IHS Chemical Process Economics Program Report 247C Land-Based Small-Scale GTL By Ron Smith December 2014 ihs.com/chemical
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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
Contents 1. Introduction... 1 Report Overview... 1 Report Focus... 3 Purpose of this Report... 4 2. Summary... 5 Overview... 5 Markets... 5 Water Requirements... 7 Technology... 8 Syngas Generation and Cleaning... 9 Fischer-Tropsch Synthesis... 10 Water Management Approaches... 10 Economics... 11 Cost Estimates... 11 Capital Costs... 12 Economics Summary... 12 Conclusion... 13 Industry status... 14 3. Introduction... 14 Small Scale GTL Projects Velocys... 15 New Projects Under Development... 15 Calumet Specialty Products... 16 Pinto Energy... 16 GreenSky London... 16 Red Rock Biofuels (DOD)... 17 Waste Management JV... 18 Small Scale GTL Projects CompactGTL... 18 New Projects Under Development... 19 Kazakhstan... 20 Component and Engineering Services Suppliers for Small Scale GTL Plants... 21 Technology Licensors - Velocys and Haldor Topsoe... 21 F-T Reactor and Catalyst Technology Suppliers... 21 Engineering, Procurement & Construction... 22 Technology Licensors Compact GTL... 23 4. Technology review... 25 Spot Gas... 34 Stockpile Gains... 34 Natural gas cleaning... 37 Sulfur... 38 December 2014 iv 2014 IHS
Sulfur Removal... 39 Chlorine... 40 Arsenic and Mercury... 41 Synthesis gas production technology... 42 Steam Methane Reforming... 44 Adiabatic Prereforming... 53 Partial Oxidation... 56 Autothermal Reforming... 61 ATR Chemistry... 64 ATR Reactor Design... 65 Autothermal Reforming Processes... 68 Fluidized Bed Autothermal Reforming... 70 Steam Methane Reforming + Autothermal Reforming... 71 Gas Heated Reforming... 72 Combined Reforming... 81 Compact Reformer... 83 Syngas technology comparisons... 89 Catalytic Membrane Reactors... 94 Microchannel Autothermal Reforming... 98 Radial Microchannel Reactors (RMRs) for Compact Steam Reforming... 99 Fischer-Tropsch synthesis technologies... 102 Fischer-Tropsch Synthesis Process Chemistry... 102 Fischer-Tropsch Reaction Engineering... 105 Conventional FTS Reactor Configurations... 109 Circulating Fluidized Bed Reactors... 114 Fixed Fluidized Bed Reactor... 116 Slurry Bed Reactor... 118 Monolith Reactor... 123 Tank Reactor... 125 Tubular Loop Reactor... 127 Small Scale Microchannel Reactor... 128 Fischer-Tropsch Syncrude Primary Products... 129 Pretreatment of Fischer-Tropsch Primary Products... 129 Fischer-Tropsch Syncrude Compositions... 130 Primary Separation of Fischer-Tropsch Syncrude... 133 Gaseous and Liquid Hydrocarbons... 136 Waxes... 137 Organic Phase Oxygenates... 137 Aqueous Phase Oxygenates... 138 Deactivation of Co-LTFT Catalysts... 138 Comparison of Fischer-Tropsch Syncrude with Conventional Crude Oil... 140 Conventional Crude Oil Refining... 142 Chemicals and Lubricant Refining... 143 December 2014 v 2014 IHS
Fischer-Tropsch Based Petrochemical Refining... 145 Lubricants... 145 Alkane Based Refining... 146 Aromatics Production... 147 Alkene and Oxygenate Recovery... 148 Fuels and chemicals co-production... 148 Production of Linear α-olefins... 149 Synthetic transportation fuels... 151 Motor Gasoline... 151 Jet Fuel... 152 Diesel Fuel... 153 Fischer Tropsch Gas Loop Configurations... 154 Open Loop Design... 155 Closed Loop Design... 155 Diesel Fuel Additives Affect Refinery Design... 157 Gas Loop for HTFT Synthesis with a Sasol-Lurgi Gasifier... 158 Gas Loop for HTFT Synthesis with a Natural Gas Feed... 160 Gas Loop for Co Catalyzed LTFT... 160 Eni Gas Loop Integration... 161 Fischer-Tropsch refining technology selection... 167 1. Fischer-Tropsch syncrude compatibility... 167 2. Waste generation... 168 3. Chemical addition... 168 4. Energy requirements... 168 Small Scale FTS Syncrude Product Upgrading... 170 Aqueous FTS Product Treatment... 173 Technology Selection for Diesel Fuel Refining... 176 Co-refining... 177 Small scale GTL Velocys... 183 Small scale GTL compactgtl... 185 Conclusions... 187 5. Velocys small scale GTL Single F-T microchannel reactor set with tail gas recycle... 190 Introduction... 190 Autothermal Reforming... 193 Microchannel Autothermal Reforming... 194 Microchannel Fischer-Tropsch Reactors... 197 Velocys microchannel reactors... 198 Microchannel Steam Methane Reforming... 200 Fischer-Tropsch Microchannel Reactors... 200 Small Scale Fischer-Tropsch GTL Technology... 204 Fischer-Tropsch Synthesis... 205 Alternative Microchannel F-T GTL Reactor Systems... 208 December 2014 vi 2014 IHS
