WORLDWIDE REFINERY PROCESSING REVIEW Monitoring Technology Development and Competition in a Single Source Third Quarter 2011 Hydrogen Production, Purification, and Recovery HYDROCARBON PUBLISHING COMPANY Translating Knowledge into Profitability SM P.O. Box 661 Southeastern, PA 19399 (U.S.A.) Phone: (610) 408-0117/ Fax: (610) 408-0118 Review@Hydrocarbonpublishing.com
Hydrogen Production, Purification, and Recovery 3Q2011 1. Hydrogen Production, Purification, and Recovery... 1 1.1 MARKET/TECHNOLOGY TRENDS & OPPORTUNITIES... 1 1.1.1 Introduction... 1 1.1.2 Market Conditions and Outlook... 2 1.1.2.1 Refinery Hydrogen Demand... 2 1.1.2.2 Production Capacity and Market Supply... 2 1.1.2.3 Impact of Opportunity Crudes Processing on Hydrogen Demand... 4 1.1.2.4 Onsite Production vs. Over-the-fence Supply... 7 1.1.2.5 Feedstock Choices... 7 1.1.2.6 Environmental Factors... 9 1.1.3 Technology Competition, Directions, and Future Prospects... 12 1.1.3.1 Evaluation of Technology Offerings... 12 1.1.3.2 Hydrogen Production... 14 1.1.3.2.1 Steam Reforming/Autothermal Reforming... 14 1.1.3.2.2 Membrane Reactors... 17 1.1.3.2.3 Renewable Feed Reforming... 17 1.1.3.3 H 2 Purification, Recovery, and Management... 18 1.1.4 Conclusion... 19 1.2 STATE-OF-THE-ART TECHNOLOGY... 20 1.2.1 Introduction... 20 1.2.2 Commercial and Near-commercial Process Technologies... 25 1.2.2.1 H 2 Production... 25 1.2.2.1.1 Caloric Anlagenbau... 25 1.2.2.1.1.1 HC Process... 25 1.2.2.1.1.2 HM Process... 26 1.2.2.1.1.3 HC Economy Ultra Process... 27 1.2.2.1.2 CB&I... 28 1.2.2.1.2.1 Steam Reforming... 28 1.2.2.1.2.2 Autothermal Reforming... 30 1.2.2.1.3 Davy Process Technology... 30 1.2.2.1.3.1 CRG Prereforming... 30 1.2.2.1.3.2 Compact Reformer... 31 1.2.2.1.4 Foster Wheeler... 32 1.2.2.1.5 Haldor Topsøe... 35 1.2.2.1.5.1 Feed Purification... 35 1.2.2.1.5.2 Prereforming... 35 1.2.2.1.5.3 Side-fired Tubular Reformer... 36 1.2.2.1.5.4 High Flux Reformer... 37 1.2.2.1.5.5 Haldor Topsøe Convection Reformer... 37 1.2.2.1.5.6 Haldor Topsøe Exchange Reformer... 40 1.2.2.1.5.7 Haldor Topsøe Bayonet Reformer... 43 1.2.2.1.5.8 Methanol-to-Shift Process... 43 1.2.2.1.5.9 Methanol Decomposition-based H 2 Plants... 44 1.2.2.1.6 JGC Corp.... 45 1.2.2.1.7 Johnson Matthey Catalysts... 45 1.2.2.1.8 KBR... 48 1.2.2.1.9 Linde BOC Process Plants... 49 1.2.2.1.9.1 Prereformer... 50 i
1.2.2.1.9.2 Steam Reformer... 50 1.2.2.1.9.3 Gas Heated Reformer... 51 1.2.2.1.10 Lurgi... 52 1.2.2.1.10.1 Pretreatment... 52 1.2.2.1.10.2 Prereforming... 52 1.2.2.1.10.3 Steam Reforming Process... 53 1.2.2.1.10.4 Lurgi Autothermal Catalytic Reforming Process... 54 1.2.2.1.10.5 Lurgi CO Shift Process... 55 1.2.2.1.11 Praxair... 56 1.2.2.1.12 Shell... 59 1.2.2.1.13 Technip... 59 1.2.2.1.13.1 Steam Reforming... 60 1.2.2.1.13.2 ART Process... 62 1.2.2.1.13.3 Enhanced Heat Transfer Reformer... 62 1.2.2.1.14 Toyo Engineering Corp... 63 1.2.2.1.15 Uhde... 64 1.2.2.1.15.1 Feed Preparation... 65 1.2.2.1.15.2 Prereforming... 65 1.2.2.1.15.3 Steam Reforming... 65 1.2.2.1.15.4 CO Shift... 66 1.2.2.1.15.5 Autothermal Reforming... 67 1.2.2.1.15.6 Combined Autothermal Reforming Process... 67 1.2.2.1.15.7 Convective Reformer... 67 1.2.2.2 H 2 Recovery and Purification... 67 1.2.2.2.1 Advanced Extraction Technologies... 68 1.2.2.2.2 Air Liquide... 