Process of conducting reactions or separation in a microchannel with internal fin support for catalyst or sorption medium

• US 7,896,935 B2
• Filed: 12/28/2006
• Issued: 03/01/2011
• Est. Priority Date: 05/16/2003
• Status: Active Grant

• Current Assignee: Velocys Incorporated (Velocys PLC)
• Original Assignee: Velocys Incorporated (Velocys PLC)
• Inventors: Yang, Barry L., Perry, Steven T., Long, Richard Q., Qiu, Dongming, Tonkovich, Anna Lee, Yuschak, Thomas
• Primary Examiner(s): BHAT, NINA NMN
• Application Number:
  US11/617,158
• Publication Number:
  US 20070140955A1
• Time in Patent Office: 1,524 Days
• Field of Search: 422/172, 422/178, 422/188, 422/190, 422/198, 422/211, 95/90, 95/96, 95/99, 951/06, 951/14, 951/15, 951/16, 961/21, 961/26, 961/46, 585/250, 585/800, 518/702, 518/726, 481/277
• US Class Current: 48/127.7
• 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
• 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
• 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 of conducting a catalyst reaction or fluid separation in comprising: at least one process microchannel having a height, width and length, the height being up to about 10 mm, the process microchannel having a base wall extending in one direction along the width of the process microchannel and in another direction along the length of the process microchannel; at least one fin projecting into the process microchannel from the base wall and extending along at least part of the length of the process microchannel; and a catalyst or sorption medium supported by the fin.

Claims

1. A process for conducting a catalytic reaction or a fluid separation in an apparatus comprising at least one process microchannel and at least one heat exchanger adjacent to the process microchannel, the process microchannel having a height, width and length, the process microchannel having a base wall extending in one direction along the width of the process microchannel and in another direction along the length of the process microchannel, at least one fin projecting into the process microchannel from the base wall and extending along at least part of the length of the process microchannel, the thermal conductivity of the fin being about 10 W/m/K or greater, and a catalyst or a sorption medium supported by the fin,

the process comprising:

flowing one or more reactants in the process microchannel in contact with the catalyst, and reacting the one or more reactants to form a product;

or flowing a fluid in the process microchannel in contact with the sorption medium, and sorbing one or more components of the fluid on the sorption medium; and

exchanging heat between the process microchannel and the heat exchanger, at least part of the heat being transferred through the fin.

2. The process of claim 1 wherein the at least one process microchannel comprises a plurality of process microchannels extending parallel to each other.

3. The process of claim 1 wherein the at least one fin comprises a plurality of parallel spaced fins.

4. The process of claim 1 wherein the process microchannel has an upper wall spaced apart from and facing the base wall, the fin extending from the base wall to the upper wall.

5. The process of claim 1 wherein the process microchannel has an upper wall spaced apart from and facing the base wall, the fin extending from the base wall part way toward the upper wall.

6. The process of claim 1 wherein the fin has an exterior surface and a porous material overlies at least part of the exterior surface of the fin, the catalyst or sorption medium being supported by the porous material.

7. The process of claim 6 wherein the porous material comprises a coating, fibers, foam or felt.

8. The process of claim 1 wherein the fin has an exterior surface and a plurality of fibers or protrusions extend from at least part of the exterior surface of the fin, the catalyst or sorption medium being supported by the protrusions.

9. The process of claim 1 wherein the fin has an exterior surface and the catalyst or sorption medium 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.

10. The process of claim 1 wherein the fin extends continuously along at least part of the length of the process microchannel.

11. The process of claim 1 wherein the fin extends discontinuously along at least part of the length of the process microchannel.

12. The process of claim 1 wherein the fin comprises a plurality of separate fin members extending along at least part of the length of the process microchannel.

13. The process of claim 1 wherein the at least one fin 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.

14. The process of claim 1 wherein the at least one fin 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.

15. The process of claim 1 wherein the cross section of the fin has the shape of a square or a rectangle.

16. The process of claim 1 wherein the cross section of the fin has the shape of a trapezoid.

17. The process of claim 1 wherein the fin is made separately from the microchannel and is inserted into the process microchannel.

