Tag der wissenschaftlichen Aussprache: 03. December 2010

2 State of the Art

An introduction to gas separation using membranes . . . . . . . . . . .

Dense inorganic membranes . . . . . . . . . . . . . . . . . . . .

Porous inorganic membranes . . . . . . . . . . . . . . . . . . . .

Porous cement membranes . . . . . . . . . . . . . . . . . . . . . . . . .

Separation and process design . . . . . . . . . . . . . . . . . . . . . . .

Possible flow patterns . . . . . . . . . . . . . . . . . . . . . . . .

Known influence of operating parameters . . . . . . . . . . . . .

Operating parameters and procedure . . . . . . . . . . . . . . . . . . .

The fundamental equations for ideal gases . . . . . . . . . . . .

Equations for transport mechanisms through porous membranes . . . .

Equations for the experimental setup . . . . . . . . . . . . . . . . . . .

Soap film flowmeter . . . . . . . . . . . . . . . . . . . . . . . . .

Mass flow controller . . . . . . . . . . . . . . . . . . . . . . . . .

Efficiency of gas separation through membrane . . . . . . . . . . . . . .

5 Experimental Results and Discussion

Controlling equipment and corresponding special procedures, calibration

Data correction of mass flow controller . . . . . . . . . . . . . .

Calibration of gas chromatograph (GC ) . . . . . . . . . . . . .

First set of experiments with Gaggls membranes . . . . . . . .

Second set of experiments with modified cell . . . . . . . . . . .

Third set of experiments with tubular membrane and cell . . . .

6 Summary and Outlook

Schematic representation of membrane separation . . . . . . . . . . . .

Transport mechanisms in porous membranes [1] . . . . . . . . . . . . .

Schematics of possible flow patterns [2, 3] . . . . . . . . . . . . . . . . .

Flow pattern in presence of sweep gas [2] . . . . . . . . . . . . . . . . .

Schemes of commercial two-stage separation [2, 3] . . . . . . . . . . . .

Schemes of commercial three-stage separation [2, 3] . . . . . . . . . . .

Novel single-stage separation with recycling [2, 3] . . . . . . . . . . . . .

Process schematic of gas separation . . . . . . . . . . . . . . . . . . . .

Process schematic of reference measurements . . . . . . . . . . . . . . .

Gas chromatographic system . . . . . . . . . . . . . . . . . . . . . . . .

Chromatogram of five-component gas . . . . . . . . . . . . . . . . . . .

LabVIEW controlling system . . . . . . . . . . . . . . . . . . . . . . .

Chromatograms of two-component gas and pure standard-gases . . . .

Flow rate of two-component gas at 2.4 bar . . . . . . . . . . . . . . . .

Flow rate of two-component gas at different pressures . . . . . . . . . .

Base line of chromatogram . . . . . . . . . . . . . . . . . . . . . . . . .

Area of H2 in two-component gas measurements with different run times 47

Area of pure H2 measurements at different temperatures . . . . . . . .

GC measurements of different reference-flow rate . . . . . . . . . . . . .

N2 amount and flow rates in automatic injection . . . . . . . . . . . . .

5.10 Flow rate calculation of standard-gases . . . . . . . . . . . . . . . . . .

5.11 Pure H2 peak area for calibration of 2M measurement . . . . . . . . . .

5.12 Calibration curve for H2 of 2M measurement . . . . . . . . . . . . . . .

5.13 Schematic of the first idea . . . . . . . . . . . . . . . . . . . . . . . . .

5.14 Schematic of the first membrane cell . . . . . . . . . . . . . . . . . . .

5.15 The first membrane cell and holders . . . . . . . . . . . . . . . . . . . .

5.16 Pore size distribution of the first membranes . . . . . . . . . . . . . . .

5.17 Gaskets for the first membrane cell . . . . . . . . . . . . . . . . . . . .

5.18 Flow rate influence at different temperatures . . . . . . . . . . . . . . .

5.19 Gas separation with different volume flows . . . . . . . . . . . . . . . .

5.20 Gas separation with different feed gases . . . . . . . . . . . . . . . . . .

5.21 Experimental and theoretic selectivity . . . . . . . . . . . . . . . . . . .

5.22 Problem of the first membrane cell . . . . . . . . . . . . . . . . . . . .