Process for humidifying synthesis gas

• US 20070137107A1
• Filed: 12/19/2005
• Published: 06/21/2007
• Est. Priority Date: 12/19/2005
• Status: Active Grant

• Current Assignee: Eastman Chemical Company
• Original Assignee: Eastman Chemical Company
• Inventors: Barnicki, Scott
• Granted Patent: US 7,503,947 B2
• Time in Patent Office: Days
• US Class Current: 48/198.300
• CPC Class Codes: C01B 2203/0233 the reforming step being a steam reforming step
• CPC Class Codes: C01B 2203/06 Integration with other chemical processes
• CPC Class Codes: C01B 2203/061 Methanol production
• CPC Class Codes: C01B 2203/062 Hydrocarbon production, e.g. Fischer-Tropsch process
• CPC Class Codes: C01B 2203/068 Ammonia synthesis
• CPC Class Codes: C01B 2203/0877 by direct injection of fluid
• CPC Class Codes: C01B 2203/0883 by indirect heat exchange
• CPC Class Codes: C01B 2203/84 Energy production
• CPC Class Codes: C01B 3/34 by reaction of hydrocarbons with gasifying agents
• CPC Class Codes: C10J 2300/093 Coal
• CPC Class Codes: C10J 2300/0959 Oxygen
• CPC Class Codes: C10J 2300/0969 Carbon dioxide
• CPC Class Codes: C10J 2300/0973 Water
• CPC Class Codes: C10J 2300/1618 Modification of synthesis gas composition, e.g. to meet some criteria
• 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 2300/1665 to alcohols, e.g. methanol or ethanol preparation of alcohols in general C07C29/00
• CPC Class Codes: C10J 2300/1668 to urea preparation of urea C07C273/00; to ammonia preparation of ammonia C01C1/0405
• CPC Class Codes: C10J 2300/1671 with the production of electricity
• 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 3/723 : Controlling or regulating the gasification process
• CPC Class Codes: C10K 1/002 : Removal of contaminants
• CPC Class Codes: C10K 1/004 : Sulfur containing contaminants, e.g. hydrogen sulfide
• CPC Class Codes: C10K 1/005 : Carbon dioxide
• CPC Class Codes: C10K 1/007 : of metal compounds
• CPC Class Codes: C10K 1/04 : by cooling to condense non-gaseous materials C10K1/001 takes precedence
• CPC Class Codes: C10K 1/101 : with water only
• CPC Class Codes: C10K 1/12 : alkaline-reacting including the revival of the used wash liquors
• CPC Class Codes: C10K 1/122 : containing only carbonates, bicarbonates, hydroxides or oxides of alkali-metals (including Mg)
• CPC Class Codes: C10K 1/143 : containing amino groups
• CPC Class Codes: C10K 1/16 : with non-aqueous liquids
• CPC Class Codes: C10K 1/20 : by treating with solids; Regenerating spent purifying masses separation by adsorption B01D53/02; separation by chemical reaction B01D53/34; refining of hydrocarbon oils with acids C10G17/02, C10G27/02, C10G29/12
• CPC Class Codes: C10K 1/32 : with selectively adsorptive solids, e.g. active carbon
• CPC Class Codes: C10K 3/04 : reducing the carbon monoxide content , e.g. water-gas shift [WGS]
• CPC Class Codes: C10K 3/06 : by mixing with gases
• CPC Class Codes: Y02E 20/14 : Combined heat and power generation [CHP]
• CPC Class Codes: Y02E 20/16 : Combined cycle power plant [CCPP], or combined cycle gas turbine [CCGT]
• CPC Class Codes: Y02E 20/18 : Integrated gasification combined cycle [IGCC], e.g. combined with carbon capture and storage [CCS]
• CPC Class Codes: Y02E 50/10 : Biofuels, e.g. bio-diesel
• CPC Class Codes: Y02E 50/30 : Fuel from waste, e.g. synthetic alcohol or diesel
• CPC Class Codes: Y02P 20/129 : Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines

Abstract

Disclosed is a process for humidifying syngas to achieve a water to carbon monoxide molar ratio in the product syngas within a desired range and in which the molar ratio which can be varied over time in response to changes in downstream syngas requirements. The raw syngas is produced by reacting a carbonaceous material with oxygen, water, or carbon dioxide and can be combined with a diluent to produce a diluted syngas stream which can be cooled and contacted with liquid water to give a humidified syngas. The H₂O:CO molar ratio of the humidified syngas may be adjusted in response to time-varying downstream syngas requirements by changing the amount and/or temperature of the diluent that is combined with the raw syngas stream, by adjusting quench and heat exchange conditions, or a combination thereof. The application of the process to the coproduction of chemicals and power are also disclosed.

