Linde Engineering Industrial Hydrogen Production & Technology Dr. Klemens Wawrzinek, Claude Keller HDV, November 21, 2007, Karlsruhe, FuncHy-Workshop
Linde Engineering
Industrial Hydrogen Production & Technology
Dr. Klemens Wawrzinek, Claude KellerHDV, November 21, 2007, Karlsruhe, FuncHy-Workshop
Linde Engineering
2 K. Wawrzinek/ HDV / Nov. 21, 2007 /Industrial H2 Production & Technology.pptLinde AG Linde Engineering Division
Industrial Hydrogen Production & Technology
— Linde Engineering´s Key Plant Types
— Hydrogen Market
— Feedstocks
— Technology: Syngas Generation, Product Recovery
— Summary
Overview
Linde Engineering
3 K. Wawrzinek/ HDV / Nov. 21, 2007 /Industrial H2 Production & Technology.pptLinde AG Linde Engineering Division
Linde EngineeringKey Plant Types
Air Separation PlantsHydrogen and Synthesis Gas Plants
— Products:
— Oxygen
— Nitrogen
— Rare gases
— Products:
— H2/CO/Syngas
— Ammonia
— Gas removal
— Gas purification
Olefin Plants— Products:
— LNG
— NGL
— LPG
— Helium
Natural Gas Plants
Products:
— Ethylene
— Propylene
— Butadiene
— Aromatics
— Polymers
Linde Engineering
4 K. Wawrzinek/ HDV / Nov. 21, 2007 /Industrial H2 Production & Technology.pptLinde AG Linde Engineering Division
Industrial Hydrogen Market
Increase of World Oil Consumption
Decline of Overall Crude Oil Quality
More Stringent Environmental Standards
New Applications(Automotive fuel, Fuel cell)
Hydrogen Consumers: Trends shaping futureHydrogen demand:
Ammonia
Electronic Industry
Metal- / Glass Industry
Food Industry
Chemical Industry /Refineries
35 %
6 %3 %2 %
54 %
Installed capacity worldwide: 600 Billion Nm³/year
Linde Engineering
5 K. Wawrzinek/ HDV / Nov. 21, 2007 /Industrial H2 Production & Technology.pptLinde AG Linde Engineering Division
Feedstocks
Refinery Gases
LPG (Propane, Butane)
Natural Gas (48 %)
Naphtha
Light Hydrocarbons
Fuel Oil (30 %)
Vacuum Tar
Asphalt
Petroleum Coke
Coal (18 %)
Heavy Hydrocarbons
Steam Reforming
Partial Oxidation
Process
Partial Oxidation
Process
Linde Engineering
6 K. Wawrzinek/ HDV / Nov. 21, 2007 /Industrial H2 Production & Technology.pptLinde AG Linde Engineering Division
Synthesis Gas Generation Principles
0
2
4
6
8
10
12
0 0.2 0.4 0.6 0.8 1 1.2Oxygen Excess Ratio λ
Stea
m t
o Ca
rbon
Rat
io
CombustionSyngas
Production
Steam Reforming (SR)Catalytic
Pyrolysis
Partial Oxidation (POX)
Non-Catalytic
Autothermal Reforming (ATR)
Catalytic
Linde Engineering
7 K. Wawrzinek/ HDV / Nov. 21, 2007 /Industrial H2 Production & Technology.pptLinde AG Linde Engineering Division
Reactions
Non Oxygen Consuming:
• Steam Methane Reforming (SMR) CH4 + H2O → CO + 3 H2 endothermal
• Carbon Monoxide Conversion (CO-Shift)CO + H2O → CO2 + H2 exothermal
Oxygen Consuming
• Hydrocarbon ConversionCnHm + n/2 O2 → nCO + m/2 H2 exothermal
• H2 Oxidation2 H2 + O2 → 2 H2O exothermal
• Carbon Monoxide Oxidation 2 CO + O2 → 2 CO2 exothermal
