Oxidation process using microchannel technology and novel catalyst useful in same

• US 7,226,574 B2
• Filed: 05/30/2003
• Issued: 06/05/2007
• Est. Priority Date: 05/16/2003
• Status: Expired due to Fees

• Current Assignee: Velcoys Inc.
• Original Assignee: Velocys Incorporated (Velocys PLC)
• Inventors: Wang, Yong, Yang, Barry L., Long, Richard Q., Tonkovich, Anna Lee, Daly, Francis P., Daymo, Eric
• Primary Examiner(s): Vanoy; Timothy C.
• Application Number:
  US10/449,913
• Publication Number:
  US 20040229752A1
• Time in Patent Office: 1,467 Days
• Field of Search: 431/2, 252/373, 423/650, 423/651, 423/652, 423/653, 423/654, 423/418.2, 423/437.1
• US Class Current: 423/650
• CPC Class Codes: B01D 2253/112 Metals or metal compounds not provided for in B01D2253/104 or B01D2253/106
• CPC Class Codes: B01D 2253/25 Coated, impregnated or composite adsorbents
• CPC Class Codes: B01D 2253/306 Surface area, e.g. BET-specific surface
• CPC Class Codes: B01D 2253/34 Specific shapes
• CPC Class Codes: B01D 53/02 by adsorption, e.g. preparative gas chromatography solid sorbent compositions B01J20/00, preparation of inorganic compounds or elements C01
• CPC Class Codes: B01D 53/0407 Constructional details of adsorbing systems
• CPC Class Codes: B01D 53/0446 Means for feeding or distributing gases
• 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 2219/00822 Metal
• CPC Class Codes: B01J 2219/00831 Glass
• CPC Class Codes: B01J 2219/00833 Plastic
• CPC Class Codes: B01J 2219/00835 Comprising catalytically active material
• CPC Class Codes: B01J 2219/00862 Dimensions of the reaction cavity itself
• CPC Class Codes: B01J 2219/00873 Heat exchange
• CPC Class Codes: B01J 2219/00889 Mixing micromixers B01F33/30
• CPC Class Codes: B01J 23/63 with rare earths or actinides
• CPC Class Codes: B01J 37/0225 of metal substrates
• CPC Class Codes: B01J 37/0244 Coatings comprising several layers
• 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 2203/0261 : containing a catalytic partial oxidation step [CPO]
• CPC Class Codes: C01B 2203/0844 : the non-combustive exothermic reaction being another reforming reaction as defined in groups C01B2203/02 - C01B2203/0294
• CPC Class Codes: C01B 2203/0872 : Methods of cooling
• CPC Class Codes: C01B 2203/0883 : by indirect heat exchange
• CPC Class Codes: C01B 2203/0894 : Generation of steam
• CPC Class Codes: C01B 2203/1011 : Packed bed of catalytic structures, e.g. particles, packing elements
• CPC Class Codes: C01B 2203/1023 : Catalysts in the form of a monolith or honeycomb
• CPC Class Codes: C01B 2203/1029 : Catalysts in the form of a foam
• CPC Class Codes: C01B 2203/1035 : Catalyst coated on equipment surfaces, e.g. reactor walls
• CPC Class Codes: C01B 2203/1052 : Nickel or cobalt catalysts
• CPC Class Codes: C01B 2203/1064 : Platinum group metal catalysts
• CPC Class Codes: C01B 2203/1082 : Composition of support materials
• CPC Class Codes: C01B 2203/1094 : Promotors or activators
• CPC Class Codes: C01B 2203/1211 : Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
• CPC Class Codes: C01B 2203/1241 : Natural gas or methane
• CPC Class Codes: C01B 2203/1247 : Higher hydrocarbons
• CPC Class Codes: C01B 2203/141 : At least two reforming, decomposition or partial oxidation steps in parallel
• CPC Class Codes: C01B 2203/1633 : Measuring the pressure
• CPC Class Codes: C01B 2203/82 : Several process steps of C01B2203/02 - C01B2203/08 integrated into a single apparatus
• CPC Class Codes: C01B 3/384 : the catalyst being continuously externally heated
• CPC Class Codes: C01B 3/386 : Catalytic partial combustion
• CPC Class Codes: C07C 45/46 : Friedel-Crafts reactions
• CPC Class Codes: F28F 21/065 : the heat-exchange apparatus employing plate-like or laminated conduits
• CPC Class Codes: F28F 2255/06 : composite, e.g. polymers with fillers or fibres
• CPC Class Codes: F28F 2260/02 : having microchannels
• CPC Class Codes: F28F 3/048 : in the form of ribs integral with the element or local variations in thickness of the element, e.g. grooves, microchannels
• CPC Class Codes: Y02C 20/20 : of methane
• CPC Class Codes: Y02P 20/52 : using catalysts, e.g. selective catalysts

