POx and Sour Shift Catalyst Applications

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(POx) Partial Oxidation and Sour Shift Catalyst Applications

Coal
Technology
Gasification
Products From Coal
Power
Conventional combustion
Integrated Gasification Combined Cycle (IGCC)
Ammonia
Methanol
Hydrogen
FT Liquids
Substitute Natural Gas (SNG)

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POx and Sour Shift Catalyst Applications

  1. 1. VULCAN Systems Technology (POx) Partial Oxidation and Sour Shift Catalyst Applications A Business Unit of GBH Enterprises, Ltd. Gerard B. Hawkins Managing Director
  2. 2. Coal An expanding market for catalysts and absorbents A Business Unit of GBH Enterprises, Ltd.
  3. 3. Worldwide Energy Use A Business Unit of GBH Enterprises, Ltd.
  4. 4. A Business Unit of GBH Enterprises, Ltd.
  5. 5. Wyoming Low-S Coal Mountain 80 ft wall of coal seam, Powder Rive basin = 40% of US Coal used today; 100yr supply A Business Unit of GBH Enterprises, Ltd.
  6. 6. Products from Coal • Power • Conventional combustion • Integrated Gasification Combined Cycle (IGCC) • Ammonia • Methanol • Hydrogen • FT Liquids • Substitute Natural Gas (SNG) A Business Unit of GBH Enterprises, Ltd.
  7. 7. Gasification applications Power - IGCC Air Sep Gasifier Gas Cleaning Sulfur Removal Power Turbine Air Coal Sulfur Flue Gas Power A Business Unit of GBH Enterprises, Ltd.
  8. 8. Gasification for Power - IGCC Demo units – 300 MW USD 300 million A Business Unit of GBH Enterprises, Ltd.
  9. 9. Gasification applications Power with CO2 Sequestration Air Sep Gasifier Sour Shift Acid Gas Removal Power Turbine Air Coal Sulfur + CO2 Flue Gas Power A Business Unit of GBH Enterprises, Ltd.
  10. 10. Coal to Chemicals Synthesis Gas Air Sep Gasifier Sour Shift Acid Gas Removal Air Coal Sulfur + CO2 Methanol FT Ammonia Hydrogen A Business Unit of GBH Enterprises, Ltd.
  11. 11. Regional variations • China – methanol, ammonia fuels • USA - SNG • India - fuels • Australia - ? • Europe – biomass gasification A Business Unit of GBH Enterprises, Ltd.
  12. 12. • A fossil fuel with low H/C composition – Means that added H2 needed to utilize it – Energy density is low – More CO2/KW of energy produced than other fossil fuels • Many impurities that should be removed – Hg, S-oxides, NOx, ash, heavy metals, Se, As – US gets 52% of its electricity from coal • Contributes to 60% of total SO2, 33% of Hg, 25% of NOx, and >33% of CO2 emissions – China gets >90% of its electricity from coal • Will China widely adopt emission controls? • CO2 does not have a clear cost-effect link – China will be the biggest emitter of CO2 in 2025 • Will China adopt CO2 emission controls? Issues with Coal A Business Unit of GBH Enterprises, Ltd.
  13. 13. VULCAN Systems Capability  Sour shift • Catalyst supplier for this duty • Many years of successful experience  Purification • Flexibility to adapt absorbent to specific requirements for COS / H2S, Mercury, Arsenic  Methanol technology • Catalyst supplier  SNG technology A Business Unit of GBH Enterprises, Ltd.
  14. 14. Gasification applications A Business Unit of GBH Enterprises, Ltd.
  15. 15. Feedstocks • Coal – China, USA • In situ coal – Australia • Tar sands - Alberta • Heavy oil – not economic • Biomass – future opportunity A Business Unit of GBH Enterprises, Ltd.
  16. 16. Gasification applications Synthesis Gas Air Sep Gasifier Sour Shift Acid Gas Removal Air Sulfur + CO2 Methanol FT Ammonia Hydrogen A Business Unit of GBH Enterprises, Ltd.
  17. 17. Gasification Technology Suppliers • GE / Texaco • Shell • ConocoPhillips • Siemens (Future Energy) • Choren • Lurgi • Advantica • Chinese A Business Unit of GBH Enterprises, Ltd.
