5 Linde Wawrzinek Funchy-2007

Industrial Hydrogen Production
& Technology
Linde Engineering
Dr. Klemens Wawrzinek, Claude Keller

HDV, November 21, 2007,
Karlsruhe, FuncHy-Workshop
Linde Engineering
Industrial Hydrogen Production &

Technology
Overview
— Linde Engineering´s Key Plant Types
— Hydrogen Market
— Feedstocks
— Technology: Syngas Generation, Product Recovery
— Summary
Linde AG Linde Engineering Division 2 K. Wawrzinek/ HDV / Nov. 21, 2007 /Industrial H2 Production & Technology.ppt
Linde Engineering
Linde Engineering
Key Plant Types
Olefin Plants Natural Gas Plants

Products: — Products:
— Ethylene — LNG
— Propylene — NGL
— Butadiene — LPG
— Aromatics — Helium
— Polymers
Hydrogen and Synthesis Gas Plants Air Separation Plants

— Products: — Products:
— H2/CO/Syngas — Oxygen
— Ammonia — Nitrogen
— Gas removal — Rare gases
— Gas purification
Linde Engineering
Industrial Hydrogen Market
Installed capacity worldwide: 600 Billion Nm³/year
Hydrogen Consumers: Trends shaping future

Hydrogen demand:
Increase of World
Ammonia 54 % Oil Consumption
Decline of Overall
Chemical Industry / 35 % Crude Oil Quality
Refineries
More Stringent
Electronic Industry 6% Environmental Standards
Metal- / Glass Industry 3%
Food Industry 2% New Applications
(Automotive fuel, Fuel cell)
Linde Engineering
Feedstocks
Light Hydrocarbons Heavy Hydrocarbons
Refinery Gases Fuel Oil (30 %)
LPG (Propane, Butane) Vacuum Tar
Natural Gas (48 %) Asphalt
Naphtha Petroleum Coke
Coal (18 %)
Process Process
Steam Reforming Partial Oxidation
Partial Oxidation
Linde Engineering
Synthesis Gas Generation Principles
12
Syngas
10 Production Combustion
Steam to Carbon Ratio
Steam Reforming (SR)

8 Catalytic
6
Autothermal
4 Reforming (ATR)
Catalytic Partial Oxidation
2 (POX)
Non-Catalytic
0
0 0.2 0.4 0.6 0.8 1 1.2
Oxygen Excess Ratio λ
Pyrolysis
Linde Engineering
Reactions
Non Oxygen Consuming:

• Steam Methane Reforming (SMR)
CH4 + H2O → CO + 3 H2 endothermal Steam
• Carbon Monoxide Conversion (CO-Shift) Reforming
CO + H2O → CO2 + H2 exothermal
Oxygen Consuming
Partial Oxidation,
• Hydrocarbon Conversion
Autothermal
CnHm + n/2 O2 → nCO + m/2 H2 exothermal
Reforming
• H2 Oxidation
2 H2 + O2 → 2 H2O exothermal
• Carbon Monoxide Oxidation
2 CO + O2 → 2 CO2 exothermal
• Synthesis Gas contains H2, CO, H2O, CO2, unreacted Hydrocarbons, Impurities
• Requested Products are H2, CO, CO+H2
• H2 Separation + Purification required
Linde Engineering
Typical Basic Block Diagrams for

H2 Production
Light Hydrocarbons
Steam Export Steam
Pressure
Feed Feed Pre- Steam Heat Hydrogen
CO-Shift Swing
treatment Reforming Recovery
Adsorption
Fuel Fuel Gas
Heavy Hydrocarbons
Oxygen Sulphur
Steam Export Steam
Pressure
Feed Feed Partial CO-Shift/ CO2,H2S,COS Hydrogen
Swing
Preparation Oxidation Heat Recovery Removal
Adsorption
Fuelgas
CO2-Byproduct
Linde Engineering
Steam Reformer
Hydrocarbon + Steam
Burners
Reformer
Tubes Flue
Gas
Syngas ~850°C, 20 - 30 bar, ~70 % H2 in dry gas

Linde Engineering
Partial Oxidation/
Autothermal Reforming Reactors
ATR (Natural Gas) POX (All Feedstocks)

Oxygen Oxygen
Feedstock Feedstock
+ steam Combustion Combustion
chamber chamber
30 – 70 bar
~35 bar
Catalyst ~1400 °C
~1000 °C
bed
Synthesis gas: H2 in dry gas ~ 61 %

Synthesis gas: H2 in dry gas ~ 65 %
Linde Engineering
CO-Shift Reactor
• Shifts undesired CO to H2
CO + H2O → CO2 + H2 exothermal
• Simple catalytic reactor
• CO conversion depends on Temperature

High Temperature Shift: ~ 75 %
Low Temperature Shift: ~ 90%
• H2 in dry gas ~ 75 %
Linde Engineering
Rectisol®Wash Unit for

POX Synthesis Gas
• e.g. for Syngas from Coal Gasification
• Methanol as washing solvent
• Rectisol® process separates CO2, H2S, COS
• H2 Purity ~ 98 %
Linde Engineering
H2 Purification:
Pressure Swing Adsorption
Pressure Swing Adsorption

for high Purity H2
based on selective adsorption

using different kinds of
adsorption materials (e.g.
molecular sieves)
H2 Purity up to 99.9999 %
H2 Recovery up to 90 %
Linde Engineering
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
Thank you
for your attention
Linde Engineering

5 Linde Wawrzinek Funchy-2007

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Industrial Hydrogen Production

Dr. Klemens Wawrzinek, Claude Keller

Industrial Hydrogen Production &

— Linde Engineering´s Key Plant Types

— Technology: Syngas Generation, Product Recovery

Olefin Plants Natural Gas Plants

Hydrogen and Synthesis Gas Plants Air Separation Plants

Industrial Hydrogen Market

Installed capacity worldwide: 600 Billion Nm³/year

Hydrogen Consumers: Trends shaping future

Light Hydrocarbons Heavy Hydrocarbons

 Refinery Gases  Fuel Oil (30 %)

 LPG (Propane, Butane)  Vacuum Tar

 Natural Gas (48 %)  Asphalt

 Naphtha  Petroleum Coke

 Steam Reforming  Partial Oxidation

Synthesis Gas Generation Principles

Steam Reforming (SR)

Non Oxygen Consuming:

Typical Basic Block Diagrams for

Steam Export Steam

Fuel Fuel Gas

Steam Export Steam

Syngas ~850°C, 20 - 30 bar, ~70 % H2 in dry gas

ATR (Natural Gas) POX (All Feedstocks)

Synthesis gas: H2 in dry gas ~ 61 %

• Simple catalytic reactor

• CO conversion depends on Temperature

Rectisol®Wash Unit for

• e.g. for Syngas from Coal Gasification

• Methanol as washing solvent

• Rectisol® process separates CO2, H2S, COS

 Pressure Swing Adsorption

based on selective adsorption

— 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

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Refinery Gases Fuel Oil (30 %)

LPG (Propane, Butane) Vacuum Tar

Natural Gas (48 %) Asphalt

Naphtha Petroleum Coke

Steam Reforming Partial Oxidation

Pressure Swing Adsorption