Outline Why Valorize Natural Gas Liquids (NGLs)? Existing Technologies Center for Innovative and Strategic Transformation of Alkanes Resources 1
Energy Density Gas 55 To extract energy, burn it! Oil 47 MJ Kg -1 Coal 15-27 Biomass 15 CO 10 2 CO 2 0 E. Iglesia, UC Berkeley
C 2 and C 3 Production Exceeds Consumption and Continues to Grow Natural Gas Plant Field Production - 2015 US Domestic Consumption - 2015 1.4 1.2 US Natural Gas Plant Field Production MMBbl/day 1 0.8 0.6 0.4 0.2 0 Ethane Propane Use of Ethane in Natural Gas and as a Feedstock for Ethylene Production in the US Has Reached Saturation EIA, Short Term Energy Outlook, 2016; Natural Gas Plant Field Production Data, EIA, 2016 3
Exporting Light Hydrocarbons The U.K. is about to receive its first American shale gas. Bloomberg, September 29, 2016. 4
Ethane supplier to the world: Chemical makers on three continents are set to tap into cheap feedstock from the U.S. 5 Chemical and Engineering News, Volume 94 Issue 44, pp. 28-29, November 7, 2016
Remote Shale Basins Lack Processing and Distribution Infrastructure US Hydrocarbon Gas Liquid Pipeline Gas Processing Capacity Bakken Niobrara Marcellus Conway, KS Planned ( 15) HGL Pipeline New or Reconfigured ( 13-14) HGL Pipeline Existing HGL Pipeline Mont Belvieu, TX 6 Drilling Productivity Report, EIA, 2016 US Natural Gas Network, EIA, 2016 Wallace, E.M. Texas A&M University. M.S. Thesis. 2014.
Shale Gas Stranded in the Remote Basins are Generally Discounted Marcellus Utica Dominion South Transco Leidy Line Tennessee Zone 4 Marcellus Henry Hub 40% Cheaper Than Hub Price 7
Daily Gas Production [MMcfd] 1.2 1.0 0.8 0.6 0.4 0.2 Challenges Associated with Regional Use of Natural Gas Liquids Bakken Eagle Ford Niobrara Permian 0.0 0 20 40 60 80 100 120 140 160 Months on Production 50% - 83% reduction in gas production in three years! Production Rate [Tcf/yr] 2.5 2.0 1.5 1.0 0.5 2010 0.0 1995 2000 2005 2010 2015 2020 2025 2030 58% reduction in overall gas production in ten years! 8 Allen, 2016 Texas RRC Bureau of Economic Geology UT Austin
Challenges Associated with Regional Use of Natural Gas Liquids Barnett Shale Basin 9 Large spatial-variation of feedstocks within the same shale basin Allen, 2016 Texas RRC Bureau of Economic Geology UT Austin
Current Shale Gas On Site Processing Landscape Shale Wells Raw Shale Gas Gas Treatment NGL Recovery CH 4 -Rich Gas Flare NGL Fractionation Ethane Propane Butane C 5+ Trucks Railways Pipeline 10 B. Ka and K. Pe, Oil Gas J., 2009.
Current Shale Gas On Site Processing Landscape Shale Wells Raw Shale Gas Gas Treatment Flare NGL Recovery CH 4 -Rich Gas High Pressure/Low NGL Temperature Required! Fractionation Ethane Propane Butane C 5+ Trucks Railways Pipeline 11 B. Ka and K. Pe, Oil Gas J., 2009.
NGL Transformation can Provide a Better Value for the Producer Shale Wells Raw Shale Gas Gas Treatment Flare NGL Recovery NGL CH 4 -Rich Gas Pipeline Fractionation Trucks Railways Pipeline Ethane Propane Butane C 5+ Pipeline NGL Transformation Pipeline Railway Liquid Trucks Hydrocarbons Chemicals 12
NGL Transformation can Provide a Better Value for the Producer Shale Wells Raw Shale Gas Gas Treatment Flare Value to the Producer ($/MMBtu): Gulf Coast Price Transportation Cost (Bakken à Gulf Coast) NGL Recovery NGL CH 4 -Rich Gas Fractionation 3.0 Trucks Railways Pipeline NGL Transformation Ethane Propane Butane C 5+ Pipeline 4.4 2.3 Pipeline 5.8 Pipeline Railway Liquid Trucks Hydrocarbons Chemicals 13
Existing Technologies Gas-to-Liquids (GTL) Fischer-Tropsch Methanol-to-Gasoline Steam Cracking of Ethane Propane Dehydrogenation SynFuels Ethane-to-Gasoline 14
GTL Fischer-Tropsch Ethane CO H 2 O CO 2 H 2 H 2 O Reformer 1123 K H 2 /CO: ~2.6 Fischer- Tropsch Product Upgrading Reformer Heat Duty: 349 MJ/kmol of Ethane Hydrocarbons Yield: 135 bbl/mmscf* Estimated CAPEX for 15 Mbbl/day: 325-525 MMUSD Hydrocarbons 15 Jacometti, J. 2000.
