Process Economics Program

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1 IHS Chemical Process Economics Program Report 247C Land-Based Small-Scale GTL By Ron Smith December 2014 ihs.com/chemical

2 IHS Chemical agrees to assign professionally qualified personnel to the preparation of the Process Economics Program s reports and will perform the work in conformance with generally accepted professional standards. No other warranties expressed or implied are made. Because the reports are of an advisory nature, neither IHS Chemical nor its employees will assume any liability for the special or consequential damages arising from the Client s use of the results contained in the reports. The Client agrees to indemnify, defend, and hold IHS Chemical, its officers, and employees harmless from any liability to any third party resulting directly or indirectly from the Client s use of the reports or other deliverables produced by IHS Chemical pursuant to this agreement. For detailed marketing data and information, the reader is referred to one of the IHS Chemical programs specializing in marketing research. THE IHS CHEMICAL ECONOMICS HANDBOOK Program covers most major chemicals and chemical products produced throughout the world. In addition the IHS DIRECTORY OF CHEMICAL PRODUCERS services provide detailed lists of chemical producers by company, product, and plant for the United States, Europe, East Asia, China, India, South & Central America, the Middle East & Africa, Canada, and Mexico. December 2014 ii 2014 IHS

3 PEP Report 247C Land-Based Small-Scale GTL By Ron Smith December 2014 Abstract Since shortly after crude was refined into petroleum fractions, governments, research organizations, and corporations have been searching for an economical method to convert natural gas, often stranded in remote locations, or copiously associated with produced oil, into liquid products. Many routes have been discovered to transform this gas or also shale gas into a product that is liquid at atmospheric conditions. All too often the processes proposed fail economically because they must handle great quantities of gas. Reactors, gas heat exchangers and compression require enormous equipment, and reaction thermodynamic requirements often cripple the value of the overall process unless designed at large refinery type scales capacities. Small Scale Land Based GTL involves conversion of methane to high molecular weight hydrocarbons from LPG to waxy paraffins utilizing the principle of process intensification. The process itself consists mainly of three steps including syngas production through steam or autothermal reforming of natural gas, In this report, we investigate the use of microchannel Fischer-Tropsch synthesis designs with one or two stage reactor configurations using cobalt catalysts, followed by product upgrading though mild hydrocracking to convert high molecular weight waxes to LPG, naphtha, jet fuel, and diesel. This intensified process is a small scale hydrid that starts at the current complexity limit for parallel numbering up parallel microchannel reactor vessel designs, and calls for important system utilities like steam (and oxygen), high temperature heat transfer fluid systems, vacuum systems, wastewater treatment, and internal power generation. This report highlights all major aspects of production of diesel, and/or aviation fuel as a liquid transportable product via Fischer-Tropsch synthesis. In addition to presenting our traditional technoeconomic analyses we look at the current technology to produce transportation fuels from stranded or shale gas and compare the autothermal syngas generation and steam-methane reforming routes to produce synthesis gas, combined with single and dual stage Fischer-Tropsch synthesis configurations using Velocys microchannel reactor technology to convert synthesis gas to syncrude, Syncrude production is followed by product upgrading into a slate of fuel products including jet fuel and diesel. Our snap-shop economic findings show that both routes for conversion of associated or shale gas using Velocys microchannel F-T technology followed by upgrading syncrude to transportation products are currently viable. December 2014 iii 2014 IHS

4 Contents 1. Introduction... 1 Report Overview... 1 Report Focus... 3 Purpose of this Report Summary... 5 Overview... 5 Markets... 5 Water Requirements... 7 Technology... 8 Syngas Generation and Cleaning... 9 Fischer-Tropsch Synthesis Water Management Approaches Economics Cost Estimates Capital Costs Economics Summary Conclusion Industry status Introduction Small Scale GTL Projects Velocys New Projects Under Development Calumet Specialty Products Pinto Energy GreenSky London Red Rock Biofuels (DOD) Waste Management JV Small Scale GTL Projects CompactGTL New Projects Under Development Kazakhstan Component and Engineering Services Suppliers for Small Scale GTL Plants Technology Licensors - Velocys and Haldor Topsoe F-T Reactor and Catalyst Technology Suppliers Engineering, Procurement & Construction Technology Licensors Compact GTL Technology review Spot Gas Stockpile Gains Natural gas cleaning Sulfur December 2014 iv 2014 IHS