Abstract

A process is disclosed for converting a hydrocarbon reactant to a product comprising CO and H₂. The process comprises: (A) flowing a reactant composition comprising the hydrocarbon reactant and oxygen or a source of oxygen through a microchannel reactor in contact with a catalyst under reaction conditions to form the product, the microchannel reactor comprising at least one process microchannel with the catalyst positioned within the process microchannel, the hydrocarbon reactant comprising methane, the contact time for the reactant composition within the process microchannel being up to about 500 milliseconds, the temperature of the reactant composition and product within the process microchannel being up to about 1150° C., the conversion of the hydrocarbon reactant to carbon oxide being at least about 50%. The product formed in step (A) may be converted to a product comprising CO₂ and H₂O in a microchannel reactor.

Claims

1. A process for converting a hydrocarbon reactant to a partial oxidation reaction product comprising CO and H₂ in a microchannel reactor, the microchannel reactor comprising at least one process microchannel and at least one partial oxidation reaction catalyst in the at least one process microchannel, the process comprising:

(A) mixing a reactant composition comprising the hydrocarbon reactant and oxygen or a source of oxygen in the at least one process microchannel and flowing the resulting mixture in the at least one process microchannel in contact with the at least one partial oxidation reaction catalyst under partial oxidation reaction conditions to form the product, the hydrocarbon reactant comprising methane, the contact time for the reactant composition within the at least one process microchannel being up to about 500 milliseconds, the temperature of the reactant composition and product within the at least one process microchannel being up to about 1500°

C., the conversion of the hydrocarbon reactant being at least about 50%.

2. The process of claim 1 wherein the product formed in step (A) is an intermediate product, the process further comprising the following additional step subsequent to step (A):

(B) flowing the intermediate product formed in step (A) through a microchannel reactor in contact with a combustion catalyst under reaction conditions to form a final product comprising CO₂ and H₂O.

3. The process of claim 1 wherein the reactant composition further comprises H₂O and the product comprises H₂, CO and CO₂.

4. The process of claim 1 wherein the reactant composition is preheated prior to step (A).

5. The process of claim 1 wherein the reactant composition and oxygen or oxygen source are mixed prior to step (A).

6. The process of claim 1 wherein the reactant composition and oxygen or oxygen source are mixed during step (A).

7. The process of claim 1 wherein the microchannel reactor comprises a plurality of process microchannels containing the catalyst, a header providing a flow passageway for fluid to enter the process microchannels, and a footer providing a flow passageway for fluid to leave the process microchannels.

8. The process of claim 7 wherein each process microchannel has an internal dimension of width or height of up to about 10 mm.

9. The process of claim 7 wherein each of the process microchannels has an entrance, an exit and an elongated section extending between the entrance and the exit, the process microchannels further comprising at least one additional entrance in the elongated section, at least one reactant entering the process microchannels through the at least one additional entrance.

10. The process of claim 7 wherein the process microchannels are made of a material comprising:

steel;

monel;

inconel;

aluminum;

titanium;

nickel;

copper;

brass;

an alloy of any of the foregoing metals;

a polymer;

ceramics;

glass;

a composite comprising a polymer and fiberglass;

quarlz;

silicon;

or a combination of two or more thereof.

11. The process of claim 7 wherein the microchannel reactor further comprises heat exchange channels in thermal contact with the process microchannels.

12. The process of claim 11 wherein the heat exchange channels comprise microchannels.

13. The process of claim 11 wherein each heat exchange channel has an internal dimension of width or height of up to about 10 mm.

14. The process of claim 11 wherein the heat exchange channels are made of a material comprising:

steel;

monel;

inconel;

aluminum;

titanium;

nickel;

copper;

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.

