DOE NETL Cooperative Agreement DE FE0012054 oil
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I. Promising catalyst candidates synthesized and tested at lab scale with 35 to 500 ppm H 2 S II. Catalyst studied showed no significant reduction in activity for ~ 220 hours for 35 ppm, 50 hours for 90 ppm H 2 S, and significant tolerance to 500 ppm H 2 S III.Significant increase in syngas yields using raw syngas feed, however no appreciable changes in H 2 :CO ratio without additional steam IV.Preliminary TEA modeling of 50,000 bpd plant indicates greatly improved FT yield for given coal feed rate (less coal needed for given FT output), but near identical costs for FT production due to much less power produced. CO 2 emission costs and power price have large impacts on economics. 50% reduction in carbon emissions per barrel of FT liquids. Pyrolysis oil Petroleum oil Biomass conversion, % 94‐98 ~90 Moisture content, % <1 25‐30 <0.1 TAN, mg KOH/g < 0.8 ~100 <1.0 DOE NETL Cooperative Agreement DE‐FE0012054 Catalyst shows high activity Southern Research in cooperation with US Department of Energy-NETL is developing a high concentration H 2 S resistant reforming catalyst for increasing syngas yields derived from low rank coal and biomass gasification. Conventional low rank coal and biomass gasified syngas streams contain sulfur, residual methane, tars and ammonia which are usually removed via gas clean up processes before Fischer-Tropsch reactor to produce liquid fuels. Highly adaptable sulfur resistant catalyst technology for coal and coal biomass syngas upgrading potentially allows lowering the capital costs, GHG emissions (via biomass utilization) and is an easy retrofit to existing gasifiers. It allows US coal industry to further improve process carbon efficiencies. CTL Process Under Development Catalytic Studies Results: Results obtained over Southern’s proprietary catalysts show resilience to H 2 S with high activity as compared to five comparable literature/commercial catalysts Catalyst Stability No catalyst deactivation observed for ~ 220 hours on stream under different feeds and reaction conditions. Catalyst adaptable for varying steam to methane ratios, H 2 S/Tar conc. and system pressure depending on feeds and type of gasifier employed. Performance in High H 2 S Concentrations No effect of 90 ppm H 2 S on methane conversion Reduced conversion in 500 ppm H 2 S, but Minimal reduction of performance over 200 hours of exposure to high concentration of H 2 S Acknowledgements: Darryl Shockley DOE/NETL Project Manager To increase the yield and possibly H 2 :CO ratio of a raw low-rank coal syngas by high temperature reforming prior to sulfur removal Develop catalysts for simultaneously reforming of tars, methane, and C 2 -C 6 hydrocarbons, and decomposing NH 3 in the presence of H 2 S Demonstrate the performance of the catalyst(s) in a lab-scale reactor version of the catalytic reforming process at commercially viable conditions Preliminary techno-economic model that will be used to evaluate the commercial viability of this process relative to the current state-of-the art Potential Technical Advantages • Tar, methane, light hydrocarbons, NH 3 conversion to additional CO and H 2 in one step • Reduce or eliminate requirements for a water-gas shift step • Potential for Fischer-Tropsch (FT) tail gas to provide heat for the reforming and increase syngas yield to FT liquids • Sulfur tolerant reforming catalyst allows use at any stage of cleanup • Adaptable to all coal or coal-biomass gasification technologies • Increasing the energy efficiency of gasification using high- temperature gas clean up Feed Compositions: Probstein, R. F. and R. E. Hicks (2006)., Driscoll D. (2008). H 2 CO CO 2 CH 4 H 2 O H 2 S NH 3 Tar TRIG - lignite 29.2% 34.3% 13.6% 2.5% 18.9% 100-250 ppm .28% .10% Lurgi’s FBDB - lignite 18.7% 7.5% 15.7% 5.2% 51.6% .29% .58% .41% High methane conversions in presence of high H 2 S Approximately ~20 % increase in syngas yields. Insignificant increase in H 2 :CO ratio without additional steam. • Transport Reactor Integrated Gasifier (TRIG) • Steam reformer prior to cooling