Steam pyrolysis as a process to enhance the hydro-gasification of carbonaceous materials

• US 20050032920A1
• Filed: 08/03/2004
• Published: 02/10/2005
• Est. Priority Date: 02/05/2002
• Status: Active Grant

• Current Assignee: Regents of the University of California (University of California)
• Original Assignee: Regents of the University of California (University of California)
• Inventors: Norbeck, Joseph M., Hackett, Colin E.
• Granted Patent: US 7,500,997 B2
• Time in Patent Office: Days
• US Class Current: 518/704
• CPC Class Codes: C01B 2203/00 Integrated processes for the production of hydrogen or synthesis gas reactors or details thereof B01J2208/00 - B01J2219/00
• CPC Class Codes: C01B 2203/0233 the reforming step being a steam reforming step
• CPC Class Codes: C01B 2203/04 containing a purification step for the hydrogen or the synthesis gas
• CPC Class Codes: C01B 2203/0495 the impurity being water
• CPC Class Codes: C01B 2203/06 Integration with other chemical processes
• CPC Class Codes: C01B 2203/062 Hydrocarbon production, e.g. Fischer-Tropsch process
• CPC Class Codes: C01B 2203/0827 at least part of the fuel being a recycle stream
• CPC Class Codes: C01B 2203/0833 Heating by indirect heat exchange with hot fluids, other than combustion gases, product gases or non-combustive exothermic reaction product gases
• CPC Class Codes: C01B 2203/0838 by heat exchange with exothermic reactions, other than by combustion of fuel
• CPC Class Codes: C01B 2203/0883 by indirect heat exchange
• CPC Class Codes: C01B 2203/0894 Generation of steam
• CPC Class Codes: C01B 2203/1205 Composition of the feed
• CPC Class Codes: C01B 2203/1258 Pre-treatment of the feed
• CPC Class Codes: C01B 2203/1276 Mixing of different feed components
• CPC Class Codes: C01B 2203/146 At least two purification steps in series
• CPC Class Codes: C01B 2203/148 involving a recycle stream to the feed of the process for making hydrogen or synthesis gas
• CPC Class Codes: C01B 2203/84 Energy production
• CPC Class Codes: C01B 3/34 by reaction of hydrocarbons with gasifying agents
• CPC Class Codes: C10G 1/002 in combination with oil conversion- or refining processes
• CPC Class Codes: C10G 2/30 from carbon monoxide with hydrogen
• CPC Class Codes: C10G 2/32 : with the use of catalysts
• CPC Class Codes: C10G 2300/1003 : Waste materials
• CPC Class Codes: C10G 2300/1011 : Biomass
• CPC Class Codes: C10G 2300/807 : Steam
• CPC Class Codes: C10G 2400/04 : Diesel oil
• CPC Class Codes: C10J 2300/06 : Modeling or simulation of processes
• CPC Class Codes: C10J 2300/0903 : Feed preparation
• CPC Class Codes: C10J 2300/0906 : Physical processes, e.g. shredding, comminuting, chopping, sorting
• CPC Class Codes: C10J 2300/0916 : Biomass
• CPC Class Codes: C10J 2300/092 : Wood, cellulose
• CPC Class Codes: C10J 2300/093 : Coal
• CPC Class Codes: C10J 2300/0946 : Waste, e.g. MSW, tires, glass, tar sand, peat, paper, lignite, oil shale
• CPC Class Codes: C10J 2300/0966 : Hydrogen
• CPC Class Codes: C10J 2300/0973 : Water
• CPC Class Codes: C10J 2300/0983 : Additives
• CPC Class Codes: C10J 2300/165 : integrated with a gas turbine or gas motor gas turbine plants provided with a gas producer F02C3/28; engines using solid fuels F02B43/08
• CPC Class Codes: C10J 2300/1659 : to liquid hydrocarbons Fischer-Tropsch process C10G2/00
• CPC Class Codes: C10J 2300/1671 : with the production of electricity
• CPC Class Codes: C10J 2300/1675 : making use of a steam turbine
• CPC Class Codes: C10J 2300/1693 : with storage facilities for intermediate, feed and/or product
• CPC Class Codes: C10J 2300/1807 : Recycle loops, e.g. gas, solids, heating medium, water
• CPC Class Codes: C10J 2300/1853 : Steam reforming, i.e. injection of steam only
• CPC Class Codes: C10J 2300/1884 : with one stream being synthesis gas
• CPC Class Codes: C10J 2300/1892 : with one stream being water/steam
• CPC Class Codes: C10J 3/00 : Production of combustible gases containing carbon monoxide from solid carbonaceous fuels destructive distillation processes C10B
• CPC Class Codes: C10J 3/54 : Gasification of granular or pulverulent fuels by the Winkler technique, i.e. by fluidisation
• CPC Class Codes: C10J 3/66 : by introducing them into the gasification zone
• CPC Class Codes: C10J 3/721 : Multistage gasification, e.g. plural parallel or serial gasification stages
• CPC Class Codes: C10J 3/723 : Controlling or regulating the gasification process
• CPC Class Codes: Y02E 20/16 : Combined cycle power plant [CCPP], or combined cycle gas turbine [CCGT]
• CPC Class Codes: Y02E 50/30 : Fuel from waste, e.g. synthetic alcohol or diesel
• CPC Class Codes: Y02E 60/32 : Hydrogen storage
• CPC Class Codes: Y02P 20/145 : the feedstock being materials of biological origin
• CPC Class Codes: Y02P 20/582 : Recycling of unreacted starting or intermediate materials
• CPC Class Codes: Y02P 30/00 : Technologies relating to oil refining and petrochemical industry
• CPC Class Codes: Y02P 30/20 : using bio-feedstock

