Catalyst structure and method of Fischer-Tropsch synthesis

Title: Catalyst structure and method of Fischer-Tropsch synthesis

Patent ID: US7585899
Issue Date: September 08, 2009

Abstract:

The present invention includes a catalyst structure and method of making the catalyst structure for Fischer-Tropsch synthesis that both rely upon the catalyst structure having a first porous structure with a first pore surface area and a first pore size of at least about 0.1 .mu.m, preferably from about 10 .mu.m to about 300 .mu.m. A porous interfacial layer with a second pore surface area and a second pore size less than the first pore size is placed upon the first pore surface area. Finally, a Fischer-Tropsch catalyst selected from the group consisting of cobalt, ruthenium, iron and combinations thereof is placed upon the second pore surface area. Further improvement is achieved by using a microchannel reactor wherein the reaction chamber walls define a microchannel with the catalyst structure placed therein through which pass reactants. The walls may separate the reaction chamber from at least one cooling chamber. The present invention also includes a method of Fischer-Tropsch synthesis.

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Inventor(s):

Wang; Yong (Richland, WA, US) ,	Email and Contact Information
Vanderwiel; David P. (Richland, WA, US) ,	Email and Contact Information
Tonkovich; Anna Lee Y. (Pasco, WA, US) ,	Email and Contact Information
Gao; Yufei (Kennewick, WA, US) ,	Email and Contact Information
Baker; Eddie G. (Pasco, WA, US)	Email and Contact Information

Assignee:

Battelle Memorial Institute; (Richland, WA, US)

Agent:

Maughan; Derek H. Rosenberg; Frank

Application No.:

11/364,595

Filing Date:

February 27, 2006

Primary Class:

518/700

Other Classes:

518/715

Field of Search:

518/700,715

Intern'l Class:

C07C 27/00 (20060101)

Primary Examiner:

Parsa; Jafar

US Related Documents:

Application No.: 10666430
Filing Date: September 30, 2003
Patent Number: 7045486

Application No.: 10038228
Filing Date: January 31, 2002
Patent Number: 6660237

Application No.: 09375610
Filing Date: August 31, 1999
Patent Number: 6451864

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Foreign Reference(s):

0869842 EP October 01, 1998
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Other References:

Bergh et al., U.S. Appl. No. 60/122,704, filed Mar. 1999. cited by other.

Parent Case Text:

RELATED APPLICATIONS This is a continuation of U.S. patent application Ser. No. 10/666,430, now U.S. Pat. No. 7,045,486, filed Sep. 19, 2003 which was a divisional of U.S. patent application Ser. No. 10/038,228, now U.S. Pat. No. 6,660,237, filed Jan. 3, 2002 which was a divisional of U.S. patent application Ser. No. 09/375,610, now U.S. Pat. No. 6,451,864, filed Aug. 17, 1999.

Claim(s):

We claim:

1. A method of conducting Fischer-Tropsch synthesis, comprising: providing a microchannel reaction chamber comprising a catalyst for Fischer-Tropsch synthesis, wherein the microchannelreaction chamber has at least one dimension of 8 mm or less; passing a feed stream comprising a mixture of hydrogen and carbon monoxide gas through the microchannel reaction chamber with a residence time of about 1 second or less and at a temperature of275.degree. C. or less; wherein the mixture comprises hydrogen and carbon monoxide in a ratio of from about 2:1 to about 3.5:1; and converting at least 50% of the carbon monoxide in the mixture to hydrocarbons.

2. The method of claim 1 wherein the microchannel reaction chamber comprises at least one reaction chamber wall and wherein said at least one reaction chamber wall separates the reaction chamber from at least one cooling chamber.