18. The process of claim 1 wherein the fin is formed on the base wall of the process microchannel.

19. The process of claim 1 wherein the fin is cut into the interior surface of the base wall of the process microchannel.

20. The process of claim 1 wherein the process microchannel is made of a material comprising:

steel;

aluminum;

titanium;

nickel;

platinum;

rhodium;

copper;

chromium;

brass;

an alloy of any of the foregoing metals;

a polymer;

ceramics;

glass;

a composite comprising a polymer and fiberglass;

quartz;

silicon;

or a combination of two or more thereof.

21. The process of claim 1 wherein the fin is made of a material comprising:

steel;

aluminum;

titanium;

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.

22. The process of claim 1 wherein the fin is made of an alumina forming material.

23. The process of claim 1 wherein the fin is made of FeCrAIY.

24. The process of claim 1 wherein the apparatus further comprises at least one heat exchange channel adjacent to the process microchannel.

25. The process of claim 24 wherein the heat exchange channel is a microchannel.

26. The process of claim 24 wherein the heat exchange channel is made of a material comprising:

steel;

aluminum;

titanium;

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.

27. The process of claim 1 wherein the catalyst comprises a catalyst useful in conducting one or more of the following chemical reactions:

acetylation addition, alkylation, dealkylation, hydrodealkylation, reductive alkylation, amination, ammonia synthesis, aromatization, arylation, autothermal reforming, carbonylation, decarbonylation, reductive carbonylation, carboxylation, reductive carboxylation, reductive coupling, condensation, cracking, hydrocracking, cyclization, cyclooligomerization, ammoxidation, water-gas shift, dehalogenation, dimerization, epoxidation, esterification, Fischer-Tropsch reaction, halogenation, hydrohalogenation, homologation, hydration, dehydration, hydrogenation, dehydrogenation, hydrocarboxylation, hydroformylation, hydrogenolysis, hydrometallation, hydrosilation, hydrolysis, hydrotreating, isomerization, methylation, demethylation, metathesis, methanol synthesis, nitration, oxidation, partial oxidation, polymerization, reduction, reformation, reverse water gas shift, sulfonation, telomerization, transesterification, trimerization, Sabatier reaction, carbon dioxide reforming, preferential oxidation, or preferential methanation.

28. The process of claim 1 wherein the catalyst comprises a metal, metal oxide or mixed metal oxide of a metal comprising Mo, W, V, Nb, Sb, Sn, Pt, Pd, Cs, Zr, Cr, Mg, Mn, Ni, Co, Ce, or a mixture of two or more thereof.

29. The process of claim 1 wherein the catalyst comprises:

a noble metal, a transition metal or combination thereof;

an oxide of an alkali metal, alkaline earth metal, boron, gallium, germanium, arsenic, selenium, tellurium, thallium, lead, bismuth, polonium, magnesium, titanium, vanadium, chromium, manganese, iron, nickel, cobalt, copper, zinc, zirconium, molybdenum, tin, calcium, aluminum, silicon, lanthanum series element;

or a combination of any two or more of the foregoing.

30. The process of claim 1 wherein the sorption medium comprises silver, gold, platinum, palladium, nickel, zeolite, silica gel, or a combination of two or more thereof.

31. The process of claim 1 wherein the sorption medium is derived from Fe(II), Co(II), Cu(I), V(II), Mn(II), Mn(III), Cr(II), Ag(I), Rh(I), Rh(II), Rh(III), U(IV), V(IV), Ru(II), Ru(IV), Ti(III), Cr(IV), Bi(III), Ni(II), W(V), W(IV), Mo(II), Mo(III), Mo(IV), Mo(V), Mo(VI), or a combination of two or more thereof.