Abstract

A process and apparatus for producing a synthesis gas for use as a gaseous fuel or as feed into a Fischer-Tropsch reactor to produce a liquid fuel in a substantially self-sustaining process. In one embodiment, a slurry of particles of carbonaceous material in water, and hydrogen from an internal source, are fed into a hydro-gasification reactor under conditions whereby methane rich producer gases are generated and fed into a steam pyrolytic reformer under conditions whereby synthesis gas comprising hydrogen and carbon monoxide are generated. A portion of the hydrogen generated by the steam pyrolytic reformer is fed through a hydrogen purification filter into the hydro-gasification reactor, the hydrogen therefrom constituting the hydrogen from an internal source. The remaining synthesis gas generated by the steam pyrolytic reformer is either used as fuel for a gaseous fueled engine to produce electricity and/or process heat or is fed into a Fischer-Tropsch reactor under conditions whereby a liquid fuel is produced. Molten salt loops are used to transfer heat from the hydro-gasification reactor, and Fischer-Tropsch reactor if liquid fuel is produced, to the steam generator and the steam pyrolytic reformer. In another embodiment of the invention, carbonaceous material can be heated simultaneously in the presence of both hydrogen and steam to undergo steam pyrolysis and hydro-gasification in a single step.

Claims

1. A process for converting carbonaceous material to energetic gases, the process comprising simultaneously heating carbonaceous material in the presence of both hydrogen and steam, at a temperature and pressure sufficient to generate methane and carbon monoxide rich producer gases.

2. The process of claim 1 wherein the temperature is about 580°

C. to 790°

C.

3. The process of claim 1 wherein the pressure is about 132 psi to 560 psi.

4. The process of claim 1 wherein the carbonaceous material has a nominal particle size of about 1 mm in diameter.

5. The process of claim 1 wherein the carbonaceous material comprises municipal waste, biomass, wood, coal, or a natural or synthetic polymer.

6. The process of claim 5 wherein the carbonaceous material comprises biomass.

7. The process of claim 5 wherein the carbonaceous material comprises municipal waste which comprises wood or a natural or synthetic polymer.

8. A process for converting carbonaceous material to energetic gases, the process comprising simultaneously heating carbonaceous material in the presence of both hydrogen and steam, at a temperature and pressure sufficient to generate methane and carbon monoxide rich producer gases, wherein the carbonaceous material comprises wood or a natural or synthetic polymer.