syngas • POX on recycled gas or natural gas to generate heat for reformer • No tar and ammonia cleanup processes needed • High-activity liquid-selective FT Catalyst that does not produce wax (SR/NETL Project DE-FE0010231) • Little to no product upgrading Disclaimer: "This report was prepared as an account of work sponsored by an agency of the United States Government. Neither the United States Government nor any agency thereof, nor any of their employees, makes any warranty, express or implied, or assumes any legal liability or responsibility for the accuracy, completeness, or usefulness of any information, apparatus, product, or process disclosed, or represents that its use would not infringe privately owned rights. Reference herein to any specific commercial product, process, or service by trade name, trademark, manufacturer, or otherwise does not necessarily constitute or imply its endorsement, recommendation, or favoring by the United States Government or any agency thereof. The views and opinions of authors expressed herein do not necessarily state or reflect those of the United States Government or any agency thereof." Lab scale micro-reactor system constructed for tests 12 reforming catalysts synthesized, characterized and screened for performance using simulated TRIG and Lurgi gasifier syngas with up to 500 ppm H 2 S. Three catalysts showed high reforming activity in the presence of H 2 S for extended periods of time Preliminary Economics for CTL with Iron catalyst DOE/NETL 2015 Gasification Systems and Coal & Coal‐Biomass to Liquids (C&CBTL) Workshop Cost of Production for 50,000 BPD plant with CO2 sequestration featuring TRIG Gasifier and Iron FT catalyst Base case With POX/ Reformer Feel Coal (Ton/day) 35,856 26,389 Output liquid products (BPD) 49,996 49,996 Net Power Production (MWe) 354 ‐47 CAPEX $MM Total Overnight Cost (TOC) $5,859 $5,625 Cost of Production (Equivalent Petroleum Diesel, $/gal) $3.41 $3.43
Transcript of DOE NETL Cooperative Agreement DE FE0012054 oil
I. Promising catalyst candidates synthesized and tested at lab scale with 35 to 500 ppm H2S
II. Catalyst studied showed no significant reduction in activity for ~ 220 hours for 35 ppm, 50 hours for 90 ppm H2S, and significant tolerance to 500 ppm H2S
III.Significant increase in syngas yields using raw syngas feed, however no appreciable changes in H2:CO ratio without additional steam
IV.Preliminary TEA modeling of 50,000 bpd plant indicates greatly improved FT yield for given coal feed rate (less coal needed for given FT output), but near identical costs for FT production due to much less power produced. CO2 emission costs and power price have large impacts on economics. 50% reduction in carbon emissions per barrel of FT liquids.
PyrolysisoilPetroleumoilBiomassconversion,%94‐98~90
Moisture content, %<125‐30<0.1TAN,mgKOH/g<0.8~100<1.0
DOENETLCooperativeAgreementDE‐FE0012054
Catalyst shows high activity
Southern Research in cooperation with USDepartment of Energy-NETL is developing a highconcentration H2S resistant reforming catalyst forincreasing syngas yields derived from low rankcoal and biomass gasification.
Conventional low rank coal and biomassgasified syngas streams contain sulfur, residualmethane, tars and ammonia which are usuallyremoved via gas clean up processes beforeFischer-Tropsch reactor to produce liquid fuels.
Highly adaptable sulfur resistant catalysttechnology for coal and coal biomass syngasupgrading potentially allows lowering the capitalcosts, GHG emissions (via biomass utilization)and is an easy retrofit to existing gasifiers. Itallows US coal industry to further improveprocess carbon efficiencies.
CTL Process Under Development
Catalytic Studies Results:
Results obtained over Southern’s proprietary catalysts show resilience to H2S with high activity as compared to five comparable literature/commercial catalysts
Catalyst Stability
No catalyst deactivation observed for ~ 220 hours on stream under different feeds and reaction conditions.
Catalyst adaptable for varying steam to methane ratios, H2S/Tar conc. and system pressure depending on feeds and type of gasifier employed.
