Advancement of Biomass to Liquids and Hydrogen Separation Technologies Through the Utilization of Pilot-Scale Gasifiers

Transcription

1 Advancement of Biomass to Liquids and Hydrogen Separation Technologies Through the Utilization of Pilot-Scale Gasifiers Gasification Technologies Conference 2011 San Francisco, California October 9 12, 2011 Josh Stanislowski, Josh Strege, and Grant Dunham, EERC Jeffery Hufton and Fei Chen, Air Products and Chemicals, Inc University of North Dakota Energy & Environmental Research Center.

2 Presentation Overview 2 What is the EERC? (briefly) Small-scale test facilities description Hydrogen separation membrane development Biomass to Fischer Tropsch (FT) liquids testing Gas separation testing with sour pressure swing adsorption (PSA)

3 What Is the EERC? Founded in 1951 as a U.S. Bureau of Mines laboratory to study lignite gasification. Defederalized in 1983 and became a part of the University of North Dakota. Has expanded into all fossil fuels, renewables, pollution prevention, environmental remediation, water, hydrogen, and materials research. 3

4 What Is the EERC? Research performed through partnerships with commercial clients and state government, sometimes leveraging federal funding to answer key technical questions. $199 million contract portfolio in FY11 Clientele: 4 Governmental: 94 Academia: 53 International Market: 154 Private Corporations: 871

5 Advanced Gasification Technology Pathways Areas where the EERC is supporting RDD&C Gerdes et al. Current and Future Technologies for Gasification Based Power Generation; NETL, Vol. 2, Revision 1, Oct 7,

6 Demonstration of Pilot-Scale Systems Chronology of Gasification Research, Development, and Demonstration (RD&D) at the EERC Transport Reactor Development Unit EntrainedFlow Gasifier Catalytic Gasification/SOFC Year Annular Externally Slagging FixedHeated Retort Bed Gasifier Mild Gasification 2005 Biomass Microgasifier

7 Small Pilot-Scale Gasification Test Systems EERC small pilot-scale gasifiers are used for syngas generation: Entrained-flow gasifier (EFG) 2850 F (1565 C) 300 psi (20 atm) High-pressure fluid-bed gasifier (HPFBG) 1800 F (980 C) 1000 psi (68 atm) Warm-gas cleanup available for each system. 8-lb/hr coal nominal feed rate.

8 Gas Cleanup and Purification/Synthesis Fluid-Bed Gasifier Hot-Gas Filter Vessel Bulk Desulfurizer RVS-1 HT WGS Chlorine Sulfur Guard/LT Polishing WGS Trace Metal Control Final Purification/End Use H 2 Separation Membrane Selective Catalytic Reduction (SCR) Catalyst EFG FT PSA

9 Hydrogen Separation Membrane Technology Development Supporting U.S. Department of Energy (DOE) goals of producing hydrogen from coal using hydrogen separation membranes and coal-derived syngas. Phase I 2 lb/day H2 Phase II 100 lb/day H2 Phase III Detailed design of demonstration scale unit. Working with several membrane developers to test membrane technology on coalderived syngas: Eltron Research Praxair United Technologies Research Center (UTRC) 9

10 Biomass-to-Liquid (BTL) Testing and Development 10

11 BTL Production Demonstration Multiyear DOE National Energy Technology Laboratory (NETL) agreement. First year $750,000 through DOE NETL, $950,000 total to study distributed coal-to-liquid (CTL) and BTL scenarios. Membership in Brigham Young University (BYU) FT Consortium offers FT reactor design and cheap, available catalyst formulations. Concept in first year was to demonstrate small-scale production of FT liquids for potential distributed systems. 11

12 FT Reactor Design Skid-mounted, modular design Design from BYU Two Dowtherm-cooled packed-bed FT reactors Space and modules for expansion to four beds Syngas preheat Both gas and FT liquid recycle Utilize catalysts produced at EERC 12

13 Gas Cleanup and Purification/Synthesis Fischer Tropsch Fluid Bed Gasifier Hot-Gas Filter Vessel Bulk Desulfurizer RVS-1 Sulfur Polishing Feeding of coal biomass blends helps to offset CO 2 generated during the production process. Biomass can have catalytic effects that improves gasifier performance. Impurities such as potassium can degrade gasifier performance, especially for fluid-bed systems (agglomeration). 13

14 Coal and Biomass Analyses ND Lignite Leached Olive Pits Leached Dried Distiller s Grains and Solubles (DDGS) Air-Drying Loss Proximate Analysis (air-dried basis) Moisture Volatile Matter Fixed Carbon Ash H C N O S ,506 19,264 19,966 Ultimate Analysis (air-dried basis) Higher Heating Value (HHV), kj/kg 14

15 Product Properties CO Conversion = 49% Selectivity to Light Gas = 28% 12/1 30% DDGS, 70% Lignite 12/2 100% DDGS 12/3 30% Olive Pits, 70% Lignite 15

16 FT Reactor Conclusions Two-stage warm-gas cleanup reduced syngas sulfur to nondetectable levels. Packed-bed FT reactor design feasible with high recycle, low single-pass conversion. Critical to capture tars from gasifier catalyst not easily regenerated after tar exposure. Also capture tars to avoid plugging, as catalyst activity does not recover after rapid shutdown. High CO2 detrimental to iron-based catalyst. For small-scale packed-bed FT reactor, may need to use cobalt-based catalyst or develop effective warmgas CO2 sorbents. 16