69 1.2.2.2.2.1 PSA... 70 1.2.2.2.2.2 Cryogenic System... 70 1.2.2.2.2.3 MEDAL Membrane Technology... 70 1.2.2.2.3 Air Products and Chemicals... 71 1.2.2.2.3.1 Gemini Hyco Adsorption Systems... 72 1.2.2.2.3.2 Prism PSA Units... 72 1.2.2.2.3.3 Prism Membrane Systems... 74 1.2.2.2.3.4 Selective Surface Flow Membranes... 75 1.2.2.2.3.5 Cryogenic Systems... 75 1.2.2.2.3.6 ACORN Methane Wash Units... 77 1.2.2.2.3.7 ACORN Partial Condensation Units... 77 1.2.2.2.4 CB&I... 78 1.2.2.2.5 Costain Oil, Gas & Process... 79 1.2.2.2.6 CRI/Criterion Catalysts & Technologies... 79 1.2.2.2.7 ExxonMobil... 80 1.2.2.2.8 Linde... 81 1.2.2.2.9 Membrane Technology Research... 81 1.2.2.2.10 Pall Corp.... 83 1.2.2.2.11 Toyo Engineering... 83 1.2.2.2.12 UOP... 84 1.2.2.2.12.1 Polybed PSA Systems... 85 1.2.2.2.12.2 Polysep Membrane Systems... 87 1.2.3 Commercial Catalysts... 89 1.2.3.1 BASF Catalysts... 89 1.2.3.2 Haldor Topsøe... 90 1.2.3.2.1 Feed Purification... 90 ii
1.2.3.2.2 Prereforming... 91 1.2.3.2.3 Steam Reforming... 91 1.2.3.2.4 Shift Conversion... 92 1.2.3.2.5 Methanation... 93 1.2.3.3 Johnson Matthey Catalysts... 93 1.2.3.3.1 Feed Purification... 93 1.2.3.3.2 Steam Reforming... 94 1.2.3.3.3 Shift Conversion... 96 1.2.3.3.4 Methanation... 97 1.2.3.4 Süd-Chemie... 97 1.2.3.4.1 Pretreatment... 97 1.2.3.4.2 Prereforming... 98 1.2.3.4.3 Steam Reforming... 98 1.2.3.4.4 Shift Conversion... 99 1.2.3.4.5 Methanation... 100 1.2.4 Hydrogen Management, Advanced Process Control, Simulation, and Monitoring... 100 1.2.4.1 Hydrogen Management... 100 1.2.4.1.1 Air Liquide... 100 1.2.4.1.2 Axens... 101 1.2.4.1.3 Foster Wheeler... 102 1.2.4.1.4 Technip... 103 1.2.4.1.5 UOP... 105 1.2.4.2 Advanced Process Control, Monitoring, and Simulation... 106 1.2.4.2.1 AspenTech... 106 1.2.4.2.2 Johnson Matthey... 107 1.2.4.2.3 H 2 Scan... 107 1.2.4.2.4 Honeywell Industry Solutions... 107 1.2.5 Summary of Commercially Available Hydrogen Technologies... 108 1.2.6 Comparison of Commercial H 2 Production Catalysts... 114 1.3 PLANT OPERATIONS AND PRACTICES... 116 1.3.1 Meeting Rising Hydrogen Demand... 116 1.3.1.1 Sourcing Hydrogen for Plant Expansion... 116 1.3.1.2 Expanding Hydrogen Plant Capacity via Revamps... 116 1.3.1.3 Hydrogen Management via Pinch Technology and Mathematical Modeling... 120 1.3.1.4 Over-the-fence Hydrogen Supply... 124 1.3.1.5 Partial Oxidation and Gasification for H 2 and Syngas Production... 125 1.3.2 Steam Reforming... 127 1.3.2.1 Feedstock Flexibility... 127 1.3.2.1.1 Natural Gas... 127 1.3.2.1.2 Naphtha and Other High-quality Refinery Streams... 128 1.3.2.1.3 Refinery Fuel Gas... 128 1.3.2.1.4 Butane... 129 1.3.2.2 Processing Heavier Hydrocarbons in Steam Reforming... 130 1.3.2.3 Pretreatment Requirements for Steam Reformers... 131 1.3.2.4 Feed Header Deposits... 133 1.3.2.5 Installing Prereforming Technology... 133 1.3.2.6 Effect of Reformer Tube Wall Temperature on Tube Life... 134 1.3.2.7 Catalyst Tube Outlet Pressure and Heater Outlet Temperature in Steam Reformers... 135 1.3.3 Hydrogen Recovery and Purification... 136 1.3.3.1 Technology Options... 136 1.3.3.2 Identifying Recoverable Hydrogen... 137 1.3.3.3 Configuration Options... 138 1.3.3.4 Improving PSA Recovery Efficiency... 139 iii
