Professional Documents
Culture Documents
RJ Allam
Air Products
Why Hydrogen?
3
Production of Hydrogen
Options
Method Characteristics
Photolysis catalytic-water splitting
Electrolysis water
Power for electrolyser ambient → high temperature
ambient → high pressure
Thermal splitting water
high temperature
≡m conc as function of temp freeze equilibrium
Fossil fuel Conversion Heat, water, oxygen, catalytic
Far Future Non fossil fuel alternatives based
on sunlight, renewables and
nuclear
Present Fossil fuels
4
Carbon Containing Fuels
5
Reactions
Reforming With Steam - Catalytic
Natural gas and light CH4 + H2O ↔ CO + 3H2 + ∆H
hydrocarbons
CO + H2O ↔ H2 + CO2 - ∆H
Partial Oxidation - Non Catalytic
Any hydrocarbon or C + ½O2 → CO - ∆H
carbonaceous feedstock
CO + H2O ↔ CO2 + H2 - ∆H
Thermal Decomposition
Only limited application as co- CH4 → 2H2 + C +∆H
product in carbon black
manufacture
6
General Arrangement For CO2-
free Hydrogen Production
Waste Fuel
Gas
7
CO2 Separation Technologies
Capabilities
Adsorption Membrane Absorption Cryogenic
8
H2 Production
Separation Methods
Separation of pure H2 and pure CO2 from syngas
Absorption
Scrubbing with a solvent
Physical solvents: Rectisol – low temperature methanol
Selexol – Polyether
Selective for H2S and CO2 following COS hydrolysis
Favour high partial pressure of impurity
Used primarily when POX coal/tar
9
10
H2 Production
Separation Methods
Separation of pure H2 and pure CO2 from syngas
Adsorption
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12
Process Characteristics
Open Systems
50,000 Nm3/hr
z External heating of a Steam Natural
catalytic reactor
Gas Reformer
z Combustion
products vented to
atmosphere
z CO2-free flue gas
requires H2 fuel for
the furnace, or
z Oxyfuel furnace
operation could be
used.
13
Current Technology
Steam Methane Reforming (SMR)
z Limitations
– Carbon formation at low steam; carbon ratio
– Higher hydrogen pressure limits CH4 conversion
– High CH4 conversion requires high temperature
– Excess steam production
– Cooling by waste heat boiler to limit Bouduard
carbon formation
– Low NOx levels required in stack gas
z Challenges
– Reduce steam to carbon ratio
– Low NOx long flame burners
– Materials limitations in alloys used for tubes
– Reduce excess steam production by air preheat
and pre-reforming
14
Process Characteristics
Closed Systems
15
Current Technology
Autothermal Reformer (ATR)
z Limitations
– Must use a clean, light hydrocarbon feed
– Cost of oxygen
– Limitation in H2 pressure
– Limitation in exit temperature
– Excess steam production
– Needs waste heat boiler to limit Bouduard
carbon formation
z Challenges
– Reduce steam to carbon ratio
– Increase CH4 conversion by increasing temp
– Carbon free burner operation
– Increase in vessel size/throughout
16
Current Technology
Partial Oxidation (POX)
Suitable for any carbonaceous feed – favoured for coal
Many configurations…
z Fixed/moving bed – Lurgi
z Fluidised bed – Winkler
z Entrained bed (1325°C → 1450°C)
– Texaco
• water slurry coal feed
• high pressure: 70 bar
• usually water quench
• favoured for H2 production because of excess H2O present
• combined sour gas CO shift and COS hydrolysis
– Shell
• dry coal feed, nitrogen entrainment
• pressure limitation: 40bar (coal)
• waste heat boiler, higher efficiency
• needs added steam for shift and H2 production
• often configured with a COS hydrolysis reactor upstream of H2S
removal and CO shift reactor downstream of H2S removal
17
CO2-Free Power and
100 bar
CO2
Hydrogen From Coal
Fuelled System
Coal
Water/N2 CO2/H2S
Quench/
Coal Shift Physical
Oxygen Heat H2 Product
Gasification reactors Absorption
Recovery
System
Ash/Slag
H2 for Power H2
Generation Purification
Shell
N2
OXYGEN
Texaco
18
Production of Hydrogen
ATR/GHR Integration
Natural Gas
Steam
z Possibility of using
high temperature Steam
H2/CO/CO2 syngas Oxygen Product
to heat a Gas H2 + CO
Heated Reformer 600°C
(GHR)
z No excess steam
production
1050°C
z Extra 30% H2
production
z Bouduard carbon
formation in GHR ATR Steam Reforming
shell side + (open ended tubes)
19
H2 Production
Emerging Technologies
z Micro reactor/Multichannel Heat
Exchanger
Either
– Low temperature POX
• Air purified
• 45% H2 – fuel cell feed (PEM)
• Followed by direct air/CO
• Oxidation to reduce CO<10ppm
z SMR
– Separate air/fuel gas catalytic combustion passages
and adjacent SMR passages
20
Production of Hydrogen
Plate-Fin Reformer
Catalyst can be a surface
coating or a porous insert.