15. The process of claim 9 wherein the at least one reactant entering the process microchannels through the at least one additional entrance comprises the oxygen or source of oxygen.

16. The process of claim 1 wherein the hydrocarbon reactant further comprises:

an aliphatic compound, an aromatic compound, or a mixture thereof.

17. The process of claim 1 wherein the hydrocarbon reactant further comprises an alkane containing 2 to about 20 carbon atoms per molecule.

18. The process of claim 1 wherein the hydrocarbon reactant further comprises ethane, propane, isopropane, butane, isobutane, a pentane, a hexane, a heptane, an octane, a nonane, a decane, or a mixture of two or more thereof.

19. The process of claim 1 wherein the hydrocarbon reactant comprises natural gas.

20. The process of claim 1 wherein the hydrocarbon reactant further comprises an alkene containing 2 to about 20 carbon atoms.

21. The process of claim 1 wherein the hydrocarbon reactant further comprises ethylene;

propylene;

1-butane;

2-butene;

isobutylene;

1-pentene;

2-pentene;

3-methyl-1-butene;

2-methyl-2-butene;

1-hexene;

2,3-dimethyl-2-butene;

1-heptene;

1-octene;

1-nonene;

1-decene;

or a mixture of two or more thereof.

22. The process of claim 1 wherein the hydrocarbon reactant further comprises a polyene containing 3 to about 20 carbon atoms.

23. The process of claim 1 wherein the hydrocarbon reactant further comprises 1,2-propadiene;

1,3-butadiene;

2-methyl-1,3-butadiene;

1,3-pentadiene;

1,4-pentadiene;

1,5-hexadiene;

2,4-hexadiene;

2,3-dimethyl-1,3-butadiene;

or a mixture of two or more thereof.

24. The process of claim 1 wherein the hydrocarbon reactant further comprises an alkyl or alkylene substituted aromatic compound.

25. The process of claim 1 wherein the hydrocarbon reactant comprises toluene, o-xylene, m-xylene, p-xylene, hemimellitene, pseudocumene, mesitylene, prehnitene, isodurene, durene, pentamethylbenzene, hexamethylbenzene, ethylbenzene, n-propylbenzene, cumene, n-butylbenzene, isobutylbenzene, sec-butylbenzene, tert-butylbenzene, p-cymene, styrene, or a mixture of two or more thereof.

26. The process of claim 1 wherein the hydrocarbon reactant further comprises a natural oil, synthetic oil, or mixture thereof.

27. The process of claim 1 wherein the hydrocarbon reactant further comprises a distillate fuel.

28. The process of claim 1 wherein the hydrocarbon reactant further comprises naphtha, diesel fuel, fuel oil, kerosene or gasoline.

29. The process of claim 1 wherein the hydrocarbon reactant further comprises a hydrocarbon derived from a vegetable source, a mineral source, or mixture thereof.

30. The process of claim 1 wherein the hydrocarbon reactant further comprises a hydrocarbon derived from soybean, rapeseed, palm, shale, coal, tar sands, or a mixture of two or more thereof.

31. The process of claim 1 wherein the source of oxygen comprises air.

32. The process of claim 1 wherein the reactant composition further comprises a diluent material.

33. The process of claim 11 wherein the process microchannels exchange heat with a heat exchange fluid flowing through the heat exchange channels.

34. The process of claim 33 wherein the heat exchange fluid undergoes a phase change as it flows through the heat exchange channels.

35. The process of claim 11 wherein the process microchannels are cooled by an endothermic chemical reaction conducted in the heat exchange channels.

36. The process of claim 35 wherein the endothermic chemical reaction comprises a steam reforming reaction or a dehydrogenation reaction.

37. The process of claim 11 wherein the reactant composition flows through the process microchannels in a first direction, and a heat exchange fluid flows through the heat exchange channels in a second direction, the second direction being cross current relative to the first direction.

38. The process of claim 11 wherein the reactant composition flows through the process microchannels flow in a first direction, and a heat exchange fluid flows through the heat exchange channels in a second direction, the second direction being cocurrent relative to the first direction.

39. The process of claim 11 wherein the hydrocarbon reactant composition flows through the process microchannels in a first direction, and a heat exchange fluid flows Through the heat exchange channels in a second direction, the second direction being counter current relative to the first direction.