1.3.3.5 Using a Membrane to Recover Hydrogen from Hydrotreaters... 140 1.3.3.6 Summary and Commercial Experience... 141 1.3.4 Operational Problems... 142 1.3.4.1 Process Variables... 142 1.3.4.1.1 Optimizing Steam-to-Carbon Ratio: Flowmeters... 142 1.3.4.1.2 Reformer Overheating Problems... 143 1.3.4.1.2.1 Startup and Shutdown... 144 1.3.4.1.2.2 Monitoring Temperature... 145 1.3.4.1.3 Metal-dusting Corrosion... 146 1.3.4.1.4 Formic Acid Formation in Shift Converters... 148 1.3.4.1.5 Preventing and Detecting Hydrogen Leaks... 148 1.3.4.1.6 CO 2 /CO Slip from the Methanator... 149 1.3.4.1.7 Process Condensate Contamination... 150 1.3.4.2 Process Hardware... 150 1.3.4.2.1 Preventing Frequent Pigtail Failures... 150 1.3.4.2.2 Sudden Severe Corrosion and Vanadium Plating in a Benfield Unit... 151 1.3.4.2.3 Cold-end Corrosion in Convection Section... 151 1.3.4.2.4 Steam Reformer Tubing Metallurgy... 152 1.3.4.2.5 Reformer Tube Failure... 152 1.3.4.2.6 Improving the Reliability of Hydrogen Reciprocating Compressors... 153 1.3.4.2.7 Best Practices for Inspecting PSA Units... 153 1.3.5 Catalyst Considerations and Management... 154 1.3.5.1 Improving Reliability for Longer Run Lengths... 154 1.3.5.2 Optimize Shape and Size... 155 1.3.5.3 Proper Catalyst Loading in the Reformer Tubes... 155 1.3.5.4 Carbon Deposition on Reformer Catalysts... 157 1.3.5.5 Preventing Wetting on the Catalyst... 157 1.3.5.6 Reformer Catalyst Deactivation... 158 1.3.5.7 Temperature Excursions during Shift Catalyst Reduction... 159 1.3.5.7.1 HTS Catalysts... 159 1.3.5.7.2 LTS Catalysts... 160 1.3.5.7.3 Adsorbents... 161 1.3.5.8 Preventing Unwanted Side Reactions... 161 1.3.5.9 Catalyst Support Selection... 162 1.3.6 Improving Energy Efficiency and Reducing CO 2 Emissions... 162 1.3.6.1 Hydrogen Plant Energy Use... 162 1.3.6.1.1 Energy Characteristics... 162 1.3.6.1.2 General Improvements... 163 1.3.6.2 Heat Integrated Steam Reforming Designs... 164 1.3.6.3 Maintaining PSA Unit Efficiency and Adsorbent Life... 165 1.3.6.4 Reducing Export Steam Production... 166 1.3.6.5 Improving the Performance of CO 2 Removal Systems... 167 1.3.6.6 Impact of Feed on Steam Reformer CO 2 Emissions... 167 1.3.6.7 Tri-generation: Hydrogen, Steam, and Power to Lower GHG Emissions... 169 1.4 REFINING R&D ALERT!... 170 1.4.1 Introduction... 170 1.4.2 Hydrogen Production Methods... 175 1.4.2.1 Steam Reforming... 175 1.4.2.1.1 Process and Hardware... 175 1.4.2.1.1.1 Patents... 175 1.4.2.1.1.2 Research... 180 1.4.2.1.2 Catalysts... 181 1.4.2.1.2.1 Patents... 181 iv
1.4.2.1.2.2 Research... 184 1.4.2.2 Autothermal Reforming... 186 1.4.2.2.1 Patents... 186 1.4.2.2.2 Research... 188 1.4.2.3 Partial Oxidation... 190 1.4.2.4 Hybrid Reforming Technologies... 191 1.4.2.5 Reforming with Membrane Reactors... 191 1.4.2.5.1 Patents... 191 1.4.2.5.2 Research... 195 1.4.2.6 Hydrogen Production from Renewable Feeds... 197 1.4.2.6.1 Patents... 197 1.4.2.6.2 Research... 198 1.4.2.6.2.1 Process... 198 1.4.2.6.2.2 Catalyst... 199 1.4.3 Hydrogen Recovery and Purification... 201 1.4.3.1 Pressure Swing Adsorption... 201 1.4.3.1.1 Patents... 201 1.4.3.1.2 Research... 203 1.4.3.2 Membrane Separation... 204 1.4.3.2.1 Patents... 204 1.4.3.2.2 Research... 205 1.4.3.3 Other... 207 1.5 WORLDWIDE INSTALLED CAPACITY... 208 1.6 CONSTRUCTION... 212 1.6.1 Recent Construction Activity... 212 1.6.2 Completed Construction Projects... 217 1.7 REFERENCES... 236 v