WORLDWIDE REFINERY PROCESSING REVIEW. Third Quarter 2011

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1 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 (U.S.A.) Phone: (610) / Fax: (610) Review@Hydrocarbonpublishing.com

2 Hydrogen Production, Purification, and Recovery 3Q Hydrogen Production, Purification, and Recovery MARKET/TECHNOLOGY TRENDS & OPPORTUNITIES Introduction Market Conditions and Outlook Refinery Hydrogen Demand Production Capacity and Market Supply Impact of Opportunity Crudes Processing on Hydrogen Demand Onsite Production vs. Over-the-fence Supply Feedstock Choices Environmental Factors Technology Competition, Directions, and Future Prospects Evaluation of Technology Offerings Hydrogen Production Steam Reforming/Autothermal Reforming Membrane Reactors Renewable Feed Reforming H 2 Purification, Recovery, and Management Conclusion STATE-OF-THE-ART TECHNOLOGY Introduction Commercial and Near-commercial Process Technologies H 2 Production Caloric Anlagenbau HC Process HM Process HC Economy Ultra Process CB&I Steam Reforming Autothermal Reforming Davy Process Technology CRG Prereforming Compact Reformer Foster Wheeler Haldor Topsøe Feed Purification Prereforming Side-fired Tubular Reformer High Flux Reformer Haldor Topsøe Convection Reformer Haldor Topsøe Exchange Reformer Haldor Topsøe Bayonet Reformer Methanol-to-Shift Process Methanol Decomposition-based H 2 Plants JGC Corp Johnson Matthey Catalysts KBR Linde BOC Process Plants Prereformer i

3 Steam Reformer Gas Heated Reformer Lurgi Pretreatment Prereforming Steam Reforming Process Lurgi Autothermal Catalytic Reforming Process Lurgi CO Shift Process Praxair Shell Technip Steam Reforming ART Process Enhanced Heat Transfer Reformer Toyo Engineering Corp Uhde Feed Preparation Prereforming Steam Reforming CO Shift Autothermal Reforming Combined Autothermal Reforming Process Convective Reformer H 2 Recovery and Purification Advanced Extraction Technologies Air Liquide PSA Cryogenic System MEDAL Membrane Technology Air Products and Chemicals Gemini Hyco Adsorption Systems Prism PSA Units Prism Membrane Systems Selective Surface Flow Membranes Cryogenic Systems ACORN Methane Wash Units ACORN Partial Condensation Units CB&I Costain Oil, Gas & Process CRI/Criterion Catalysts & Technologies ExxonMobil Linde Membrane Technology Research Pall Corp Toyo Engineering UOP Polybed PSA Systems Polysep Membrane Systems Commercial Catalysts BASF Catalysts Haldor Topsøe Feed Purification ii

4 Prereforming Steam Reforming Shift Conversion Methanation Johnson Matthey Catalysts Feed Purification Steam Reforming Shift Conversion Methanation Süd-Chemie Pretreatment Prereforming Steam Reforming Shift Conversion Methanation Hydrogen Management, Advanced Process Control, Simulation, and Monitoring Hydrogen Management Air Liquide Axens Foster Wheeler Technip UOP Advanced Process Control, Monitoring, and Simulation AspenTech Johnson Matthey H 2 Scan Honeywell Industry Solutions Summary of Commercially Available Hydrogen Technologies Comparison of Commercial H 2 Production Catalysts PLANT OPERATIONS AND PRACTICES Meeting Rising Hydrogen Demand Sourcing Hydrogen for Plant Expansion Expanding Hydrogen Plant Capacity via Revamps Hydrogen Management via Pinch Technology and Mathematical Modeling Over-the-fence Hydrogen Supply Partial Oxidation and Gasification for H 2 and Syngas Production Steam Reforming Feedstock Flexibility Natural Gas Naphtha and Other High-quality Refinery Streams Refinery Fuel Gas Butane Processing Heavier Hydrocarbons in Steam Reforming Pretreatment Requirements for Steam Reformers Feed Header Deposits Installing Prereforming Technology Effect of Reformer Tube Wall Temperature on Tube Life Catalyst Tube Outlet Pressure and Heater Outlet Temperature in Steam Reformers Hydrogen Recovery and Purification Technology Options Identifying Recoverable Hydrogen Configuration Options Improving PSA Recovery Efficiency iii

5 Using a Membrane to Recover Hydrogen from Hydrotreaters Summary and Commercial Experience Operational Problems Process Variables Optimizing Steam-to-Carbon Ratio: Flowmeters Reformer Overheating Problems Startup and Shutdown Monitoring Temperature Metal-dusting Corrosion Formic Acid Formation in Shift Converters Preventing and Detecting Hydrogen Leaks CO 2 /CO Slip from the Methanator Process Condensate Contamination Process Hardware Preventing Frequent Pigtail Failures Sudden Severe Corrosion and Vanadium Plating in a Benfield Unit Cold-end Corrosion in Convection Section Steam Reformer Tubing Metallurgy Reformer Tube Failure Improving the Reliability of Hydrogen Reciprocating Compressors Best Practices for Inspecting PSA Units Catalyst Considerations and Management Improving Reliability for Longer Run Lengths Optimize Shape and Size Proper Catalyst Loading in the Reformer Tubes Carbon Deposition on Reformer Catalysts Preventing Wetting on the Catalyst Reformer Catalyst Deactivation Temperature Excursions during Shift Catalyst Reduction HTS Catalysts LTS Catalysts Adsorbents Preventing Unwanted Side Reactions Catalyst Support Selection Improving Energy Efficiency and Reducing CO 2 Emissions Hydrogen Plant Energy Use Energy Characteristics General Improvements Heat Integrated Steam Reforming Designs Maintaining PSA Unit Efficiency and Adsorbent Life Reducing Export Steam Production Improving the Performance of CO 2 Removal Systems Impact of Feed on Steam Reformer CO 2 Emissions Tri-generation: Hydrogen, Steam, and Power to Lower GHG Emissions REFINING R&D ALERT! Introduction Hydrogen Production Methods Steam Reforming Process and Hardware Patents Research Catalysts Patents iv

6 Research Autothermal Reforming Patents Research Partial Oxidation Hybrid Reforming Technologies Reforming with Membrane Reactors Patents Research Hydrogen Production from Renewable Feeds Patents Research Process Catalyst Hydrogen Recovery and Purification Pressure Swing Adsorption Patents Research Membrane Separation Patents Research Other WORLDWIDE INSTALLED CAPACITY CONSTRUCTION Recent Construction Activity Completed Construction Projects REFERENCES v