Claims

1. A process for humidifying syngas comprising:

(a) reacting a carbonaceous material with oxygen, water, or carbon dioxide to produce a raw syngas stream comprising hydrogen, carbon monoxide, and carbon dioxide;

(b) combining said raw syngas stream of step (a) with a diluent to produce a diluted syngas stream;

(c) passing said diluted syngas stream of step (b) to a heat exchanger to produce a cooled syngas stream; and

(d) contacting said cooled syngas stream of step (c) with liquid water to produce a humidified syngas stream having a H₂O;

CO molar ratio of about 0.2;

1 to about 4;

1.

2. The process according to claim 1 wherein said carbonaceous material comprises methane, petroleum residuum, coal, coke, lignite, oil shale, oil sands, peat, biomass, petroleum refining residues, petroleum cokes, asphalts, vacuum resid, heavy oils, or combinations thereof.

3. The process according to claim 2 wherein said carbonaceous material of step (a) is reacted in a gasifier, partial oxidizer, or reformer.

4. The process according to claim 3 wherein said carbonaceous material comprises methane and is reacted with water in a reformer.

5. The process according to claim 3 wherein said carbonaceous material comprises coal or petroleum coke and is reacted with oxygen in a gasifier.

6. The process according to claim 1 wherein said diluent of step (b) comprises water, methane, ethane, propane, butane, recycled syngas, nitrogen, argon, helium, carbon dioxide, waste gases, combustion stack gases, or combinations thereof.

7. The process according to claim 6 wherein said diluent comprises water.

8. The process according to claim 1 wherein the amount of said diluent is about 1 to 100 mole % of said raw syngas stream.

9. The process according to claim 1 wherein the amount and/or temperature of said diluent in step (b) combined with said raw syngas stream varies in response to a downstream syngas requirement.

10. The process according to claim 1 wherein said H₂O:

CO molar ratio in step (d) is a chosen in response to a downstream syngas requirement.

11. The process according to claim 10 wherein said amount and/or temperature of said diluent in step (b) combined with said raw syngas stream is chosen to satisfy said H₂O:

CO molar ratio.

12. The process according to claim 1 wherein said heat exchanger of step (c) comprises a radiant heat exchanger, convective heat exchanger, or a combination thereof.

13. The process according to claim 12 further comprising generating steam in step (c).

14. The process according to claim 13 wherein the pressure of said steam generated in step (c) varies in response to a downstream syngas requirement.

15. The process according to claim 10 further comprising generating steam in step (c) at a pressure chosen to satisfy said H₂O:

CO molar ratio.

16. The process according to claim 1 wherein said raw syngas in step (a) has a temperature of about 1000 to about 2000°

C.

17. The process according to claim 1 wherein the temperature of said diluent is lower than the temperature of said raw syngas stream.

18. The process according to claim 1 wherein step (d) is carried in a water quench system having influent and effluent flows of water.

19. The process according to claim 18 wherein the amount of said influent and/or effluent flows of water vary in response to a downstream syngas requirement.

20. The process according to claim 10 wherein step (d) is carried in a water quench system having influent and effluent flows of water wherein the amount of said influent and/or effluent flow of water is chosen to satisfy said H₂O:

CO molar ratio.

21. The process according to claim 1 where said water:

carbon monoxide molar ratio is about 1;

1 to about 3;

1.

22. The process according to claim 9 wherein said downstream syngas requirement comprises a feedstock requirement for a chemical process, a fuel requirement for a power producing process, or a combination thereof.

23. The process according to claim 22 wherein said chemical process comprises a process for methanol, alkyl formates, dimethyl ether, oxo aldehydes, ammonia, methane, hydrogen, Fischer-Topsch products, or a combination thereof.

24. The process according to claim 23 wherein said chemical process comprises a water-gas shift process, a methanol process, or a combination thereof.

25. The process according to claim 22 wherein said power producing process comprises a combined cycle system.

26. The process according to claim 1 further comprising passing up to 100 volume percent of said humidified syngas from step (d) to a water-gas shift reactor to produce a shifted syngas stream comprising additional hydrogen and carbon dioxide.

27. The process according to claim 26 further comprising passing up to 100 volume percent of said shifted syngas stream to a chemical process to produce methanol, alkyl formates, dimethyl ether, oxo aldehydes, ammonia, methane, Fischer-Topsch products, or a combination thereof.

28. The process according the claim 27 wherein the amount of said diluent in step (b) combined with said raw syngas stream is chosen in response to a syngas feedstock requirement for said chemical process.