5 Sulfur Removal Chlorine Arsenic and Mercury Synthesis gas production technology Steam Methane Reforming Adiabatic Prereforming Partial Oxidation Autothermal Reforming ATR Chemistry ATR Reactor Design Autothermal Reforming Processes Fluidized Bed Autothermal Reforming Steam Methane Reforming + Autothermal Reforming Gas Heated Reforming Combined Reforming Compact Reformer Syngas technology comparisons Catalytic Membrane Reactors Microchannel Autothermal Reforming Radial Microchannel Reactors (RMRs) for Compact Steam Reforming Fischer-Tropsch synthesis technologies Fischer-Tropsch Synthesis Process Chemistry Fischer-Tropsch Reaction Engineering Conventional FTS Reactor Configurations Circulating Fluidized Bed Reactors Fixed Fluidized Bed Reactor Slurry Bed Reactor Monolith Reactor Tank Reactor Tubular Loop Reactor Small Scale Microchannel Reactor Fischer-Tropsch Syncrude Primary Products Pretreatment of Fischer-Tropsch Primary Products Fischer-Tropsch Syncrude Compositions Primary Separation of Fischer-Tropsch Syncrude Gaseous and Liquid Hydrocarbons Waxes Organic Phase Oxygenates Aqueous Phase Oxygenates Deactivation of Co-LTFT Catalysts Comparison of Fischer-Tropsch Syncrude with Conventional Crude Oil Conventional Crude Oil Refining Chemicals and Lubricant Refining December 2014 v 2014 IHS

6 Fischer-Tropsch Based Petrochemical Refining Lubricants Alkane Based Refining Aromatics Production Alkene and Oxygenate Recovery Fuels and chemicals co-production Production of Linear α-olefins Synthetic transportation fuels Motor Gasoline Jet Fuel Diesel Fuel Fischer Tropsch Gas Loop Configurations Open Loop Design Closed Loop Design Diesel Fuel Additives Affect Refinery Design Gas Loop for HTFT Synthesis with a Sasol-Lurgi Gasifier Gas Loop for HTFT Synthesis with a Natural Gas Feed Gas Loop for Co Catalyzed LTFT Eni Gas Loop Integration Fischer-Tropsch refining technology selection Fischer-Tropsch syncrude compatibility Waste generation Chemical addition Energy requirements Small Scale FTS Syncrude Product Upgrading Aqueous FTS Product Treatment Technology Selection for Diesel Fuel Refining Co-refining Small scale GTL Velocys Small scale GTL compactgtl Conclusions Velocys small scale GTL Single F-T microchannel reactor set with tail gas recycle Introduction Autothermal Reforming Microchannel Autothermal Reforming Microchannel Fischer-Tropsch Reactors Velocys microchannel reactors Microchannel Steam Methane Reforming Fischer-Tropsch Microchannel Reactors Small Scale Fischer-Tropsch GTL Technology Fischer-Tropsch Synthesis Alternative Microchannel F-T GTL Reactor Systems December 2014 vi 2014 IHS

7 Microchannel Fischer-Tropsch Catalysts Microchannel reactor module components Overview of the small scale F-T process Fuels from Fischer-Tropsch Syncrude Fischer-Tropsch Diesel Fischer-Tropsch Jet Fuel Naphtha Fischer-Tropsch GTL Process Basis for estimates and evaluation Process description Section Syngas Generation Section Fischer-Tropsch Synthesis Section Refinery Upgrading Process discussion Gas Pretreatment Natural Gas Reforming Operating pressure Syngas composition F-T catalyst type F-T operating conditions F-T reactor type Fischer Tropsch reactor microchannel heat exchange fouling Product recovery Product refining Olefin oligomerization Wax hydrocracking Conclusion Cost estimates Capital costs Production costs Velocys small scale GTL two stage F-T microchannel reactor set Introduction Microchannel steam methane reforming Fischer-Tropsch Microchannel Reactors Small Scale Fischer-Tropsch GTL Technology Fischer-Tropsch Two Stage GTL Process Basis for estimates and evaluation Steam Reforming Catalysts Process description Section Syngas Generation Section 200 Fischer-Tropsch Synthesis Section 300 Refinery Upgrading December 2014 vii 2014 IHS