9. A process for producing a synthesis gas, the process comprising:

a) simultaneously heating carbonaceous material in the presence of both hydrogen and steam at a temperature and pressure sufficient to generate methane and carbon monoxide rich producer gases; and

b) subjecting the methane and carbon monoxide rich producer gases to steam reforming reactions under conditions whereby synthesis gas comprising hydrogen and carbon monoxide is generated.

10. The process of claim 9 wherein the carbonaceous material is non-pyrolyzed carbonaceous material.

11. The process of claim 9 wherein the carbonaceous material comprises municipal waste, biomass, wood, coal, or a natural or synthetic polymer.

12. The process of claim 11 wherein the carbonaceous material comprises biomass.

13. The process of claim 11 wherein the carbonaceous material comprises municipal waste which comprises wood or a natural or synthetic polymer.

14. A process for producing a synthesis gas, the process comprising:

a) simultaneously heating carbonaceous material in the presence of both hydrogen and steam at a temperature and pressure sufficient to generate methane and carbon monoxide rich producer gases, wherein the carbonaceous material comprises wood or a natural or synthetic polymer; and

b) subjecting the methane and carbon monoxide rich producer gases to steam reforming reactions under conditions whereby synthesis gas comprising hydrogen and carbon monoxide is generated.

15. A process for producing a liquid fuel, the process comprising:

a) simultaneously heating carbonaceous material in the presence of both hydrogen and steam at a temperature and pressure sufficient to generate methane and carbon monoxide rich producer gases;

b) subjecting the methane and carbon monoxide rich producer gases to steam reforming reactions under conditions whereby synthesis gas comprising hydrogen and carbon monoxide is generated; and

c) subjecting the synthesis gas to Fischer-Tropsch reactions under conditions whereby a liquid fuel is produced.

16. The process of claim 15 wherein the carbonaceous material is non-pyrolyzed carbonaceous material.

17. The process of claim 15 wherein the carbonaceous material comprises municipal waste, biomass, wood, coal, or a natural or synthetic polymer.

18. The process of claim 17 wherein the carbonaceous material comprises biomass.

19. The process of claim 17 wherein the carbonaceous material comprises municipal waste which comprises wood or a natural or synthetic polymer.

20. A process for producing a synthesis gas for use as a gaseous fuel or as feed into a Fischer-Tropsch reactor to produce a liquid fuel, the process comprising:

a) feeding hydrogen from an internal source, superheated steam from a steam generator, and a slurry of non-pyrolyzed carbonaceous material in water into a hydro-gasification reactor under conditions whereby methane and carbon monoxide rich producer gases are generated;

b) feeding the methane and carbon monoxide rich producer gases from the hydro-gasification reactor into a steam pyrolytic reformer under conditions whereby synthesis gas comprising hydrogen and carbon monoxide is generated;

c) feeding a portion of the hydrogen generated by the steam pyrolytic reformer into the hydro-gasification reactor as said hydrogen from an internal source; and

d) either utilizing said synthesis gas generated by the steam pyrolytic reformer for process heat or as fuel for an engine to produce electricity, or feeding said synthesis gas into the Fischer-Tropsch reactor under conditions whereby a liquid fuel is produced.

21. The process of claim 20 in which said slurry is formed by grinding said non-pyrolyzed carbonaceous material in water.

22. The process of claim 20 in which said carbonaceous material comprises municipal waste, biomass, wood, coal, or a natural or synthetic polymer.

23. The process of claim 22 wherein the carbonaceous material comprises biomass.

24. The process of claim 22 wherein the carbonaceous material comprises municipal waste which comprises wood or a natural or synthetic polymer.

25. The process of claim 20 in which synthesis gas generated by the steam pyrolytic reformer is fed into a Fischer-Tropsch reactor under conditions whereby a liquid fuel is produced.

26. The process of claim 25 wherein said conditions and the relative amounts of hydrogen and carbon monoxide in the Fischer-Tropsch reactor are such that said liquid fuel is produced exothermally.

27. The process of claim 26 comprising transferring exothermic heat from one or both of the hydro-gasification reactor and Fischer-Tropsch reactor to one or both of the steam generator and the steam pyrolytic reformer.

28. The process of claim 26 comprising transferring exothermic heat from the hydro-gasification reactor and Fischer-Tropsch reactor to the steam generator and the steam pyrolytic reformer.