29. A process for the coproduction of power and chemicals, comprising:

(a) reacting a carbonaceous material with an oxidant stream in a gasifier to produce a raw syngas stream comprising hydrogen, carbon monoxide, and carbon dioxide;

(b) combining said raw syngas stream of step (a) with a diluent to produce a diluted syngas stream;

(c) passing said diluted syngas stream of step (b) to a heat exchanger to produce a cooled syngas stream;

(d) contacting said cooled syngas stream of step (c) with liquid water to produce a humidified syngas stream having a H₂O;

CO molar ratio of about 0.2;

1 to about4;

1;

(e) passing up to 100 volume percent of said humidified syngas stream to a water-gas shift reactor to produce a shifted syngas stream comprising additional hydrogen and carbon dioxide during a period of off-peak power demand;

(f) passing up to 100 volume percent of said shifted syngas stream from step (e) to a chemical process to produce a chemical product; and

(g) passing up to 100 volume percent of said humidified syngas stream from step (d) to a power producing process to produce electricity during a period of peak power demand.

30. The process according to claim 29 wherein said carbonaceous material comprises coal or petroleum coke.

31. The process according to claim 29 wherein said oxidant stream comprises at least 85 volume % oxygen, based on the total volume of said oxidant stream.

32. The process according to claim 31 wherein said oxidant stream comprises at least 95 volume % oxygen.

33. The process according to claim 29 wherein the temperature of said diluent is lower than the temperature of said raw syngas stream.

34. The process according to claim 29 wherein the amount and/or temperature of said diluent in step (b) combined with said raw syngas stream varies in response to a syngas feedstock requirement for said water gas shift reactor, a fuel requirement for said power producing process, or a combination thereof.

35. The process according to claim 29 wherein said H₂O:

CO molar ratio in step (d) is chosen in response to a syngas feedstock requirement for said water gas shift reactor, a fuel requirement for said power producing process, or a combination thereof.

36. The process according to claim 35 wherein said amount and/or temperature of said diluent in step (b) combined with said raw syngas stream is chosen to satisfy said H₂O:

CO molar ratio.

37. The process according to claim 29 wherein said diluent of step (b) comprises water, methane, ethane, propane, butane, recycled syngas, nitrogen, argon, helium, carbon dioxide, waste gases, combustion stack gases, or combinations thereof.

38. The process according to claim 37 wherein said diluent comprises water.

39. The process according to claim 29 wherein said heat exchanger of step (c) comprises a radiant heat exchanger, convective heat exchanger, or a combination thereof.

40. The process according to claim 29 further comprising generating steam in step (c).

41. The process according to claim 40 wherein the pressure of said steam generated in step (c) varies in response to a syngas feedstock requirement for said water gas shift reactor, a fuel requirement for said power producing process, or a combination thereof.

42. The process according to claim 35 further comprising generating steam in step (c) at a pressure chosen to satisfy said H₂O:

CO molar ratio.

43. The process according to claim 29 wherein said raw syngas in step (a) has a temperature of about 1000 to about 2000°

C.

44. The process according to claim 29 wherein step (d) is carried in a water quench system having influent and effluent flows of water.

45. The process according to claim 44 wherein the amount of said influent and/or effluent flows of water varies in response to a syngas feedstock requirement for said water gas shift reactor, a fuel requirement for said power producing process, or a combination thereof.

46. The process according to claim 35 wherein step (d) is carried in a water quench system having influent and effluent flows of water, wherein the amount of said influent and/or effluent flow of water is chosen to satisfy said H₂O:

CO molar ratio.

47. The process according to claim 29 where said H₂O:

CO molar ratio is about 1;

1 to about 3;

1.

48. The process according to claim 29 further comprising generating steam by recovering heat from said water-gas shift reactor.

49. The process according to claim 29 wherein said shifted syngas stream has a molar ratio of hydrogen to carbon monoxide of about 1:

1 to about 20;

1,

50. The process according to claim 48 wherein said chemical producing process comprises a methanol process.

51. The process according to claim 29 wherein said power producing process comprises a combined cycle system.

52. The process according to claim 29 wherein said chemical product comprises methanol, alkyl formates, dimethyl ether, oxo aldehydes, ammonia, methane, Fischer-Topsch products, or combinations thereof.

