Industrial Hydrogen Production & Technology
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1 Industrial Hydrogen Production & Technology Dr. Klemens Wawrzinek, Claude Keller HDV, November 21, 2007, Karlsruhe, FuncHy-Workshop
2 Industrial Hydrogen Production & Technology Overview s Key Plant Types Hydrogen Market Feedstocks Technology: Syngas Generation, Product Recovery Summary 2 K. Wawrzinek/ HDV / Nov. 21, 2007 /Industrial H2 Production & Technology.ppt
3 Key Plant Types Olefin Plants Products: Ethylene Propylene Butadiene Aromatics Polymers Natural Gas Plants Products: LNG NGL LPG Helium Hydrogen and Synthesis Gas Plants Air Separation Plants Products: H 2 /CO/Syngas Ammonia Gas removal Gas purification Products: Oxygen Nitrogen Rare gases 3 K. Wawrzinek/ HDV / Nov. 21, 2007 /Industrial H2 Production & Technology.ppt
4 Industrial Hydrogen Market Installed capacity worldwide: 600 Billion Nm³/year Hydrogen Consumers: Trends shaping future Hydrogen demand: Ammonia Chemical Industry / Refineries Electronic Industry Metal- / Glass Industry Food Industry 54 % 35 % 6 % 3 % 2 % Increase of World Oil Consumption Decline of Overall Crude Oil Quality More Stringent Environmental Standards New Applications (Automotive fuel, Fuel cell) 4 K. Wawrzinek/ HDV / Nov. 21, 2007 /Industrial H2 Production & Technology.ppt
5 Feedstocks Light Hydrocarbons Refinery Gases LPG (Propane, Butane) Natural Gas (48 %) Naphtha Heavy Hydrocarbons Fuel Oil (30 %) Vacuum Tar Asphalt Petroleum Coke Coal (18 %) Process Steam Reforming Process Partial Oxidation Partial Oxidation 5 K. Wawrzinek/ HDV / Nov. 21, 2007 /Industrial H2 Production & Technology.ppt
6 Synthesis Gas Generation Principles Steam to Carbon Ratio Steam Reforming (SR) Catalytic Autothermal Reforming (ATR) Catalytic Syngas Production Partial Oxidation (POX) Non-Catalytic Combustion Oxygen Excess Ratio λ Pyrolysis 6 K. Wawrzinek/ HDV / Nov. 21, 2007 /Industrial H2 Production & Technology.ppt
7 Reactions Non Oxygen Consuming: Steam Methane Reforming (SMR) CH 4 + H 2 O CO + 3 H 2 endothermal Carbon Monoxide Conversion (CO-Shift) CO + H 2 O CO 2 + H 2 exothermal Oxygen Consuming Hydrocarbon Conversion C n H m + n/2 O 2 nco + m/2 H 2 exothermal H 2 Oxidation 2 H 2 + O 2 2 H 2 O exothermal Carbon Monoxide Oxidation 2 CO + O 2 2 CO 2 exothermal Steam Reforming Partial Oxidation, Autothermal Reforming Synthesis Gas contains H 2, CO, H 2 O, CO 2, unreacted Hydrocarbons, Impurities Requested Products are H 2, CO, CO+H 2 H 2 Separation + Purification required 7 K. Wawrzinek/ HDV / Nov. 21, 2007 /Industrial H2 Production & Technology.ppt
8 Typical Basic Block Diagrams for H 2 Production Light Hydrocarbons Steam Export Steam Feed Feed Pretreatment Steam Reforming Heat Recovery CO-Shift Pressure Swing Adsorption Hydrogen Fuel Fuel Gas Oxygen Steam Heavy Hydrocarbons Sulphur Export Steam Feed Feed Preparation Partial Oxidation CO-Shift/ Heat Recovery CO 2,H 2 S,COS Removal Pressure Swing Adsorption Hydrogen Fuelgas CO 2 -Byproduct 8 K. Wawrzinek/ HDV / Nov. 21, 2007 /Industrial H2 Production & Technology.ppt
9 Steam Reformer Burners Hydrocarbon + Steam Reformer Tubes Flue Gas Syngas ~850 C, bar, ~70 % H 2 in dry gas 9 K. Wawrzinek/ HDV / Nov. 21, 2007 /Industrial H2 Production & Technology.ppt
10 Partial Oxidation/ Autothermal Reforming Reactors ATR (Natural Gas) Feedstock + steam Oxygen Combustion chamber Feedstock POX (All Feedstocks) Oxygen Combustion chamber Catalyst bed ~35 bar ~1000 C bar ~1400 C Synthesis gas: H 2 in dry gas ~ 65 % Synthesis gas: H 2 in dry gas ~ 61 % 10 K. Wawrzinek/ HDV / Nov. 21, 2007 /Industrial H2 Production & Technology.ppt
11 CO-Shift Reactor Shifts undesired CO to H 2 CO + H 2 O CO 2 + H 2 exothermal Simple catalytic reactor CO conversion depends on Temperature High Temperature Shift: ~ 75 % Low Temperature Shift: ~ 90% H 2 in dry gas ~ 75 % 11 K. Wawrzinek/ HDV / Nov. 21, 2007 /Industrial H2 Production & Technology.ppt
12 Rectisol Wash Unit for POX Synthesis Gas e.g. for Syngas from Coal Gasification Methanol as washing solvent Rectisol process separates CO 2, H 2 S, COS H 2 Purity ~ 98 % 12 K. Wawrzinek/ HDV / Nov. 21, 2007 /Industrial H2 Production & Technology.ppt
13 H 2 Purification: Pressure Swing Adsorption Pressure Swing Adsorption for high Purity H 2 based on selective adsorption using different kinds of adsorption materials (e.g. molecular sieves) H 2 Purity up to % H 2 Recovery up to 90 % 13 K. Wawrzinek/ HDV / Nov. 21, 2007 /Industrial H2 Production & Technology.ppt
14 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 H 2 Separation from Syngas and Purification depend on Demand and Syngas Process 14 K. Wawrzinek/ HDV / Nov. 21, 2007 /Industrial H2 Production & Technology.ppt
15 Thank you for your attention
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