40. The process of claim 11 wherein a heat exchange fluid flows through the heat exchange channels, the heat exchange fluid comprising air, steam, liquid water, carbon dioxide, gaseous nitrogen, liquid nitrogen, a gaseous hydrocarbon or a liquid hydrocarbon.

41. The process of claim 1 wherein the catalyst is in the form of particulate solids.

42. The process 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.

43. The process 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.

44. The process 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.

45. The process 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.

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

47. The process of claim 46 wherein the fin assembly comprises a plurality of parallel spaced fins.

48. The process of claim 46 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.

49. The process of claim 48 wherein the porous material comprises a costing, fibers, foam or felt.

50. The process of claim 46 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.

51. The process of claim 46 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.

52. The process of claim 46 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.

53. The process of claim 46 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.

54. The process of claim 46 wherein the fin has a cross section having the shape of a square or a rectangle.

55. The process of claim 46 wherein the fin has a cross section having the shape of a trapezoid.

56. The process of claim 46 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.

57. The process of claim 46 wherein the fin is made of an alloy comprising Ni, Cr and Fe, or an alloy comprising Fe, Cr, Al and Y.

58. The process of claim 46 wherein the fin is made of Al₂O₃ forming material.

59. The process of claim 46 wherein the fin is made of a Cr₂O₃ forming material.

60. The process of claim 1 wherein the catalyst comprises Rh, Pt, Ni, Cr, Ru, Pd, Os, Ir, or an oxide thereof, or a mixture of two or more thereof.

61. The process of claim 1 wherein the catalyst comprises a composition represented by the formula

M¹_aM²_bM³_cAl_dO_x

wherein

M¹ is Rh, Ni, Pd, Pt, Ru, Co or a mixture of two or more thereof;

M² is Ce, Pr, Tb or a mixture of two or more thereof;

M³ is La, Ba, Zr, Mg, Ca or a mixture of two or more thereof;

a is a number In the range of about 0.0001 to about 1;

b is a number in the range of zero to about 0.9999;

c is a number in the range of about 0.0001 to about 0.9999;

d is a number in the range of about 0.0001 to about 0.9999; and

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

the catalyst being coated on an interior wall of the process microchannel, or supported on a foam, felt, wad or fin positioned within the process microchannel.

62. The process of claim 2 wherein the combustion catalyst comprises a noble metal or an oxide thereof, a pervoskite or an aluminate.

63. The process of claim 62 wherein the combustion catalyst further comprises Ce, Tb or Pr, or an oxide thereof, or a mixture of two or more thereof.

64. The process of claim 2 wherein the combustion catalyst comprises Pt, Rh, Pd, Co. Mn, Fe, Ni, or an oxide thereof, or a mixture of two or more thereof.

65. The process of claim 1 wherein the contact time of the reactant composition and/or product with the catalyst is from about 0.1 milliseconds to about 100 seconds.

66. The process of claim 1 wherein the temperature of the reactant composition entering the process microchannel is in the range of about 200°

C. to about 1000°

C.

67. The process of claim 1 wherein the pressure of the reactant composition entering the process microchannel is in the range of about 0.1 to about 100 atmospheres.

68. The process of claim 1 wherein the space velocity for the flow of the reactant composition and product through the process microchannel is at least about 100 hr⁻

1.

69. The process of claim 1 wherein the pressure drop for the flow of the reactant composition and product through the process microchannel is up to about 2 atmospheres per meter of length of the process microchannel.

70. The process of claim 11 wherein a heat exchange fluid flows through the heat exchange channels, the total pressure drop for the heat exchange fluid flowing through the heat exchange channels being up to about 10 atmospheres.

