FISCHER-TROPSCH SYNTHESIS USING MICROCHANNEL TECHNOLOGY AND NOVEL CATALYST AND MICROCHANNEL REACOTR

• US 20100160463A1
• Filed: 03/05/2010
• Published: 06/24/2010
• Est. Priority Date: 01/28/2004
• Status: Active Grant

• Current Assignee: Anna Lee Tonkovich, Charles Kibby, Chunshe Cao, Dave Vanderwiel, Francis P Daly, Jianli Hu, Michael D. Briscoe, Nathan Gano, Terry Mazanec, Xiaohong Shari Li, Ya-Huei Chin, Yong Wang
• Original Assignee: Anna Lee Tonkovich, Charles Kibby, Chunshe Cao, Dave Vanderwiel, Francis P Daly, Jianli Hu, Michael D. Briscoe, Nathan Gano, Terry Mazanec, Xiaohong Shari Li, Ya-Huei Chin, Yong Wang
• Inventors: Wang, Yong, Chin, Ya-Huei, Tonkovich, Anna Lee, Cao, Chunshe, Daly, Francis P., Mazanec, Terry, Hu, Jianli, Li, Xiaohong Shari, Gano, Nathan, Kibby, Charles, Briscoe, Michael D., VanderWiel, Dave
• Granted Patent: US 8,188,153 B2
• Time in Patent Office: Days
• US Class Current: 518/712
• CPC Class Codes: B01J 19/0093 Microreactors, e.g. miniaturised or microfabricated reactors laboratory containers with capillary fluid transport in microfabricated channels or chambers B01L3/5027
• CPC Class Codes: B01J 21/04 Alumina
• CPC Class Codes: B01J 2219/00783 Laminate assemblies, i.e. the reactor comprising a stack of plates
• CPC Class Codes: B01J 2219/00822 Metal
• CPC Class Codes: B01J 2219/00824 Ceramic
• CPC Class Codes: B01J 2219/00826 Quartz
• CPC Class Codes: B01J 2219/00831 Glass
• CPC Class Codes: B01J 2219/00835 Comprising catalytically active material
• CPC Class Codes: B01J 2219/00844 Comprising porous material
• CPC Class Codes: B01J 2219/0086 Dimensions of the flow channels
• CPC Class Codes: B01J 2219/00873 Heat exchange
• CPC Class Codes: B01J 23/75 Cobalt
• CPC Class Codes: B01J 23/8896 Rhenium
• CPC Class Codes: B01J 23/8913 Cobalt and noble metals
• CPC Class Codes: B01J 35/394 Metal dispersion value, e.g. percentage or fraction
• CPC Class Codes: B01J 35/615 100-500 m2/g
• CPC Class Codes: B01J 35/633 less than 0.5 ml/g
• CPC Class Codes: B01J 35/635 0.5-1.0 ml/g
• CPC Class Codes: B01J 37/0205 in several steps
• CPC Class Codes: C10G 2/332 of the iron-group
• CPC Class Codes: C10G 2/341 : with stationary catalyst bed
• CPC Class Codes: C10G 2300/301 : Boiling range
• CPC Class Codes: C10G 2300/4018 : Spatial velocity, e.g. LHSV, WHSV
• CPC Class Codes: C10G 2300/4025 : Yield
• CPC Class Codes: C10G 2300/70 : Catalyst aspects
• CPC Class Codes: C10G 2400/04 : Diesel oil
• CPC Class Codes: C10G 2400/10 : Lubricating oil
• CPC Class Codes: Y02P 20/582 : Recycling of unreacted starting or intermediate materials

Abstract

The disclosed invention relates to a process for converting a reactant composition comprising H₂ and CO to a product comprising at least one aliphatic hydrocarbon having at least about 5 carbon atoms, the process comprising: flowing the reactant composition through a microchannel reactor in contact with a Fischer-Tropsch catalyst to convert the reactant composition to the product, the microchannel reactor comprising a plurality of process microchannels containing the catalyst; transferring heat from the process microchannels to a heat exchanger; and removing the product from the microchannel reactor; the process producing at least about 0.5 gram of aliphatic hydrocarbon having at least about 5 carbon atoms per gram of catalyst per hour; the selectivity to methane in the product being less than about 25%. The disclosed invention also relates to a supported catalyst comprising Co, and a microchannel reactor comprising at least one process microchannel and at least one adjacent heat exchange zone.

Claims

1. A microchannel reactor comprising at least one microchannel, the at least one microchannel comprising at least one catalyst, the catalyst comprising a composition represented by the formula

CoM¹_aM²_bO_x

wherein

M¹ is Fe, Ni, Ru, Re, Os, or a mixture of two or more thereof;

M² is Li, B, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Sc, Y, La, Ac, Ti, Zr, La, Ac, Ce or Th, or a mixture of two or more thereof;

a is a number in the range of zero to about 0.5;

b is a number in the range of zero to about 0.5; and

x is the number of oxygens needed to fulfill the valency requirements of the elements present.