8 Process discussion Conclusion Cost estimates Capital Costs Production Costs Appendix A: Patent Summaries Appendix B: Design and cost bases Design conditions Cost bases Capital investment Production costs Effect of operating level on production costs Appendix C: Bibliographic citations Appendix D: Patents by assignee Appendix E: Process flow diagrams Tables Table 2.1: Total Capital Costs, $ Million U.S. Gulf Coast Table 2.2: Economics Summary Table 4.1: Process Unit Configurations At Different GTL Plant Capacities Table 4.2: Typical Conversion Rates of a Methane Steam Reformer at Various Process Stages Table 4.3: Key Reactions In Steam Reforming Table 4.4: Steam Reforming Catalyst Requirements Table 4.5: Sources of Common Reformer Poisons Table 4.6: Routes To Carbon Formation Table 4.7: Typical Operating Conditions for a Gas Fired POx Unit Table 4.8: Typical POx Syngas Compositions Table 4.9: Comparison of Conventional Syngas Technologies Table 4.10: Capital Cost Savings With GHR Table 4.11: Syngas Technology Comparisons Table 4.12: A Comparison Of Syngas Production Technologies Table 4.13: Comparison Of Gas Reforming Technologies That Are Industrially Applied In Combination With Fischer Tropsch Table 4.14: Syncrude Compositions Typical of Iron Based High Temperature Fischer Tropsch (Fe- HTFT) Synthesis, Low Temperature Iron Based Fischer Tropsch (Fe-LTFT) Synthesis, and Cobalt Based Low Temperature Fischer Tropsch (Co-LTFT) Synthesis December 2014 viii 2014 IHS

9 Table 4.15: Characteristics of the Main Reactor Types Used for Fischer-Tropsch Synthesis Table 4.16: Comparison Of The Catalyst And Volumetric Reactor Productivity Of Iron Based Catalysts In Different Reactor Types Table 4.17: Rank Order Of The 10 Most Abundant Chemicals In HTFT Syncrude (Excluding Methane and Water Gas Shift Products) Table 4.18: Product Composition Of Straight Run Unrefined C 5 -C 11 Naphtha And C 12 -C 19 Distillage Cuts From Fixed Bed Fe-LTFT And Circulating Fluidized Bed Fe-LTFT Synthesis Table 4.19: American Petroleum Institute (API) Classification Of Lubricant Base Oils Table 4.20: LTFT Syncrude Composition Table 4.21: Industrial Applications Of n-1 Alkenes Table 4.22: Mass Balances For Combined Fuels And Chemicals Refining Table 4.23: Main Technical Features Of The ENI GTL Gas Loop Integration Table 4.24: Refinery Technologies For Processing Fischer-Tropsch Syncrude In Terms Or Compatability Environmental Impact And Recommended Use Table 4.25: Characteristics Of Different Naphtha Fractions Produced From Co-LTFT Synthesis and Refining Table 4.26: Fischer-Tropsch Aqueous Product From Co-LTFT Synthesis Table 4.27: Diesel Fuel Specifications Employed For Syncrude Refinery Design Table 4.28: Products From LTFT Diesel Fuel Refinery Design Table 5.1: Comparison Of Fischer-Tropsch Reactor Types Table 5.2: Typical Properties Of Syncrude - Vs. Crude Oil Table 5.3: Specification of F-T Diesel Compared To Conventional Diesel Table 5.4: Fischer-Tropsch Jet Fuel Table 5.5: Design Bases and Assumptions Production of Integrated Fuels By The Haldor-Topsoe Autothermal Syngas Process Table 5.6: Small scale land-based GTL (Case 1) Stream flows Table 5.7: Small Scale Land Based GTL Velocys Single Stage F-T Reactor Major Equipment Table 5.8: Small Scale Land Based GTL Velocys Single Stage F-T Reactor Utilities Summary Table 5.9: Small Scale Land Based GTL Velocys Single Stage F-T Reactor Total Capital Investment Table 5.10: Small Scale Land Based GTL - Velocys Single Stage F-T Reactor Capital Investment By Section Table 5.11: Small Scale Land Based GTL - Velocys Single Stage F-T Reactor Production Costs Production costs Table 6.1 : Small Scale Land Based GTL Velocys Two-Stage F-T Reactor System Design Bases Table 6.2: Small scale land-based GTL (Case 2) Stream flows Table 6.3: Small Scale Land Based GTL - Velocys Two-Stage F-T Reactor System Major Equipment Table 6.4: Small Scale Land Based GTL - Velocys Two-Stage F-T Reactor System Utilities Summary Table 6.5: Small Scale Land Based GTL - Velocys Two-Stage F-T Reactor System Total Capital Investment Table 6.6: Small Scale Land Based GTL - Velocys Two-Stage F-T Reactor System Capital Investment By Section Table 6.7: Small Scale Land Based GTL - Velocys Two-Stage F-T Reactor System Production Costs. 291 December 2014 ix 2014 IHS