72. The process of claim 1 wherein the catalyst is represented by the formula Rh/LaAl₁₁O₁₈ or Rh/LaAlO₃.

71. A process for converting a hydrocarbon reactant to a partial oxidation reaction product comprising H₂ and CO, the process comprising:

(A) flowing a reactant composition comprising the hydrocarbon reactant and oxygen or a source of oxygen in a microchannel reactor in contact with a partial oxidation reaction catalyst under partial oxidation reaction conditions to convert the reactant composition to the product, the hydrocarbon reactant comprising methane, the microchannel reactor comprising at least one process microchannel, the catalyst being in the process microchannel, the partial oxidation reaction catalyst comprising a composition represented by the formula

M¹_aM²_bM³_cAl_dO_x

wherein

M¹ is Rh, Ni, Pd, Pt, Ru, Co or a mixture of two or more thereof;

M² is Ce, Pr, Tb or a mixture of two or more thereof;

M³ is La, Ba, Zr, Mg, Ca or a mixture of two or more thereof;

a is a number in the range of about 0.0001 to about 1;

b is a number in the range of zero to about 0.9999;

c is a number in the range of about 0.0001 to about 0.9999;

d is a number in the range of about 0.0001 to about 0.9999; and

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

the catalyst being coated on an interior wall of the process microchannel, or supported on a foam, felt, wad or fin positioned within the process microchannel.

73. A process for converting a hydrocarbon reactant to a partial oxidation reaction product comprising CO and H₂, comprising:

flowing a reactant composition comprising the hydrocarbon reactant and oxygen or a source of oxygen in a microchannel reactor in contact with a partial oxidation reaction catalyst under partial oxidation reaction conditions to form the product, the microchannel reactor comprising at least one process microchannel, the catalyst being in the at least one process microchannel, the hydrocarbon reactant comprising methane and at least one additional hydrocarbon capable of undergoing an oxidation reaction, the contact time for the reactant composition within the process microchannel being up to about 500 milliseconds, the temperature of the reactant composition and product within the process microchannel being up to about 1150°

C., the conversion of the hydrocarbon reactant being at least about 50%.

74. A process for converting a hydrocarbon reactant to a partial oxidation reaction product comprising CO and H₂, comprising:

flowing a reactant composition comprising the hydrocarbon reactant and oxygen or a source of oxygen in a microchannel reactor in contact with a partial oxidation reaction catalyst under partial oxidation reaction conditions to form the product, the microchannel reactor comprising at least one process microchannel, the catalyst being in the at least one process microchannel, the at least one process microchannel exchanging heat with a heat exchange fluid in at least one heat exchange channel, the at least one heat exchange channel being in thermal contact with the at least one process microchannel, the heat exchange fluid undergoing a phase change in the at least one heat exchange channel, the hydrocarbon reactant comprising methane, the contact time for the reactant composition in the at least one process microchannel being up to about 500 milliseconds, the temperature of the reactant composition and product in the at least one process microchannel being up to about 1150°

C., the conversion of the hydrocarbon reactant being at least about 50%.

75. A process for converting a hydrocarbon reactant to a partial oxidation reaction product comprising CO and H₂ in a microchannel reactor, comprising:

mixing a reactant composition comprising the hydrocarbon reactant and oxygen or a source of oxygen in at least one process microchannel and flowing the mixture into a process microchannel in contact with a partial oxidation reaction catalyst under partial oxidation reaction conditions to form the product, the microchannel reactor comprising at least one process microchannel, the catalyst being in the process microchannel, the at least one process microchannel exchanging heat with a heat exchange fluid in at least one heat exchange channel, the at least one heat exchange channel being in thermal contact with the at least one process microchannel, an endothermic reaction being conducted in the at least one heat exchange channel, the hydrocarbon reactant comprising methane, the contact time for the reactant composition in the at least one process microchannel being up to about 500 milliseconds, The temperature of the reactant composition and product in the at least one process microchannel being up to about 1150°

C., the conversion of the hydrocarbon reactant being at least about 50%.

76. A process for converting a hydrocarbon reactant to a partial oxidation reaction product comprising CO and H₂, comprising:

flowing a reactant composition comprising the hydrocarbon reactant and oxygen or a source of oxygen in a microchannel reactor in contact with a partial oxidation reaction catalyst under partial oxidation reaction conditions to form the product, the microchannel reactor comprising at least one process microchannel, the catalyst being in the at least one process microchannel, the catalyst comprising Rh/LaAl₁₁O₁₈ or Rh/LaAlO₃, the hydrocarbon reactant comprising methane, the contact time for the reactant composition in the at least one process microchannel being up to about 500 milliseconds, the temperature of the reactant composition and product in the at least one process microchannel being up to about 1150°

C., the conversion of the hydrocarbon reactant being at least about 50%.