3. The method of claim 2 wherein the microchannel reaction chamber has at least one dimension of 1 mm or less.

4. The method of claim 3 further comprising a methane selectivity of 24% or less.

5. The method of claim 1 wherein the catalyst comprises Co and Ru.

6. The method of claim 5 further comprising a methane selectivity of 24% or less.

7. The method of claim 6 wherein the catalyst comprises a metal foam support.

8. The method of claim 1 wherein the catalyst comprises a metal foam support.

9. The method of claim 1 wherein the temperature is in the range of 264 to 275.degree. C.

10. The method of claim 9 further comprising a methane selectivity of 24% or less.

11. The method of claim 1 further comprising a methane selectivity of 24% or less.

12. The method of claim 2 wherein the temperature is in the range of 264 to 275.degree. C.

13. The method of claim 2 wherein the catalyst comprises a metal foam support.

14. The method of claim 13 wherein the microchannel reaction chamber has at least one dimension of 1.5 mm or less.

15. The method of claim 12 wherein the microchannel reaction chamber has at least one dimension of 1.5 mm or less.

16. The method of claim 9 wherein the microchannel reaction chamber has at least one dimension of 1.5 mm or less.

17. A method of conducting Fischer-Tropsch synthesis, comprising: providing a microchannel reaction chamber comprising a catalyst for Fischer-Tropsch synthesis, wherein the microchannel reaction chamber has at least one dimension of 8 mm orless; passing a feed stream comprising a mixture of hydrogen and carbon monoxide gas through the microchannel reaction chamber with a residence time of about 2 seconds or less and at a temperature of 275.degree. C. or less; wherein the mixturecomprises hydrogen and carbon monoxide in a ratio of from about 2:1 to about 3.5:1; and converting at least 50% of the carbon monoxide in the mixture to hydrocarbons.

18. The method of claim 17 wherein the microchannel reaction chamber comprises at least one reaction chamber wall and wherein said at least one reaction chamber wall separates the reaction chamber from at least one cooling chamber.

19. The method of claim 17 wherein the microchannel reaction chamber has at least one dimension of 1 mm or less.

20. The method of claim 18 wherein the catalyst comprises Co and Ru.

21. The method of claim 17 comprising converting at least about 80% of the carbon monoxide in the mixture to hydrocarbons.

22. The method of claim 18 comprising a selectivity to methane of no more than about 10%.

23. The method of claim 17 wherein the microchannel reaction chamber comprises a porous interfacial layer having a thickness of less than 50 microns.

24. The method of claim 3 wherein the microchannel reaction chamber comprises a porous interfacial layer having a thickness of less than 50 microns.

25. The method of claim 17 wherein the microchannel reaction chamber comprises a porous interfacial layer having a thickness of less than 20 microns.

26. The method of claim 3 wherein the microchannel reaction chamber comprises a porous interfacial layer having a thickness of less than 20 microns.

27. The method of claim 23 wherein the porous interfacial layer comprises a metal oxide impregnated with a catalyst metal selected from the group consisting of Fe, Co, Ru, Re, Os, and combinations thereof.

28. The method of claim 24 wherein the porous interfacial layer comprises a metal oxide impregnated with a catalyst metal selected from the group consisting of Fe, Co, Ru, Re, Os, and combinations thereof.

29. The method of claim 25 wherein the porous interfacial layer comprises a metal oxide impregnated with a catalyst metal selected from the group consisting of Fe, Co, Ru, Re, Os, and combinations thereof.

30. The method of claim 26 wherein the porous interfacial layer comprises a metal oxide impregnated with a catalyst metal selected from the group consisting of Fe, Co, Ru, Re, Os, and combinations thereof.

31. The method of claim 17 wherein the microchannel reaction chamber comprises a porous interfacial layer having a thickness of less than 20 microns.

32. A method of conducting Fischer-Tropsch synthesis, comprising: passing a feed stream comprising a mixture of hydrogen and carbon monoxide gas through a reaction chamber; wherein the microchannel reaction chamber has at least one dimensionof 8 mm or less; wherein the reaction chamber comprises catalyst structure comprising a porous interfacial layer having a thickness of less than 20 microns; and converting at least 50% of the carbon monoxide in the mixture to hydrocarbons.