10 Figures Figure 3.1: GreenSky London Biorefinery Block Flow Diagram Figure 4.1: GTL Process Steps Figure 4.2: Large Scale Fischer-Tropsch Based GTL Plant Investment Profile Figure 4.3: GTL Project Financial Risk Figure 4.4: Conventional Shale Gas Processing Plant Integration with Ethylene Cracking Figure 4.5: Syngas Clean-up Process Flow Schematic Figure 4.6: Process Flow Schematic For Hydrosulfurization and Subsequent Sulfur Removal From Gaseous Reforming Feedstocks Figure 4.7: Chlorine Guard Bed On Top of Desulfurization Bed Figure 4.8: Steam Methane Reforming Process Flow Schematic Figure 4.9: Process Flow Schematics for Direct and Pre-Reforming Multifeed Steam Reforming Configurations Figure 4.10: Schematic Representations of Tubular Steam Reforming Technologies of Different Furnace Firing Configurations Figure 4.5: Sources of Common Reformer Poisons Figure 4.11: Adiabatic Preforming Process Flow Schematic Figure 4.12: Partial Oxidation of Methane to Synthesis Gas Figure 4.13: The Boiler System for Partial Oxidation of Gaseous and Liquid Hydrocarbons Figure 4.14: Sour Water Stripping Process Flow Schematic Figure 4.15: Autothermal Reformer Process Flow Schematic Figure 4.16: Autothermal Reforming Process Flow Schematic Figure 4.17: Process Flow Schematic of Gas Heated Reforming Figure 4.18: Johnson Matthey/Davy Gas Heated Reformer Schematic Figure 4.19: Incorporation of a Heat Exchange Post Reformer With Steam Methane Reforming Figure 4.20: Conventional Straight Tube Heat Exchanger Figure 4.21: Conventional U-Tube Heat Exchanger Figure 4.22: Different Process Gas Heat Exchange Reformer Design Types Figure 4.23: Heat Exchange Reformers Combined With ATR Figure 4.24: Haldor Topsøe Heat Exchange Reformer Schematic Figure 4.25: Parallel Gas Fed ATR/GHR Syngas Production Combination Figure 4.26: Series Gas Fed ATR/GHR Combination Figure 4.27: Combined Reforming Figure 4.28: Compact Reformer Figure 4.29: Process Flow Schematic of Compact Reforming Principles Figure 4.30: Simplified Process Flow Schematic For Use Of Compact Reforming In The BP/Davy Integrated GTL Process To Produce Syncrude Figure 4.31: Typical Single Train Syngas Reforming Capacities Figure 4.32: Process Flow Schematic Of Velocys SMR Microchannel Reactor Block Figure 4.33: Prototype Experimental Steam Reforming RMR Reactor Figure 4.34: Generic Schematic Of a Multitibular Fixed Bed Reactor Figure 4.35: Multitubular Fixed Bed Reactor (Arge) Figure 4.36: Gas-Solid CFB F-T Reactor Figure 4.37: Generic Schematic Of A Fixed Fluidized Bed Reactor December 2014 x 2014 IHS