GTL Fischer-Tropsch Ethane CO H 2 O CO 2 H 2 H 2 O Reformer 1123 K H 2 /CO: ~2.6 Fischer- Tropsch Product Upgrading Reformer Heat Duty: 349 MJ/kmol of Ethane Hydrocarbons Yield: 135 bbl/mmscf* Estimated CAPEX for 15 Mbbl/day: 325-525 MMUSD Hydrocarbons Examples: Infra Technology GreyRock Direct Fuel Production 16 Jacometti, J. 2000.
Methanol-to-Gasoline (MTG) Ethane CO H 2 O CO 2 H 2 H 2 O Reformer 1123 K H 2 /CO: ~2.6 MeOH Synthesis MTG Reformer Heat Duty: 349 MJ/kmol of Ethane Gasoline Yield: 111 Bbl/MMSCF Gasoline Estimated CAPEX for 15 MBbl/day: 1,500 MMUSD 17 Helton and Hindman, GTL Tech. Forum, 2014
Steam Cracking of Ethane Steam Ethane Steam Cracking 650 680 C Olefins C 2,C 1, Benzene, Acetylene H 2 O Cracker Heat Duty:103 MJ/kmol of Ethane (30% of heat for steam generation!) Ethane Conversion: 67% Ethane Selectivity: 81% Water Removal H 2 O Olefins C 2,C 1, Benzene, Acetylene 18 Cutler, J. 2013
Steam Cracking of Ethane Steam Ethane Steam Cracking 650 680 C Olefins C 2,C 1, Benzene, Acetylene H 2 O Cracker Heat Duty:103 MJ/kmol of Ethane (30% of heat for steam generation!) Ethane Conversion: 67% Ethane Selectivity: 81% Water Removal H 2 O Olefins C 2,C 1, Benzene, Acetylene By-products leads to the need for further downstream processes! Estimated CAPEX for 90 MBbl of Ethane/day: 6 Billion USD 19 Cutler, J. 2013
Propane Dehydrogenation Net Gas (H 2 Rich) Hydrogen C 2 Oleflex SHP Deethanizer Propylene Propane Feed Depropanizer Per Pass Propane Conversion: 40% 90 % of propane conversion is selective to propylene and hydrogen. P-P Splitter C 4+ Estimated CAPEX for 958 ton of Propylene/day: 215 MMUSD 20 Meyers, R.A, Handbook of Petroleum Refining Processes, 2004.
SynFuel Ethane-to-Gasoline Oxygen Ethane Thermal Cracker Ethylene Reactor Product Reactor Hydrocarbons Fuel Gas Liquid Hydrocarbons Yield: 183 bbl/mmscf of Ethane Estimated CAPEX for 15 Mbbl/day: 349 MMUSD 21 J. Cantrell, J. A. Bullin, C. Butts, and B. Cheatham, Economic Alternative for Remote and Stranded Natural Gas and Ethane in the US.
Summary of Existing Technologies Technologies to produce value added products from shale gas do exist, but 22
Summary of Existing Technologies Technologies to produce value added products from shale gas do exist, but It is unclear whether small scale process can accommodate for temporal and spatial variations in NGL production The choices are somewhat limited Only syngas and olefins route All existing choices have been proven only at large to regional scales 23
CISTAR Strives to Innovate at All Scales and Considers Many Chemistries Raw Shale Gas Pipeline Gas Treatment NGL Recovery CH4-Rich Gas Shale Wells Flare NGL Fractionation Ethane Propane Butane C5+ Pipeline Trucks Railways Pipeline CISTAR NGL Transformation 24 Pipeline Railway Liquid Trucks Hydrocarbons Chemicals
National Science Foundation Engineering Research Center Funded at $5M per year for 10 years
26 Innovation Ecosystem Partners
Integrated Academic and Industrial Experience Olefin Conversion Olefin Intermediates Developed working processes Over 600 patents Over 120 years of industrial experience 27 Methane Activation 8 NAE members, 1 NAS member 1 National Medal of Technology 1 National Medal of Science
CISTAR Strives to Innovate at All Scales and Considers Many Chemistries CISTAR is working on multiple fronts: Catalysts Chemistries Separations Processes 28
Process Intensification and Modularization Toward Distributed Production of Liquid Fuel Variable Feed Rate Challenges Varying Scales Variable Composition Small Scale Medium Scale Large Scale Innovation Process Synthesis Variable Production Rate: 100%-15% 29 Process Design Optimal Process Process Intensification
Conclusion Existing technologies have only been proven at large scales The current choices are: Limited to only syngas and olefin routes Unlikely to handle temporal and spatial variations in shale gas feed There is a need for new chemistry, catalysts, separations and processes CISTAR will provide innovations to address these issues. 30
Acknowledgments Prof. Rakesh Agrawal Prof. Thomas F. Degnan Prof. Jeffrey T. Miller Prof. Jeffrey Siirola Dr. Emre Gençer Yiru Li Taufik Ridha Funding: 31
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