Steam Reforming
Partial Oxidation, AutothermalReforming
• Synthesis Gas contains H2, CO, H2O, CO2, unreacted Hydrocarbons, Impurities• Requested Products are H2, CO, CO+H2• H2 Separation + Purification required
Linde Engineering
8 K. Wawrzinek/ HDV / Nov. 21, 2007 /Industrial H2 Production & Technology.pptLinde AG Linde Engineering Division
Typical Basic Block Diagrams forH2 Production
Feed Pre-treatment
SteamReforming
HeatRecovery CO-Shift
PressureSwing
Adsorption
Steam
Feed
Fuel
Export Steam
Hydrogen
Fuel Gas
Light Hydrocarbons
Heavy Hydrocarbons
FeedPreparation
PartialOxidation
CO-Shift/Heat Recovery
CO2,H2S,COSRemoval
PressureSwing
Adsorption
Oxygen
Steam
Feed
Export Steam
Hydrogen
Fuelgas
CO2-Byproduct
Sulphur
Linde Engineering
9 K. Wawrzinek/ HDV / Nov. 21, 2007 /Industrial H2 Production & Technology.pptLinde AG Linde Engineering Division
Steam Reformer
Syngas ~850°C, 20 - 30 bar, ~70 % H2 in dry gas
Hydrocarbon + Steam
Reformer Tubes Flue
Gas
Burners
Linde Engineering
10 K. Wawrzinek/ HDV / Nov. 21, 2007 /Industrial H2 Production & Technology.pptLinde AG Linde Engineering Division
Partial Oxidation/Autothermal Reforming Reactors
ATR (Natural Gas) POX (All Feedstocks)Oxygen Oxygen
Synthesis gas: H2 in dry gas ~ 61 %
Feedstock+ steam
FeedstockCombustionchamber
Catalystbed
Combustionchamber
30 – 70 bar~1400 °C
Synthesis gas: H2 in dry gas ~ 65 %
~35 bar~1000 °C
Linde Engineering
11 K. Wawrzinek/ HDV / Nov. 21, 2007 /Industrial H2 Production & Technology.pptLinde AG Linde Engineering Division
CO-Shift Reactor
• Shifts undesired CO to H2CO + H2O → CO2 + H2 exothermal
• Simple catalytic reactor
• CO conversion depends on TemperatureHigh Temperature Shift: ~ 75 %Low Temperature Shift: ~ 90%
• H2 in dry gas ~ 75 %
Linde Engineering
12 K. Wawrzinek/ HDV / Nov. 21, 2007 /Industrial H2 Production & Technology.pptLinde AG Linde Engineering Division
Rectisol® Wash Unit forPOX Synthesis Gas
• e.g. for Syngas from Coal Gasification
• Methanol as washing solvent
• Rectisol® process separates CO2, H2S, COS
• H2 Purity ~ 98 %
Linde Engineering
13 K. Wawrzinek/ HDV / Nov. 21, 2007 /Industrial H2 Production & Technology.pptLinde AG Linde Engineering Division
H2 Purification: Pressure Swing Adsorption
Pressure Swing Adsorptionfor high Purity H2
based on selective adsorptionusing different kinds of adsorption materials (e.g. molecular sieves)
H2 Purity up to 99.9999 %
H2 Recovery up to 90 %
Linde Engineering
14 K. Wawrzinek/ HDV / Nov. 21, 2007 /Industrial H2 Production & Technology.pptLinde AG Linde Engineering Division
Summary
— Major Hydrogen Market is Chemical Industry
— Feedstocks are Hydrocarbons from Methane to Coal
— Syngas Generation by Steam Reforming, Partial Oxidation, Autothermal
Reforming, and CO-Shift Conversion
— H2 Separation from Syngas and Purification depend on Demand and
Syngas Process
Linde Engineering
Thank youfor your attention