32. The process of claim 1 wherein the sorption medium is derived from:

dipyridyl;

2,6-[1-(2-imidazol-4-ylethylimino) ethyl pyridine];

cyclen;

cyclam;

a Schiff base ligand;

acetyl acetonate or an oligomer or polymer thereof;

a carboxylate;

bipyridyl or an oligomer or polymer thereof;

a porphyrin or an oligomer or polymer thereof;

a corin or an oligomer or polymer thereof;

a polyamide;

a protein;

8-hydroxy quinoline or an oligomer or polymer thereof;

ethyl cysteinate or an oligomer or polymer thereof;

an N-alkyl alkanohydroxamic acid;

dimethylglyoxime;

sym-diethylethylenediamine;

or a combination of two or more thereof.

33. The process of claim 1 wherein the sorption medium is derived from an imidazole, histidine amino acid, pyridine, piperidine, 4-methyl aminopyridine, 4-dimethyl aminopyridine, a nitrate, a thiocyanate, a halide, or a combination of two or more thereof.

34. The process of claim 1 wherein the sorption medium comprises:

hemoglobin;

hemoerythyrin;

hemocyanin;

myoglobin;

Co(II) (acacen);

Co(II) (dry cave) (N-methyl imidazole);

Fe(II) (H2TpivPP)B;

Fe(II)(capped porphyrin)B;

Fe(ophen)₂²⁺;

bis(ethyl cysteinato) oxovanadium (IV);

Cu(I) (bimp);

bis(dimethylglyoximato)cobalt(II);

bis(histidine)cobalt(II);

dinitrato-bis(sym-diethylethylenediamine)cobalt(II);

dichloro-bis(sym-diethylethylenediamine)cobalt(II);

[m-tetra(a,a,a,a-o-pivalamidophenyl)porphyrin]cobalt(II);

[N,N-bis(salicylidene)dipropylenetriamine] cobalt(II);

[2,3,10,11,13,19-hexamethyl-3,10, 14,18,21,25-hexaazabicyclo[10.7.7] hexacosa-1,11,13,18,20,25-hexene-k⁴N)cobalt(II)hexafluorophosphate;

[N,N′

-bis(salicylicylidene) ethylenediamine]cobalt(II);

[N,N′

-bis(3-methoxysalicylicylidene)ethylenediamine]cobalt(II);

[N,N′

-bis(salicylicylidene)tetramethylethylenediamine]cobalt(II);

[N,N′

-bis(3-methoxysalicylicylidene)tetramethylethylenediamine]cobalt(II);

[N,N′

-bis(3-isoprpoxysalicylicylidene)tetramethylethylenediamine]cobalt(II);

[N,N′

-bis(3-ethoxysalicylicylidene)tetramethylethylenediamine]cobalt(II);

[N,N′

-bis(5-methoxysalicylicylidene)tetramethylethylenediamine]cobalt(II);

[N,N′

-bis(5-n-butoxysalicylicylidene)tetramethylethylenediamine]cobalt(II);

[N,N′

-bis(salicylidene)ethylenediamine]cobalt(II));

a cobalt (II) porphyrin complex;

a metal-cyanide complex encapsulated within a zeolite;

a cyanocobaltate;

hemoglobin, hemerythrin or hemocyanin containing a diiron(III,IV), dicopper(II) or dimanganese core;

N,N′

-disalicylideneethylenediamine cobalt(II);

cobalt di-(3-methoxysalicylal tertbutylamine);

[N,N′

-bis(salicylidene)n-propyldipropylenetriamine]cobalt(II);

1-methylimidazole;

2-methylimidazole;

4-dimethylaminopyridine;

cyanopyridine;

cobalt chelated copolymer derived from ethylene-diamine-tetraacetic acid, methyl methacrylate and butyl acrylate;

bis(histidine) cobalt(II);

[a-mono(o-methacrylamidophenyl)-a,a,a-tris(o-pivalamidophenyl)porphinato]cobalt;