33. The method of claim 32 wherein the catalyst structure comprises a first porous structure having a first pore size of at least about 0.1 .mu.m and wherein the porous interfacial layer is disposed over the first porous structure and whereinthe porous interfacial layer has a second pore size that is less than the first pore size; and further wherein the step of converting the carbon monoxide is conducted at a temperature of at least 200.degree. C. and wherein the selectivity to methane isat most 25%.

34. The method of claim 33 wherein the porous interfacial layer comprises a metal oxide impregnated with a catalyst metal selected from the group consisting of Fe, Co, Ru, Re, Os, and combinations thereof.

35. The method of claim 32 wherein the reaction chamber comprises at least one reaction chamber wall and wherein said at least one reaction chamber wall separates the reaction chamber from at least one cooling chamber; and wherein theresidence time of the mixture in the reaction channel is less than 5 seconds.

36. The method of claim 35 wherein the reaction chamber has at least one dimension of 1 mm or less.

37. The method of claim 34 wherein the reaction chamber has at least one dimension of 8 mm or less.

38. The method of claim 32 wherein the porous interfacial layer comprises a metal oxide impregnated with a catalyst metal selected from the group consisting of Fe, Co, Ru, Re, Os, and combinations thereof.

39. The method of claim 38 wherein the reaction chamber comprises at least one reaction chamber wall and wherein said at least one reaction chamber wall separates the reaction chamber from at least one cooling chamber; and wherein theresidence time of the mixture in the reaction channel is less than 5 seconds.

40. The method of claim 35 wherein the reaction chamber has at least one dimension of 1 mm or less.

41. The method of claim 40 wherein the residence time of the mixture in the reaction channel is less than 2 seconds.

Description:

FIELD OF THE INVENTION

The present invention is a catalyst structure and method of making, and a method of Fischer-Tropsch synthesis.

BACKGROUND OF THE INVENTION

Fischer-Tropsch synthesis is carbon monoxide hydrogenation that is usually performed on a product stream from another reaction including but not limited to steam reforming (product stream H.sub.2/C0.about.3), partial oxidation (product streamH.sub.2/C0.about.2), autothermal reforming (product stream H.sub.2/C0.about.2.5), CO.sub.2 reforming (H.sub.2/C0.about.1) coal gassification (product stream H.sub.2/C0.about.1) and combinations thereof.

Fundamentally, Fischer-Tropsch synthesis has fast surface reaction kinetics. However, the overall reaction rate is severely limited by heat and mass transfer with conventional catalysts or catalyst structures. The limited heat transfer togetherwith the fast surface reaction kinetics may result in hot spots in a catalyst bed. Hot spots favor methanation. In commercial processes, fixed bed reactors with small internal diameters or slurry type and fluidized type reactors with small catalystparticles (>50 .mu.m) are used to mitigate the heat and mass transfer limitations. In addition, Fischer-Tropsch reactors are operated at lower conversions per pass to minimize temperature excursion in the catalyst bed. Because of the necessaryoperational parameters to avoid methanation, conventional reactors are not improved even with more active Fischer-Tropsch synthesis catalysts. Detailed operation is summarized in Table 1 and FIG. 1.

TABLE-US-00001 TABLE 1 Comparison of Residence Times Effects in Fischer- Tropsch Experimentation Residence CH.sub.4 Ref.sup.(A) Catalyst Conditions time Conversion selectivity 1 Co/ZSM-5 240.degree. C., 20-atm, H.sub.2/CO = 2 3.6-sec 60% 21% 2Co/MnO 220.degree. C., 21-atm, H.sub.2/CO = 2 0.72-sec 13% 15% 3 Co--Ru/TiO.sub.2 200.degree. C., 20-atm, H.sub.2/CO = 2 3-sec 61% 5% Co/TiO.sub.2 '' 8-sec 49% 7% 4 Co/TiO.sub.2 200.degree. C., 20-atm, H.sub.2/CO = 2.1 2-sec 9.5%

US Patent:

7585899