53. A process for the coproduction of power and methanol, comprising:

(a) reacting coal, petroleum coke, or mixture thereof with an oxidant stream in a gasifier to produce a raw syngas stream comprising hydrogen, carbon monoxide, carbon dioxide, and sulfur containing compounds;

(b) combining said raw syngas stream of step (a) with a diluent to produce a diluted syngas stream;

(c) passing said diluted syngas stream of step (b) to a heat exchanger to produce a cooled syngas stream;

(d) contacting said cooled syngas stream of step (c) with liquid water to produce a humidified syngas stream having a target H₂O;

CO molar ratio of about 0.2;

1 to about 4;

1;

(e) passing up to 100 volume percent of said humidified syngas stream to a water-gas shift reactor to produce a shifted syngas stream having a molar ratio of hydrogen to carbon monoxide of about 1;

1 to about 20;

1 during a period of off-peak power demand;

(f) contacting up to 100 volume percent of said shifted syngas stream with a catalyst effective for converting hydrogen and carbon monoxide into methanol; and

(g) passing up to 100 volume percent of said humidified syngas stream from step (d) to a power producing process to produce electricity during a period of peak power demand.

54. The process according to claim 53 wherein said target H₂O:

CO molar ratio is chosen in response said periods of peak and off peak power demand.

55. The process according to claim 54 wherein the amount and/or temperature of said diluent in step (b) is chosen to satisfy said target H₂O:

CO molar ratio of step (d).

56. The process according to claim 54 further comprising generating steam in step (c) at a pressure chosen to satisfy said target H₂O:

CO molar ratio.

57. The process according to claim 54 wherein step (d) is carried in a water quench system having influent and effluent flows of water, wherein the amount of said influent and/or effluent flow of water is chosen to satisfy said H₂O:

CO molar ratio.

58. The process according to claim 53 wherein said shifted syngas stream has a molar ratio of hydrogen to carbon monoxide of about 1.5:

1 to about 3;

1.

59. The process according to claim 53 further comprising removing at least 95 mole percent of the total of said sulfur-containing compounds present in said shifted syngas streams from step (e).

60. The process according to claim 53 further comprising removing a portion of said carbon dioxide from said shifted syngas stream in step (e).

61. The process according to claim 53 wherein up to 100 volume percent of said shifted syngas stream of step (f) is contacted with said catalyst in a fixed bed methanol reactor.

62. The process according to claim 53 wherein up to 100 volume percent of said shifted syngas stream of step (f) is contacted with said catalyst in a liquid slurry phase methanol reactor.

63. A system for coproducing power and chemicals from syngas, comprising:

(a) a gasifier for reacting a carbonaceous material with an oxidant stream to produce a raw syngas stream comprising hydrogen, carbon monoxide, carbon dioxide, and sulfur containing compounds;

(b) a dilution section for combining said raw syngas steam of step (a) with a diluent to produce a diluted syngas stream, wherein the amount of said diluent combined with said raw syngas is chosen in response to peak and off-peak power demands;

(c) a heat exchange section for cooling said diluted syngas stream of step (b) by a heat exchange process;

(d) a water quench section for contacting the cooled syngas stream of step (c) with liquid water to produce a humidified syngas stream having a H₂O;

CO molar ratio of about 0.2;

1 to about 4;

1;

(e) a water-gas shift reaction section for converting up to 100 volume percent of said humidified syngas stream to a shifted syngas stream comprising additional hydrogen and carbon dioxide;

(f) a chemical producing section for converting up to 100 volume percent of said shifted syngas stream into a chemical product selected from methanol, alkyl formates, dimethyl ether, oxo aldehydes, ammonia, methane, Fischer-Topsch products, and combinations thereof during a period of off-peak power demand; and

(g) a power producing section comprising a combustion turbine for converting up to 100 volume percent of said a humidified syngas stream from step (a) to electrical power during a period of peak power demand.

64. The system according to claim 63 wherein said chemical producing section comprises a methanol reactor.

65. The system according to claim 64 wherein said methanol reactor is a fixed bed or a liquid slurry phase reactor.

66. The system according to claim 63 wherein said oxidant stream comprises at least 95 volume % oxygen.

67. The system according to claim 63 wherein said diluent comprises one or more substances selected from water, methane, ethane, propane, butane, recycled syngas, nitrogen, argon, helium, carbon dioxide, waste gases, and combustion stack gases.

68. The system according to claim 67 wherein said diluent comprises water.

69. The system according to claim 63 wherein said heat exchange section (c) comprises a radiant heat exchanger, convective heat exchanger, or a combination thereof.

70. The system according to claim 63 wherein said water quench section (d) comprises a water reservoir with influent and effluent flows of water.

71. The system according claim 63 wherein said power producing section comprises a combined cycle system.

72. The system according to claim 63 which further comprises an acid gas removal section for removing all or a portion of said carbon dioxide, sulfur-containing compounds, or a combination thereof.