2. The microchannel reactor of claim 1 wherein the catalyst comprises Co supported on alumina, the Co loading being at least about 5% by weight.

3. The microchannel reactor of claim 1 wherein the catalyst comprises Co supported on alumina, the Co loading being at least about 25%.

4. The microchannel reactor of claim 1 wherein the catalyst comprises Co supported on alumina, the Co dispersion being at least about 3%.

5. The microchannel reactor of claim 1 wherein the catalyst is in the form of particulate solids.

6. The microchannel reactor of claim 1 wherein the catalyst is coated on interior walls of a microchannel, grown on interior walls of a microchannel, or coated in situ on a fin structure.

7. The microchannel reactor of claim 1 wherein the catalyst is supported by a support structure made of a material comprising an alloy comprising Ni, Cr and Fe, or an alloy comprising Fe, Cr, Al and Y.

8. The microchannel reactor of claim 1 wherein the catalyst is supported on a support structure having a flow-by configuration, a flow-through configuration, or a serpentine configuration.

9. The microchannel reactor of claim 1 wherein the catalyst is supported on a support structure having the configuration of a foam, felt, wad, fin, or a combination of two or more thereof.

10. The microchannel reactor of claim 1 wherein the catalyst is supported on a support structure having a flow-by configuration with an adjacent gap, a foam configuration with an adjacent gap, a fin structure with gaps, a washcoat on a substrate, or a gauze configuration with a gap for flow.

11. The microchannel reactor of claim 1 wherein the catalyst is supported on a support structure in the form of a fin assembly comprising at least one fin.

12. The microchannel reactor of claim 11 wherein the fin assembly comprises a plurality of parallel spaced fins.

13. The microchannel reactor of claim 11 wherein the fin has an exterior surface and a porous material overlies at least part of the exterior surface of the fin, the catalyst being supported by the porous material.

14. The microchannel reactor of claim 13 wherein the porous material comprises a coating, fibers, foam or felt.

15. The microchannel reactor of claim 11 wherein the fin has an exterior surface and a plurality fibers or protrusions extend from at least part of the exterior surface of the fin, the catalyst being supported by the protrusions.

16. The microchannel reactor of claim 11 wherein the fin has an exterior surface and the catalyst is:

washcoated on at least part of the exterior surface of the fin;

grown on at least part of the exterior surface of the fin from solution;

or deposited on at least part of the exterior surface of the fin using vapor deposition.

17. The microchannel reactor of claim 11 wherein the fin assembly comprises a plurality of parallel spaced fins, at least one of the fins having a length that is different than the length of the other fins.

18. The microchannel reactor of claim 11 wherein the fin assembly comprises a plurality of parallel spaced fins, at least one of the fins having a height that is different than the height of the other fins.

19. The microchannel reactor of claim 11 wherein the fin has a cross section having the shape of a square, a rectangle, or a trapezoid.

20. The microchannel reactor of claim 11 wherein the fin is made of a material comprising:

steel;

aluminum;

titanium;

iron;

nickel;

platinum;

rhodium;

copper;

chromium;

brass;

an alloy of any of the foregoing metals;

a polymer;

ceramics;

glass;

a composite comprising polymer and fiberglass;

quartz;

silicon;

or a combination of two or more thereof.

21. The microchannel reactor of claim 1 wherein the catalyst comprises Co and a support, the catalyst being made by the process comprising:

(A) impregnating the support with a composition comprising Co to provide an intermediate catalytic product;

(B) calcining the intermediate catalytic product formed in (A);

(C) impregnating the calcined intermediate product formed in (B) with a composition comprising Co to provide another intermediate catalytic product; and

(D) calcining the another intermediate catalytic product formed in (C) to form the catalyst, the catalyst having a Co loading of at least about 25% by weight.

22. A process for conducting a Fischer-Tropsch reaction in a microchannel reactor, the microchannel reactor comprising a plurality of process microchannels and a plurality of heat exchange channels, the heat exchange channels extending lengthwise at right angles relative to the lengthwise direction of the process microchannels, the process comprising:

flowing reactants comprising CO and H₂ in the process microchannels in contact with a Fischer-Tropsch catalyst to form a reaction product comprising one or more aliphatic hydrocarbons, the catalyst comprising cobalt supported on an alumina support and being in the form of particulate solids, the cobalt loading being at least about 25% by weight;

exchanging heat between the process microchannels and a heat exchange fluid in the heat exchange channels, the heat exchange fluid undergoing a phase change in the heat exchange channels.