Metal Metal
Fuel Gas
+ Air
Natural Gas
+ Steam
Metal Metal
21
H2 Production
Emerging Technologies
z Micro reactor/Multichannel Heat Exchanger
In General
– Catalyst can be deposited on metal surfaces or used in a
porous insert
– Removable catalyst elements are possible
– Very high volumetric productivity for SMR reactor
– Whole H2 plant can be integrated with a plate-fin reformer
configuration
Challenges
– Novel arrangements to allow catalyst change out
– Capable of either small scale or very large scale use
– Requires balanced performance between SMR/fuel
combustion
22
ITM Hydrogen/Syngas: A Revolutionary
Technology Using Ceramic Membranes
z Ion Transport Membranes (ITM)
– Non-porous multi-component ceramic membranes
– High oxygen flux and high selectivity for oxygen
– Operate at high temperatures, typically over 700 °C
z ITM Hydrogen/Syngas combines air separation and methane
partial oxidation into a single unit operation, resulting in
significant cost savings
Natural Gas & Steam Syngas
CH4 H2
Oxygen Oxygen
H2O CO
vacancy anion
I TM
Me
mb
CH4 + O2- → CO + 2H2 + 2e-
ran
e
O2- 2e-
Metal
Air Spent Air cation
Nitrogen Oxygen
23
Integrated Development Program
Addresses Key Technical Challenges
with Broad Development Team
24
Advantages of
Planar Membrane Systems
d C O)
H an
(
cts
2
od u
g as Pr
z Compactness Syn al)
e r n
z Good mass and ed (ext
a s Fe
heat transfer
t ur al G
Na
z Amenable to
r nal )
standard (inte
e d
ceramic Fe
Air
processing
Porous Support/
methods
Catalyst
Active Membrane
Flow Channels
z Membrane fabrication
processes are robust
and scaleable
26
ITM Hydrogen/Syngas: Combines Oxygen
Production and Syngas Production Into a Single
Reactor to Achieve Over 30% Capital Cost
Savings
Low
Pressure
Column
Oxygen Conventional Process
Natural N2
(ATR and Air Sep Unit)
Gas Feed O2
Autothermal
Reformer
with Separate Oxygen
Waste
Steam
Main Air Front End Main and Syngas Production
Compressor -
Cleanup Reboiler
High
Pressure
Fuel Feed Preheat Column
and Treatment
Syngas to Main Heat
Exchanger
Over 30% Capital
Product Conversion
Cost Savings
Fuel Air
Natural
Gas Feed
in-line blower
ITM Hydrogen/Syngas Reactor Steam ITM H2/Syngas burner
27
Production of Hydrogen
Simultaneous Separation/Reaction
z Enhanced conversion of feedstock to hydrogen by
removing one of the product continuously
z H2 removal from steam reformer using a palladum diffusion
surface
– low pressure H2, high pressure CO2
CH4 + 2H2O → CO2 + 4H2
CO + H2O → CO2 + H2
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Production of Hydrogen
Steam Electrolysers
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