  18. 18. Air Separation Technology Suppliers • Praxair • Air Products • Linde • Air Liquide A Business Unit of GBH Enterprises, Ltd.
  19. 19. Acid Gas Removal Technology Suppliers • Linde (Rectisol) • Lurgi (Rectisol) • UOP (Selexol) • BASF (MDEA) A Business Unit of GBH Enterprises, Ltd.
  20. 20. Technology Suppliers E-Gas Slag Raw gas Coke Slurry Quench water Krupp-Uhde/Shell Raw gas HRSG Burner Slag Cooling screen Burner Slag Raw gas Burner Raw gas Slag Refractory lining FUTURE ENERGY Texaco Conoco Phillips/ A Business Unit of GBH Enterprises, Ltd.
  21. 21. Technology Suppliers FUTURE ENERGY GmbH Chevron Texaco Shell / Krupp-Uhde Conoco Phillips / E-Gas Cooling screen Cooling wall Shell / Prenflow Shell Feed fuel coal, ash containing materials oil, ash free materials coal oil coal oil coal, residues Fuel feeding system pneumatic, slurry slurry pneumatic slurry (50 – 70 % coal) Fuel ash content > 1% < 1 % Slag molten, granulated molten, granulated molten, granulated molten, granulated Pressure up to 80 bar up to 80 bar up to 40 bar up to 80 bar up to 40 bar Capacity up to 500 MW up to 500 MW up to 500 MW Reactor lining cooling screen cooling wall (refr. lining) refractory lining partial cooling screen refractory lining refractory lining Relining interval 10 years 5 years 1 – 2 years 5 years 5 years 5 years Reactor heat loss 1 – 5 % low medium low low low Quench / gas cooling total quench radiant heat exchanger total or partial qu. radiant heat exchanger total quench/radiant heat exch. (dependent on feedstock) integr. radiant HE and pre-cooling by syngas total or partial qu. external radiant heat exchanger pre-quench (2 nd gas. stage) on coal slurry (900 - 1000 °C) Start-up time 1 hour 3 days 3 days 3 days 3 days Availability (single gasifier) 90 - 95 % 95 % 85 % 95 % 70 – 80 % 95 % 70 % Carbon conversion rate > 99 % > 99 % > 84 % > 99 % > 94 % Cold gas efficiency 78 - 83 % 83.5 % 70.5 % 83 % 83.5 % 84.0 % Reference plants (number) 5 plants 130 licenses / 72 plants 85 plants 1 plant
  22. 22. Gasification for Ammonia / Methanol Chinese project using Shell technology A Business Unit of GBH Enterprises, Ltd.
  23. 23. A Business Unit of GBH Enterprises, Ltd.
  24. 24. GSP gasifier building at Schwarze Pumpe A Business Unit of GBH Enterprises, Ltd.
  25. 25. Technology Suppliers Choren… • Biomass to FT diesel • Part-owned by Shell • Building demo plant A Business Unit of GBH Enterprises, Ltd.
  26. 26. Choren demonstration plant in Freiberg A Business Unit of GBH Enterprises, Ltd.
  27. 27. Technology Suppliers Lurgi… • Long history • Alberta hydrogen project • European research efforts A Business Unit of GBH Enterprises, Ltd.
  28. 28. High pressure test gasifier at Freiberg A Business Unit of GBH Enterprises, Ltd.
  29. 29. Use of VULCAN Sour Shift System  Increases hydrogen production  Produce syngas suitable for ammonia or methanol production  Produce syngas for methanation to SNG  Converts COS to H2S  Converts HCN to NH3 A Business Unit of GBH Enterprises, Ltd.
  30. 30. Partial Oxidation Process Oil or Coal Condensate Oxygen Quench Chamber Soot Scrubber Sour Shift Beds Syngas Product Gasifier A Business Unit of GBH Enterprises, Ltd.
  31. 31. Catalyst Impact on Shift System Design  VIG SGS-201/202/203 operates over a wide range of steam ratios  VIG SGS-201/202/203 achieves maximum CO conversion, as determined by reaction equilibrium  VIG SGS-201/202/203 resists the possibility of methanation  VIG SGS-201/202/203 operates with a wide range of sulfur in the feed A Business Unit of GBH Enterprises, Ltd.
  32. 32. Dew point flexibility  VIG SGS-201/202/203 is active enough to operate within + 30-50 deg C of the gas dew point and give high CO conversion A Business Unit of GBH Enterprises, Ltd.