23. The process of claim 22 wherein the reactants enter the process microchannels and the product exits the process microchannels, the temperature of the reactants entering the process microchannels being within about 200°

C. of the temperature of the product exiting the process microchannels.

24. The process of claim 22 wherein the mole ratio of H₂ to CO is in the range of about 0.8 to about 10.

25. The process of claim 22 wherein the reactants further comprise H₂O, CO₂, a hydrocarbon of 1 to about 4 carbon atoms, or a mixture of two or more thereof.

26. The process of claim 22 wherein the heat exchange fluid undergoes partial boiling in the heat exchange channels.

27. The process of claim 22 wherein the reactants and product flow in the process microchannels in a first direction, and the heat exchange fluid flows in the heat exchange channels in a second direction, the second direction being cross current relative to the first direction.

28. The process of claim 22 wherein the heat exchange fluid comprises air, steam, water, carbon dioxide, gaseous nitrogen, a gaseous hydrocarbon or a liquid hydrocarbon.

29. The process of claim 22 wherein the heat exchange fluid comprises water, the water undergoing partial boiling in the heat exchange channels.

30. The process of claim 22 wherein the catalyst further comprises Re, Ru or a mixture thereof.

31. The process of claim 22 wherein the process microchannels have a bulk flow path comprising about 5% to about 95% of the cross sections of such process microchannels.

32. The process of claim 22 wherein the contact time of the reactants and/or product with the catalyst is up to about 2000 milliseconds.

33. The process of claim 22 wherein the temperature of the reactants entering the process microchannels is in the range of about 150°

C. to about 270°

C.

34. The process of claim 22 wherein the pressure within the process microchannels is at least about 5 atmospheres.

35. The process of claim 22 wherein the space velocity for the flow of the reactants and product in the process microchannels is at least about 1000 hr.⁻

1

36. The process of claim 22 wherein the pressure drop for the flow of the reactants and product in the process microchannels is up to about 10 atmospheres per meter of length of the process microchannels.

37. The process of claim 22 wherein the heat exchange fluid flows in the heat exchange channels, the pressure drop for the heat exchange fluid flowing in the heat exchange channels being up to about 10 atmospheres per meter of length of the heat exchange channels.

38. The process of claim 22 wherein the conversion of CO is at least about 50%, the selectivity to methane in the product is about 25% or less, and the yield of product is at least about 35%.

39. The process of claim 22 wherein the catalyst comprises particulate solids with a particle size in the range of about 1 to about 1000 μ

m.

40. The process of claim 22 wherein the product comprises hydrocarbons boiling at a temperature at or below about 350°

C. at atmospheric pressure.

41. The process of claim 22 wherein the product comprises hydrocarbons boiling at or above a temperature of about 350°

C. at atmospheric pressure.

42. The process of claim 22 wherein the product comprises a middle distillate.

43. The process of claim 22 wherein the product comprises at least one olefin.

44. The process of claim 22 wherein the product comprises a normal paraffin, isoparaffin, or mixture thereof.

45. The process of claim 22 wherein the product is further processed using hydrocracking, hydroisomerizing or dewaxing.

46. The process of claim 22 wherein the product is further processed to form a lubricating base oil or a diesel fuel.

47. The process of claim 22 wherein the product flows out of the microchannel reactor and subsequent to the product flowing out of the microchannel reactor a regenerating fluid flows through the process microchannels in contact with the catalyst, the residence time for the regenerating fluid in the process microchannels being from about 0.01 to about 1000 seconds.

48. The process of claim 22 wherein each process microchannel has an internal dimension of up to about 10 mm.

49. The process of claim 22 wherein each heat exchange channel has an internal dimension of up to about 10 mm.

50. The process of claim 22 wherein the process microchannels and heat exchange channels are made of a material comprising:

aluminum;

titanium;

nickel;

copper;

an alloy of any of the foregoing metals;

steel;

monel;

inconel;

brass;

a polymer;

ceramics;

glass;

a composite comprising polymer and fiberglass;

quartz;

silicon;

or a combination of two or more thereof.

51. The process of claim 22 wherein the process microchannels and heat exchange channels are made of stainless steel.

52. The process of claim 22 wherein the microchannel reactor comprises a microchannel reactor core, a reactant header and a product footer.

53. The process of claim 52 wherein the microchannel reactor further comprises a heat exchange header and a heat exchange footer.

54. The process of claim 52 wherein the process microchannels and the heat exchange channels are positioned in the microchannel reactor core.

55. The process of claim 52 wherein the microchannel reactor core comprises layers of the process microchannels and layers of the heat exchange channels aligned one above another or side by side.

56. The process of claim 22 wherein each process microchannel has a cross section having the shape of a square, rectangle, circle or semi-circle.

57. The process of claim 22 wherein each process microchannel has a cross section having the shape of a rectangle.

58. The process of claim 22 wherein each process microchannel has a width and a length, the width tapering from a relatively small dimension to a relatively large dimension over the length of the process microchannel.

59. The process of claim 22 wherein each process microchannel has a width in the range up to about 3 meters, and a length in the range up to about 10 meters.