17 Scale-up to Truck-Mounted System for BTL Production Portable so it can be moved to the wood source. Can gasify wood with up to 50% moisture. Can produce a higher H2/C ratio syngas for easier conversion to liquid fuels. Minimal operational labor requirements. Up to 1 MW thermal throughput. 17

18 Sour PSA Development With Air Products and Chemicals, Inc. 18

19 Sour PSA the Concept Standard Petcoke Gasification with CO 2 Recovery H 2 O Petcoke LP Fuel Gas H 2 Production ASU O 2 H 2 PSA H 2 H 2 Compression ~1000 psi Gasifiers 1000 psi MP Steam LP Steam H 2 S to SRU H 2 O Shift Reactors LT Heat Recovery Selexol AGR CO 2 Syngas H 2 S/CO 2 PSA H 2 H 2 S+CO 2 Sulfur Disposition Technology CO 2 Compression CO 2 19 Sulfur Species

20 Adsorbent Feasibility Testing Need robust adsorbent that survives sour syngas environments and exhibits high, reversible H 2 S capacity. Six-month exposure testing of five adsorbents to simulated syngas containing H 2 S. Analysis of samples indicated that two adsorbent materials can handle H 2 S exposure. But what about?? Tolerance to other trace components? Impact of tar species? Adsorption behavior in fixed bed? Cyclic PSA performance? 20 Air Products and Chemicals, Inc All Rights Reserved

21 Interface Gasifier with Sour PSA Unit Fluidized-bed or EFG Sour syngas taken after sour shift/cooling Sour PSA unit contains two packed beds and can be operated with a simple PSA cycle Flow/composition analysis for process performance H 2 S breakthrough tests to evaluate adsorbent stability PRB coal + sulfur oxygen H 2 S-free product gas Sour PSA cycle (30C) Sour syngas feed at 400 psig (300s) dep to 1-3 psig (120s) product purge at 1-3 psig (60s) product repress (120s) steam Sour syngas PSA packed with single layer of adsorbent 21 Fluidized-Bed Coal Gasifier Sour PSA Unit Air Products and Chemicals, Inc All Rights Reserved

22 Gas Cleanup and Purification/Synthesis EFG Hot-Gas Filter Vessel PSA Sour WGS Sour WGS No H 2 S removal needed. Two beds used for sour shift (higher temp./lower temp.) Gas was quenched and compressed prior to sour PSA testing (compression not needed in commercial application). 22

23 Demonstration of PSA Operation Conducted a total of 1500 PSA cycles with EFG and Albertan petcoke. Performance stable over period of a few days. Micro GC Analysis (%) H2 N2 CO CO2 FEED DEP PURGE PROD H2, % N2, % CM, % CD, % H2S, ppm Feed H 2 S level of 0.75% reduced to ~3 ppm in product, stable /24/2010 7:00 5/24/ :00 5/24/ :00 5/25/2010 7:00 5/25/ :00 5/25/ :00 5/26/2010 7:00 5/26/ :00 Time 5/26/ :00 5/27/2010 7:00 5/27/ :00 5/27/ :00 5/28/2010 7: % H 2 S rejection, 98.7% CO 2 rejection, 65% H 2 recovery 23 Air Products and Chemicals, Inc All Rights Reserved

24 Evaluation of Adsorbent Capacity Stability First assessment of impact of the many components of sour syngas (sulfur compounds [predominantly H 2 S, COS], HCl, NH 3, metal carbonyls, organic tars, Hg, As, and others) H 2 S adsorption capacity determined via breakthrough tests remains stable for entire EFG campaign 1.20 Relative H 2 S Capacity Bed A Bed B Number of PSA Cycles 24 Air Products and Chemicals, Inc All Rights Reserved

25 Adsorbent Postmortem Useful for understanding syngas/adsorbent interactions. Pulled samples of the adsorbent at the end of testing. Yellowish color toward feed end XRF analysis indicates slight accumulation of sulfur. Fe, Ni not present above fresh adsorbent levels (no carbonyl issues). No evidence of tar species. 25 Air Products and Chemicals, Inc All Rights Reserved

26 Sour PSA Conclusions and Next Steps Sorbent performance was shown to be stable over thousands of cycles on coal derived syngas. Additional testing will take place with EERC gasifiers to validate sorbent performance on additional fuels. Runs with high pressure fluid bed gasifier are planned to eliminate the need to compress before the sour PSA unit. Plans to scale up the technology are in progress and designs will utilize the results of additional testing.

27 Final Summary Understanding the impact of all coal derived impurities is critical to developing the data necessary to move new technologies out of the laboratory and into the commercial marketplace. Small scale gasifiers enable first-of-a-kind exposure to coal derived syngas for novel and advanced gasification technologies. The EERC is well positioned to continue to support gasification technology development.

28 Contact Information Energy & Environmental Research Center University of North Dakota 15 North 23rd Street, Stop 9018 Grand Forks, North Dakota World Wide Web: Telephone No. (701) Fax No. (701) Josh Stanislowski, Research Manager 28