29. The process of claim 28 in which molten salt loops are used to transfer said exothermic heat.

30. The process of claim 25 in which the relative amounts of hydrogen and carbon monoxide in the synthesis gas fed into the Fischer-Tropsch reactor are such that said liquid fuel is substantially cetane.

31. A substantially self-sustaining process for producing a liquid fuel from carbonaceous feed, comprising:

a) grinding said carbonaceous material in water to from a slurry of carbonaceous particles;

b) feeding hydrogen from an internal source, superheated steam from a steam generator, and the slurry into a hydro-gasification reactor in amounts and under conditions whereby methane and carbon monoxide rich producer gases are generated exothermally under super-atmospheric pressure;

c) feeding the methane and carbon monoxide rich producer gases from the hydro-gasification reactor and superheated steam from the steam generator into a steam pyrolytic reformer under conditions whereby synthesis gas comprising hydrogen and carbon monoxide are generated;

d) feeding a portion of the hydrogen generated by the steam pyrolytic reformer, obtained through a hydrogen purification filter, into the hydro-gasification reactor, the hydrogen therefrom constituting said hydrogen from an internal source;

e) feeding the remainder of the synthesis gas generated by the steam pyrolytic reformer into the Fischer-Tropsch reactor under conditions whereby a liquid fuel is produced exothermally; and

d) transferring exothermic heat from the hydro-gasification reactor and Fischer-Tropsch reactor to the steam generator and the steam pyrolytic reformer, whereby said process is substantially self-sustaining.

32. The process of claim 31 in which molten salt loops are used to transfer said exothermic heat.

33. The process of claim 31 in which said carbonaceous material comprises municipal waste, biomass, wood, coal, or a natural or synthetic polymer.

34. The process of claim 33 wherein the carbonaceous material comprises biomass.

35. The process of claim 33 wherein the carbonaceous material comprises municipal waste which comprises wood or a natural or synthetic polymer.

36. An apparatus for producing a synthesis gas for use as a gaseous fuel or as feed into a Fischer-Tropsch reactor to produce a liquid fuel, comprising:

a source of carbonaceous material and water;

a hydro-gasification reactor; and

a steam pyrolytic reformer;

piping connecting said source of carbonaceous material and water to the hydro-gasification reactor for feeding carbonaceous material and water thereto to generate methane and carbon monoxide;

piping connecting the hydro-gasification reactor to the steam pyrolytic reformer for feeding methane rich producer gases generated in the hydro-gasification reactor to the steam pyrolytic reformer to generate synthesis gas comprising hydrogen and carbon monoxide;

piping connecting the steam pyrolytic reformer to the hydro-gasification reactor for feeding a portion of the hydrogen generated by the steam pyrolytic reformer into the hydro-gasification reactor;

a Fischer-Tropsch reactor and piping connecting the steam pyrolytic reformer to the Fischer-Tropsch reactor for feeding the remainder of the synthesis gas generated by the steam pyrolytic reformer into the Fischer-Tropsch reactor to produce a liquid fuel; and

water-steam loops to transfer heat from one or both of the hydro-gasification reactor and Fischer-Tropsch reactor to one or both of the steam generator and the steam pyrolytic reformer.

37. An apparatus for producing a liquid fuel in a substantially self-sustaining process, comprising:

a source of carbonaceous material and water;

a hydro-gasification reactor;

a steam pyrolytic reformer;

a hydrogen purification filter;

a Fischer-Tropsch reactor;

a grinder forming particles of the carbonaceous material;

a receptacle for the particles and water to form a slurry of the carbonaceous particles;

a steam generator to heat the slurry and activate the carbon by pyrolysis with superheated steam;

piping connecting the steam separator to the hydro-gasification reactor for feeding the slurry and superheated steam thereto to generate methane and carbon monoxide;

piping connecting the hydro-gasification reactor to the steam pyrolytic reformer for feeding methane rich producer gases generated in the hydro-gasification reactor to the steam pyrolytic reformer to form a synthesis gas comprising hydrogen and carbon monoxide;

piping connecting the steam pyrolytic reformer to the hydro-gasification reactor through the hydrogen purification filter for feeding a portion of hydrogen generated by the steam pyrolytic reformer into the hydro-gasification reactor;

piping connecting the steam pyrolytic reformer to the Fischer-Tropsch reactor for feeding the remainder of the synthesis gas generated by the steam pyrolytic reformer into the Fischer-Tropsch reactor to produce a liquid fuel; and

water-steam loops to transfer heat from one or both of the hydro-gasification reactor and Fischer-Tropsch reactor to one or both of the steam generator and the steam pyrolytic reformer.