[meso-a,a,a,a-tetrakis(o-pivalamidophenyl)porphinato]-iron(II);

cobalt(II) meso-tetra-phenyl-porphyrin;

cobalt(II) meso-tetrakis(2-chlorophenyl) prophyrin;

cobalt(II) meso-tetrakis(4-chlorophenyl) porphyrin;

cobalt(II) meso-tetrakis(4-methoxy phenyl) porphyrin;

cobalt(II) meso-tetrakis(2,4-dimethoxy phenyl) porphyrin;

ruthenium (III) bis(salicylaldehyde)ethylenediimine;

ruthenium (III) bis(salicylaldehyde)diethlenetriimine;

ruthenium (III) bis(picolinaldehyde)-o-phenylenediimine;

ruthenium (III) bis(picolinaldehyde)ethylenediimine;

ruthenium (III) bis(picolinaldehyde)diethylenetriimine;

bis(dimethylglyoximato)nickel(II);

bis(dimethylglyoximato)cobalt(II);

bis(dimethylglyoximato)copper(II);

dinitrato-bis(sym-diethylenediamine)cobalt(II);

dithiocyanato-bis(sym-diethylethelenediamine)cobalt(II);

dichloro-bis(sym-diethylethylenediamine)cobalt(II);

cobalt di-(salicylal)-3,3′

-diimino-di-n-propylamine;

N,N′

-disalicyclidene ethylene diamine cobalt (II);

N,N′

-ethylene-bis(5-nitro-salicyliden-iminato) cobalt(II), or a combination of two or more thereof.

35. The process of claim 1 wherein the sorption medium comprises Sb₂O₅, AgO, PtO, CrO₂, PbO, HgO, Cu₂O, MnO, Mn₂O₃, Bi₂O₄, NiO, NiO₂, Cu₂O₃, SnO, SnO₂, WO₂, WO₃, W₂O₅, perfluorinated film, Pt/g-alumina, Fe/g-alumina, Co/g-alumina, Zn/g-alumina, Co/g-alumina, zeolite, or a combination of two or more thereof.

36. The process of claim 1 wherein the sorption medium comprises a metal cyanide oligomer or polymer.

37. The process of claim 36 wherein the metal cyanide oligomer or polymer is represented by the formula [Cu(I)(CN)_x]_n, [Fe(ii)(CN)_y]_{n or[Co(II)(CN)y}]_{n, wherein x is} 3, y is 5 and n is a number that is at least 2.

38. The process of claim 1 wherein the sorption medium comprises silica gel, foamed copdper, sintered stainless steel fiber, alumina, poly(methyl methacrylate), polysulfonate, poly(tetrafluoroethylene), iron, nickel sponge, nylon, polyvinylidene difluoride, polypropylene, polyethylene, polyethylene ethylketone, polyvinyl alcohol, polyvinyl acetate, polyacrylate, polymethylmethacrylate, polystyrene, polyphenylene sulfide, polysulfone, polybutylene, or a combination of two or more thereof.

39. The process of claim 1 wherein the sorption comprises a secondary amine, phenolic phosphate, phosphite, phenolic, bisphenolic, hydroxylamine, olefinic carboxylate, amino carboxylate, tocopherol, di-tertiarybutyl-p-cresol, stannous salt, stannous oxide, sorbate, polysorbate, or a combination of two or more thereof.

40. The process of claim 1 wherein the sorption medium comprises a deposit derived from methane and hydrogen.

41. The process of claim 1 wherein the process is a steam/methane reforming process.

42. The process of claim 1 wherein the process is a Fischer-Tropsch reaction process.

43. The process of claim 1 wherein the process is a hydrogenation process.

44. The process of claim 24 wherein a combustion reaction is conducted in the heat exchange channel.

45. The process of claim 24 wherein a steam/methane reforming process is conducted in the process microchannel, and a combustion reaction is conducted in the heat exchange channel.

46. The process of claim 1 wherein a partial oxidation process is conducted in the process microchannel.

47. The process of claim 1 wherein nitrogen or methane is separated from a mixture of nitrogen and methane in the process microchannel.

48. The process of claim 1 wherein the thermal conductivity of the fin exceeds 100 W/m/K.