Microchannel Fischer-Tropsch Catalysts... 212 Microchannel reactor module components... 217 Overview of the small scale F-T process... 217 Fuels from Fischer-Tropsch Syncrude... 219 Fischer-Tropsch Diesel... 220 Fischer-Tropsch Jet Fuel... 220 Naphtha... 222 Fischer-Tropsch GTL Process... 223 Basis for estimates and evaluation... 228 Process description... 231 Section 100 - Syngas Generation... 232 Section 200 - Fischer-Tropsch Synthesis... 233 Section 300 - Refinery Upgrading... 234 Process discussion... 247 Gas Pretreatment... 247 Natural Gas Reforming... 249 Operating pressure... 251 Syngas composition... 251 F-T catalyst type... 252 F-T operating conditions.... 253 F-T reactor type... 254 Fischer Tropsch reactor microchannel heat exchange fouling... 254 Product recovery... 254 Product refining... 255 Olefin oligomerization... 255 Wax hydrocracking... 255 Conclusion... 256 Cost estimates... 256 Capital costs... 256 Production costs... 257 6. Velocys small scale GTL two stage F-T microchannel reactor set... 262 Introduction... 262 Microchannel steam methane reforming... 262 Fischer-Tropsch Microchannel Reactors... 264 Small Scale Fischer-Tropsch GTL Technology... 264 Fischer-Tropsch Two Stage GTL Process... 265 Basis for estimates and evaluation... 266 Steam Reforming Catalysts... 269 Process description... 269 Section 100 - Syngas Generation... 270 Section 200 Fischer-Tropsch Synthesis... 271 Section 300 Refinery Upgrading... 271 December 2014 vii 2014 IHS
Process discussion... 286 Conclusion... 287 Cost estimates... 288 Capital Costs... 288 Production Costs... 288 Appendix A: Patent Summaries... 293 Appendix B: Design and cost bases... 307 Design conditions... 307 Cost bases... 307 Capital investment... 307 Production costs... 308 Effect of operating level on production costs... 309 Appendix C: Bibliographic citations... 310 Appendix D: Patents by assignee... 320 Appendix E: Process flow diagrams... 323 Tables Table 2.1: Total Capital Costs, $ Million U.S. Gulf Coast... 12 Table 2.2: Economics Summary... 13 Table 4.1: Process Unit Configurations At Different GTL Plant Capacities... 29 Table 4.2: Typical Conversion Rates of a Methane Steam Reformer at Various Process Stages... 46 Table 4.3: Key Reactions In Steam Reforming... 47 Table 4.4: Steam Reforming Catalyst Requirements... 51 Table 4.5: Sources of Common Reformer Poisons... 52 Table 4.6: Routes To Carbon Formation... 55 Table 4.7: Typical Operating Conditions for a Gas Fired POx Unit... 57 Table 4.8: Typical POx Syngas Compositions... 61 Table 4.9: Comparison of Conventional Syngas Technologies... 78 Table 4.10: Capital Cost Savings With GHR... 78 Table 4.11: Syngas Technology Comparisons... 89 Table 4.12: A Comparison Of Syngas Production Technologies... 90 Table 4.13: Comparison Of Gas Reforming Technologies That Are Industrially Applied In Combination With Fischer Tropsch... 97 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... 105 December 2014 viii 2014 IHS