Performance in High H2S Concentrations
No effect of 90 ppm H2S on methane conversion Reduced conversion in 500 ppm H2S, but Minimal reduction of performance over 200 hours
of exposure to high concentration of H2S
Acknowledgements: Darryl Shockley DOE/NETLProject Manager
To increase the yield and possibly H2:CO ratio of araw low-rank coal syngas by high temperaturereforming prior to sulfur removal
Develop catalysts for simultaneously reforming oftars, methane, and C2-C6 hydrocarbons, anddecomposing NH3 in the presence of H2S
Demonstrate the performance of the catalyst(s) in alab-scale reactor version of the catalytic reformingprocess at commercially viable conditions
Preliminary techno-economic model that will beused to evaluate the commercial viability of thisprocess relative to the current state-of-the art
Potential Technical Advantages• Tar, methane, light hydrocarbons, NH3 conversion to
additional CO and H2 in one step
• Reduce or eliminate requirements for a water-gas shift step
• Potential for Fischer-Tropsch (FT) tail gas to provide heat for the reforming and increase syngas yield to FT liquids
• Sulfur tolerant reforming catalyst allows use at any stage of cleanup
• Adaptable to all coal or coal-biomass gasification technologies
• Increasing the energy efficiency of gasification using high-temperature gas clean up
Feed Compositions: Probstein,R.F.andR.E.Hicks(2006).,DriscollD.(2008).
H2 CO CO2 CH4 H2O H2S NH3 TarTRIG -lignite
29.2% 34.3% 13.6% 2.5% 18.9% 100-250 ppm .28% .10%
Lurgi’s FBDB -lignite
18.7% 7.5% 15.7% 5.2% 51.6% .29% .58% .41%
High methane conversions in presence of high H2S
Approximately ~20 % increase in syngas yields. Insignificant increase in H2:CO ratio without additional steam.
• Transport Reactor Integrated Gasifier (TRIG) • Steam reformer prior to cooling syngas • POX on recycled gas or natural gas to generate heat for reformer• No tar and ammonia cleanup processes needed• High-activity liquid-selective FT Catalyst that does not produce wax
(SR/NETL Project DE-FE0010231) • Little to no product upgrading
Disclaimer:"ThisreportwaspreparedasanaccountofworksponsoredbyanagencyoftheUnitedStatesGovernment.NeithertheUnitedStatesGovernmentnoranyagencythereof,noranyoftheiremployees,makesanywarranty,expressorimplied,orassumesanylegalliabilityorresponsibilityfortheaccuracy,completeness,orusefulnessofanyinformation,apparatus,product,orprocessdisclosed,orrepresentsthatitsusewouldnotinfringeprivatelyownedrights.Referencehereintoanyspecificcommercialproduct,process,orservicebytradename,trademark,manufacturer,orotherwisedoesnotnecessarilyconstituteorimplyitsendorsement,recommendation,orfavoringbytheUnitedStatesGovernmentoranyagencythereof.TheviewsandopinionsofauthorsexpressedhereindonotnecessarilystateorreflectthoseoftheUnitedStatesGovernmentoranyagencythereof."
Lab scale micro-reactor system constructed for tests
12 reforming catalysts synthesized, characterized and screened for performance using simulated TRIG and Lurgi gasifier syngas with up to 500 ppm H2S.
Three catalysts showed high reforming activity in the presence of H2S for extended periods of time
Preliminary Economics for CTL with Iron catalyst
DOE/NETL2015GasificationSystemsandCoal&Coal‐BiomasstoLiquids(C&CBTL)Workshop
Cost of Production for 50,000 BPD plant with CO2 sequestration featuring TRIG Gasifier and Iron FT catalyst Base case
With POX/ Reformer
Feel Coal (Ton/day) 35,856 26,389
Output liquid products (BPD) 49,996 49,996
Net Power Production (MWe) 354 ‐47
CAPEX $MM Total Overnight Cost (TOC) $5,859 $5,625
Cost of Production (Equivalent Petroleum Diesel, $/gal) $3.41 $3.43