38. An apparatus for producing a synthesis gas for use as a gaseous fuel or as feed into Fischer-Tropsch reactor to produce a liquid fuel, comprising:

a source of carbonaceous material and water;

a hydro-gasification reactor;

a steam pyrolytic reformer; and

a steam generator to provide superheated steam;

piping connecting said source of carbonaceous material and water to the hydro-gasification reactor for feeding carbonaceous material and water thereto to generate methane and carbon monoxide in the presence of hydrogen and superheated steam;

piping connecting the hydro-gasification reactor to the steam pyrolytic reformer for feeding methane and carbon monoxide rich producer gases generated in the hydro-gasification reactor to the steam pyrolytic reformer to generate synthesis gas comprising hydrogen and carbon monoxide;

piping connecting the steam pyrolytic reformer to the hydro-gasification reactor for feeding a portion of the hydrogen generated by the steam pyrolytic reformer into the hydro-gasification reactor;

piping connecting the steam generator to the hydro-gasification reactor for feeding superheated steam thereto; and

piping connecting the steam generator to the steam pyrolytic reformer for feeding superheated steam thereto to react with the methane and carbon monoxide rich producer gases.

39. The apparatus of claim 38 including a Fischer-Tropsch reactor and piping connecting the steam pyrolytic reformer to the Fischer-Tropsch reactor for feeding the remainder of the synthesis gas generated by the steam pyrolytic reformer into the Fischer-Tropsch reactor to produce a liquid fuel.

40. The apparatus of claim 39 including molten salt loops or water-steam loops to transfer heat from one or both of the hydro-gasification reactor and Fischer-Tropsch reactor to one or both of the steam generator and the steam pyrolytic reformer.

41. The apparatus of claim 39 including molten salt loops or water-steam loops to transfer heat from the hydro-gasification reactor and Fischer-Tropsch reactor to the steam generator and the steam pyrolytic reformer.

42. An apparatus for producing a liquid fuel in a substantially self-sustaining process, comprising:

a source of carbonaceous material and water;

a hydro-gasification reactor;

a steam pyrolytic reformer;

a hydrogen purification filter;

a Fischer-Tropsch reactor;

a grinder forming particles of the carbonaceous material;

a receptacle for the particles and water to form a slurry of the carbonaceous particles;

a steam generator to provide superheated steam;

piping connecting the receptacle to the hydro-gasification reactor for feeding the slurry thereto to generate methane and carbon monoxide in the presence of hydrogen and superheated steam;

piping connecting the steam generator to the hydro-gasification reactor for feeding superheated steam thereto;

piping connecting the hydro-gasification reactor to the steam pyrolytic reformer for feeding methane and carbon monoxide rich producer gases generated in the hydro-gasification reactor to the steam pyrolytic reformer to form a synthesis gas comprising hydrogen and carbon monoxide;

piping connecting the steam pyrolytic reformer to the hydro-gasification reactor through the hydrogen purification filter for feeding a portion of hydrogen generated by the steam pyrolytic reformer into the hydro-gasification reactor; and

piping connecting the steam pyrolytic reformer to the Fischer-Tropsch reactor for feeding the remainder of the synthesis gas generated by the steam pyrolytic reformer into the Fischer-Tropsch reactor to produce a liquid fuel.

43. The apparatus of claim 42 including molten salt loops or water-steam loops to transfer heat from one or both of the hydro-gasification reactor and Fischer-Tropsch reactor to one or both of the steam generator and the steam pyrolytic reformer.

44. The apparatus of claim 42 including molten salt loops or water-steam loops to transfer heat from the hydro-gasification reactor and Fischer-Tropsch reactor to the steam generator and the steam pyrolytic reformer.