  33. 33. Sulfur & Shift Equilibrium
  34. 34. Metal-S+H2O Metal Oxide+H2S Sulfur Tolerant Shift Catalyst Sulfur Requirement/Catalyst Hydrolysis -Catalyst to remain Sulfided for Maximum activity - Steam/Sulfur ratio and temperature critical A Business Unit of GBH Enterprises, Ltd.
  35. 35. Steam Requirement  VIG SGS-201 /202/203 can operate at low steam ratio without risk of methanation: CO + H2O CO2 + H2 CO + 3H2 CH4 + H20 Likely to require a steam : CO ratio of 2.0 A Business Unit of GBH Enterprises, Ltd.
  36. 36. Effect of Trace components  COS - converted to H2S (COS hydrolysis)  Metal carbonyls - decomposed and deposited as sulfides (FeS/NiS)  Nitrogen compounds - HCN almost completely removed  Halogens - catalyst not affected at typical concentrations  C, dust - deposited on catalyst A Business Unit of GBH Enterprises, Ltd.www.gbhenterprises.com
  37. 37. Catalyst Attributes  high mechanical strength to resist external fouling, water impingement  resist deposit build-up  stability to withstand high steam partial pressure at high temperature  high activity - low CO, close approach to shift equilibrium  operation close to dew point - occasional wetting  low pressure drop - minimum pressure drop increase A Business Unit of GBH Enterprises, Ltd.
  38. 38. Robustness/Regenerability  Maximum physical robustness  Can be regenerated if Carbon/Coke like polymer formation  Partial activity recovery A Business Unit of GBH Enterprises, Ltd.
  39. 39. Operating Experience  Long lives • Upstream bed : 2 - 5 years • Downstream bed : 3 - 7 years  Operating Temperature • Normal : 200 - 500 deg C • Excursions up to 550 deg C  Operating Pressures • Experience with wide pressure range • Up to 80 bar • Tested successfully up to 100 bar • Can tolerate high steam partial pressure ~ 50 bar A Business Unit of GBH Enterprises, Ltd.
  40. 40. Resistance to Fouling SHIFT CATALYST A Business Unit of GBH Enterprises, Ltd. Trap for Deposits and contamination
  41. 41. Catalyst Developments  Improved activity variants - smaller reactors, higher CO conversion  Lower pressure drop - optimization of particle size/shape  Manufacturing at new locations A Business Unit of GBH Enterprises, Ltd.
  42. 42. Catalyst Developments - Geometry Particle size / shape optimisation  scope to lower initial pressure drop and rate of pressure drop increase  potentially some small impact on activity  options for radial flow configurations A Business Unit of GBH Enterprises, Ltd.
  43. 43. Catalyst Developments - VIG SGS- 201/202/203 - High activity sour gas shift catalyst - CoO/MoO3 on MgO/Al2O3 support A Business Unit of GBH Enterprises, Ltd.
  44. 44. Catalyst Developments - VIG SGS- 201/202/203  Higher external surface area to trap poisons  good resistance to impurities including heavy metals (Pb, Hg, As) and soot  Higher voidage  lower pressure drop  High thermal resistance & high mechanical strength  slow rate of PD increase  Optimized loading with VIG SGS-202, VIG SGS- 203 and AST Support to suit requirements A Business Unit of GBH Enterprises, Ltd.
  45. 45. Conclusion – Sour shift  Requirement for POX increasing in response to several factors  Potential for successful integration of Sour Shift application with gasification technology  Opportunities to build on success of VIG SGS-201/202/203 with developments to meet particular client needs A Business Unit of GBH Enterprises, Ltd.
  46. 46. Conclusions GBH Enterprises have a leading position in supplying technology, catalysts and absorbents for gasification applications • Full capability for sour shift, purification and methanol synthesis A Business Unit of GBH Enterprises, Ltd.

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