Table 4.15: Characteristics of the Main Reactor Types... 106 Used for Fischer-Tropsch Synthesis... 106 Table 4.16: Comparison Of The Catalyst And Volumetric Reactor Productivity Of Iron Based Catalysts In Different Reactor Types... 122 Table 4.17: Rank Order Of The 10 Most Abundant Chemicals In HTFT Syncrude (Excluding Methane and Water Gas Shift Products)... 132 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... 138 Table 4.19: American Petroleum Institute (API) Classification Of Lubricant Base Oils... 145 Table 4.20: LTFT Syncrude Composition... 146 Table 4.21: Industrial Applications Of n-1 Alkenes... 149 Table 4.22: Mass Balances For Combined Fuels And Chemicals Refining... 151 Table 4.23: Main Technical Features Of The ENI GTL Gas Loop Integration... 167 Table 4.24: Refinery Technologies For Processing Fischer-Tropsch Syncrude In Terms Or Compatability Environmental Impact And Recommended Use... 169 Table 4.25: Characteristics Of Different Naphtha Fractions Produced From Co-LTFT Synthesis and Refining... 171 Table 4.26: Fischer-Tropsch Aqueous Product From Co-LTFT Synthesis... 173 Table 4.27: Diesel Fuel Specifications Employed For Syncrude Refinery Design... 179 Table 4.28: Products From LTFT Diesel Fuel Refinery Design... 182 Table 5.1: Comparison Of Fischer-Tropsch Reactor Types... 208 Table 5.2: Typical Properties Of Syncrude - Vs. Crude Oil... 210 Table 5.3: Specification of F-T Diesel Compared To Conventional Diesel... 220 Table 5.4: Fischer-Tropsch Jet Fuel... 221 Table 5.5: Design Bases and Assumptions Production of Integrated Fuels By The Haldor-Topsoe Autothermal Syngas Process... 228 Table 5.6: Small scale land-based GTL (Case 1) Stream flows... 235 Table 5.7: Small Scale Land Based GTL Velocys Single Stage F-T Reactor Major Equipment... 244 Table 5.8: Small Scale Land Based GTL Velocys Single Stage F-T Reactor Utilities Summary... 246 Table 5.9: Small Scale Land Based GTL Velocys Single Stage F-T Reactor Total Capital Investment... 258 Table 5.10: Small Scale Land Based GTL - Velocys Single Stage F-T Reactor Capital Investment By Section... 259 Table 5.11: Small Scale Land Based GTL - Velocys Single Stage F-T Reactor Production Costs... 260 Production costs... 261 Table 6.1 : Small Scale Land Based GTL Velocys Two-Stage F-T Reactor System Design Bases... 267 Table 6.2: Small scale land-based GTL (Case 2) Stream flows... 273 Table 6.3: Small Scale Land Based GTL - Velocys Two-Stage F-T Reactor System Major Equipment... 283 Table 6.4: Small Scale Land Based GTL - Velocys Two-Stage F-T Reactor System Utilities Summary... 286 Table 6.5: Small Scale Land Based GTL - Velocys Two-Stage F-T Reactor System Total Capital Investment... 289 Table 6.6: Small Scale Land Based GTL - Velocys Two-Stage F-T Reactor System Capital Investment By Section... 290 Table 6.7: Small Scale Land Based GTL - Velocys Two-Stage F-T Reactor System Production Costs. 291 December 2014 ix 2014 IHS
Figures Figure 3.1: GreenSky London Biorefinery Block Flow Diagram... 17 Figure 4.1: GTL Process Steps... 25 Figure 4.2: Large Scale Fischer-Tropsch Based GTL Plant Investment Profile... 26 Figure 4.3: GTL Project Financial Risk... 27 Figure 4.4: Conventional Shale Gas Processing Plant Integration with Ethylene Cracking... 33 Figure 4.5: Syngas Clean-up Process Flow Schematic... 37 Figure 4.6: Process Flow Schematic For Hydrosulfurization and Subsequent Sulfur Removal From Gaseous Reforming Feedstocks... 39 Figure 4.7: Chlorine Guard Bed On Top of Desulfurization Bed... 41 Figure 4.8: Steam Methane Reforming Process Flow Schematic... 44 Figure 4.9: Process Flow Schematics for Direct and Pre-Reforming Multifeed Steam Reforming Configurations... 45 Figure 4.10: Schematic Representations of Tubular Steam Reforming Technologies of Different Furnace Firing Configurations... 48 Figure 4.5: Sources of Common Reformer Poisons... 52 Figure 4.11: Adiabatic Preforming Process Flow Schematic... 54 Figure 4.12: Partial Oxidation of Methane to Synthesis Gas... 56 Figure 4.13: The Boiler System for Partial Oxidation of Gaseous and Liquid Hydrocarbons... 58 Figure 4.14: Sour Water Stripping Process Flow Schematic... 60 Figure 4.15: Autothermal Reformer Process Flow Schematic... 65 Figure 4.16: Autothermal Reforming Process Flow Schematic... 69 Figure 4.17: Process Flow Schematic of Gas Heated Reforming... 72 Figure 4.18: Johnson Matthey/Davy Gas Heated Reformer Schematic... 73 Figure 4.19: Incorporation of a Heat Exchange Post Reformer With Steam Methane Reforming... 74 Figure 4.20: Conventional Straight Tube Heat Exchanger... 