11 Figure 4.38: Advanced Synthol FFB Reactor Figure 4.39: Generic Schematic Of A Slurry Bubble Column Reactor Figure 4.40: F-T Slurry Bubble Column Reactor Figure 4.41: ASF Carbon Number Distributions Figure 4.42: Generic Process Flow Schematic Of HTFT Reactor Product Recovery Figure 4.43: Generic Process Flow Schematic Of LTFT Reactor Product Recovery Section Figure 4.44: Boiling Point Cut Range Nomenclature Overlaps Figure 4.45: Two Types Of Closed Gas Loop Designs Figure 4.46: Gas Loop Design For Sasol-Lurgi Gasifier With HTFT Synthesis Figure 4.47: Mossel Bay Gas Loop Block Flow Diagram Figure 4.48: Gas Loop Scheme For LTFT With POx Figure 4.49: ENI Gas Loop Integration Figure 4.50: HTCR Reactor Figure 4.51: Haldor Topsøe Compact Convective Reformer Process Figure 4.5: Typical Layout Of A HTCR Twin Process Figure 4.53: Process Flow Schematic Of Refinery Upgrading Section For Small Scale GTL Figure 4.54: Wax Hydrocracking Process Flow Schematic Figure 4.55: Complex Wax Hydrocracking Configuration Process Flow Schematic Figure 4.56: Fischer-Tropsch Oxygenates Recovery From Synthesis Reaction Water Figure 4.57: Process Flow Schematics Of Options For Fischer-Tropsch Aqueous Product Refining Figure 4.58: Generic Fischer-Tropsch Refinery Configuration Designed To Increase Distillate Yield Figure 4.59: Technology Selection For The Refining Of Syncrude To Diesel Fuel When There Is No Minimum Diesel Fuel Density Requirement Figure 4.60: Integrated Crude Oil And Gas Based F-T Refinery Figure 4.61: LTFT Diesel Fuel Refinery Design Process Flow Schematic Figure 4.62: LTFT Jet Fuel Refinery Design That Maximizes Diesel Fuel Yield With Minimum Density Requirement Figure 5.1: Velocys Simplified Fischer-Tropsch Block Flow Diagram Figure 5.2: Fischer Tropsch Relative Reactor/Co Catalyst Reactivity Comparison Figure 5.3: Velocys Fischer-Tropsch Microchannel Reactor Block Figure 5.4: Commercial Designs For Single Smr And F-T Microchannel Reactor Modules Figure 5.5: Integration Of Wellhead Gas Processing With F-T GTL MicroGTL Block Flow Diagram. 209 Figure 5.6: Micro-GTL Block Process Flow Diagram Figure 5.7: LTFT Jet Fuel Refinery Block Flow Diagram Figure 5.7: Small Scale Land Based Fischer-Tropsch Process Figure 5.8: Small Scale Land Based Fischer-Tropsch GTL Block Flow Process Diagram Figure 5.9: Fischer-Tropsch Synthesis Quad Block Reactor Module Figure 5.10: Two Stage Fischer-Tropsch Reactor Operation Impact Of Hydrocarbon Conversion And C5+ Selectivity On C5+ Yield Figure 5.11: Single Stage Fischer-Tropsch Reactor Operation with Tail Gas Recycle Figure 6.1: Two Stage Once-Through Fischer-Tropsch Synthesis Reactor Operation December 2014 xi 2014 IHS