75 Figure 4.21: Conventional U-Tube Heat Exchanger... 75 Figure 4.22: Different Process Gas Heat Exchange Reformer Design Types... 77 Figure 4.23: Heat Exchange Reformers Combined With ATR... 77 Figure 4.24: Haldor Topsøe Heat Exchange Reformer Schematic... 79 Figure 4.25: Parallel Gas Fed ATR/GHR Syngas Production Combination... 80 Figure 4.26: Series Gas Fed ATR/GHR Combination... 80 Figure 4.27: Combined Reforming... 82 Figure 4.28: Compact Reformer... 84 Figure 4.29: Process Flow Schematic of Compact Reforming Principles... 86 Figure 4.30: Simplified Process Flow Schematic For Use Of Compact Reforming In The BP/Davy Integrated GTL Process To Produce Syncrude... 88 Figure 4.31: Typical Single Train Syngas Reforming Capacities... 91 Figure 4.32: Process Flow Schematic Of Velocys SMR Microchannel Reactor Block... 99 Figure 4.33: Prototype Experimental Steam Reforming RMR Reactor... 101 Figure 4.34: Generic Schematic Of a Multitibular Fixed Bed Reactor... 110 Figure 4.35: Multitubular Fixed Bed Reactor (Arge)... 111 Figure 4.36: Gas-Solid CFB F-T Reactor... 115 Figure 4.37: Generic Schematic Of A Fixed Fluidized Bed Reactor... 116 December 2014 x 2014 IHS
Figure 4.38: Advanced Synthol FFB Reactor... 118 Figure 4.39: Generic Schematic Of A Slurry Bubble Column Reactor... 119 Figure 4.40: F-T Slurry Bubble Column Reactor... 120 Figure 4.41: ASF Carbon Number Distributions... 130 Figure 4.42: Generic Process Flow Schematic Of HTFT Reactor Product Recovery... 134 Figure 4.43: Generic Process Flow Schematic Of LTFT Reactor Product Recovery Section... 135 Figure 4.44: Boiling Point Cut Range Nomenclature Overlaps... 144 Figure 4.45: Two Types Of Closed Gas Loop Designs... 156 Figure 4.46: Gas Loop Design For Sasol-Lurgi Gasifier With HTFT Synthesis... 159 Figure 4.47: Mossel Bay Gas Loop Block Flow Diagram... 160 Figure 4.48: Gas Loop Scheme For LTFT With POx... 161 Figure 4.49: ENI Gas Loop Integration... 162 Figure 4.50: HTCR Reactor... 164 Figure 4.51: Haldor Topsøe Compact Convective Reformer Process... 165 Figure 4.5: Typical Layout Of A HTCR Twin Process... 166 Figure 4.53: Process Flow Schematic Of Refinery Upgrading Section For Small Scale GTL... 170 Figure 4.54: Wax Hydrocracking Process Flow Schematic... 172 Figure 4.55: Complex Wax Hydrocracking Configuration Process Flow Schematic... 173 Figure 4.56: Fischer-Tropsch Oxygenates Recovery From Synthesis Reaction Water... 174 Figure 4.57: Process Flow Schematics Of Options For Fischer-Tropsch Aqueous Product Refining... 175 Figure 4.58: Generic Fischer-Tropsch Refinery Configuration Designed To Increase Distillate Yield... 176 Figure 4.59: Technology Selection For The Refining Of Syncrude To Diesel Fuel When There Is No Minimum Diesel Fuel Density Requirement... 177 Figure 4.60: Integrated Crude Oil And Gas Based F-T Refinery... 178 Figure 4.61: LTFT Diesel Fuel Refinery Design Process Flow Schematic... 180 Figure 4.62: LTFT Jet Fuel Refinery Design That Maximizes Diesel Fuel Yield With Minimum Density Requirement... 183 Figure 5.1: Velocys Simplified Fischer-Tropsch Block Flow Diagram... 192 Figure 5.2: Fischer Tropsch Relative Reactor/Co Catalyst Reactivity Comparison... 197 Figure 5.3: Velocys Fischer-Tropsch Microchannel Reactor Block... 201 Figure 5.4: Commercial Designs For Single Smr And F-T Microchannel Reactor Modules... 209 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... 210 Figure 5.7: LTFT Jet Fuel Refinery Block Flow Diagram... 212 Figure 5.7: Small Scale Land Based Fischer-Tropsch Process... 218 Figure 5.8: Small Scale Land Based Fischer-Tropsch GTL Block Flow Process Diagram... 224 Figure 5.9: Fischer-Tropsch Synthesis Quad Block Reactor Module... 226 Figure 5.10: Two Stage Fischer-Tropsch Reactor Operation Impact Of Hydrocarbon Conversion And C5+ Selectivity On C5+ Yield... 227 Figure 5.11: Single Stage Fischer-Tropsch Reactor Operation with Tail Gas Recycle... 227 Figure 6.1: Two Stage Once-Through Fischer-Tropsch Synthesis Reactor Operation... 266 December 2014 xi 2014 IHS