SYNTHESIS OF LIQUID FUELS FROM BIOMASS

• US 20100076233A1
• Filed: 08/27/2009
• Published: 03/25/2010
• Est. Priority Date: 08/27/2008
• Status: Active Grant

• Current Assignee: Virent, Inc. (Marathon Petroleum Corporation)
• Original Assignee: Virent, Inc. (Marathon Petroleum Corporation)
• Inventors: Vanstraten, Matthew R., Werner, Michael J., Cortright, Randy D., Blommel, Paul G.
• Granted Patent: US 8,350,108 B2
• Time in Patent Office: Days
• US Class Current: 585/251
• CPC Class Codes: B01J 21/06 Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
• CPC Class Codes: B01J 21/066 Zirconium or hafnium; Oxides or hydroxides thereof
• CPC Class Codes: B01J 2229/20 to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
• CPC Class Codes: B01J 2229/42 Addition of matrix or binder particles
• CPC Class Codes: B01J 23/6567 Rhenium
• CPC Class Codes: B01J 29/46 Iron group metals or copper
• CPC Class Codes: C01B 2203/0233 the reforming step being a steam reforming step
• CPC Class Codes: C01B 2203/062 Hydrocarbon production, e.g. Fischer-Tropsch process
• 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 3/323 Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents
• CPC Class Codes: C07C 27/12 with oxygen
• CPC Class Codes: C10G 2300/1011 Biomass
• CPC Class Codes: C10G 2300/1014 of vegetal origin
• CPC Class Codes: C10G 2300/42 Hydrogen of special source or of special composition
• CPC Class Codes: C10G 2400/02 Gasoline
• CPC Class Codes: C10G 2400/04 Diesel oil
• CPC Class Codes: C10G 2400/08 Jet fuel
• CPC Class Codes: C10G 2400/20 C2-C4 olefins
• CPC Class Codes: C10G 2400/22 Higher olefins
• CPC Class Codes: C10G 29/205 by reaction with hydrocarbons added to the hydrocarbon oil
• CPC Class Codes: C10G 3/45 : containing iron group metals or compounds thereof
• CPC Class Codes: C10G 3/46 : in combination with chromium, molybdenum, tungsten metals or compounds thereof
• CPC Class Codes: C10G 3/47 : containing platinum group metals or compounds thereof
• CPC Class Codes: C10G 3/48 : further characterised by the catalyst support
• CPC Class Codes: C10G 3/49 : containing crystalline aluminosilicates, e.g. molecular sieves
• CPC Class Codes: C10G 3/52 : Hydrogen in a special composition or from a special source
• CPC Class Codes: C10G 45/02 : to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
• CPC Class Codes: C10G 45/06 : containing nickel or cobalt metal, or compounds thereof
• CPC Class Codes: C10G 45/08 : in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
• CPC Class Codes: C10G 45/22 : with hydrogen dissolved or suspended in the oil
• CPC Class Codes: C10G 45/60 : characterised by the catalyst used
• CPC Class Codes: C10G 45/62 : containing platinum group metals or compounds thereof
• CPC Class Codes: C10G 45/64 : containing crystalline alumino-silicates, e.g. molecular sieves
• CPC Class Codes: C10G 69/123 : alkylation
• CPC Class Codes: Y02P 20/50 : Improvements relating to the production of bulk chemicals
• CPC Class Codes: Y02P 20/52 : using catalysts, e.g. selective catalysts

Abstract

Processes and reactor systems are provided for the conversion of oxygenated hydrocarbons to paraffins useful as liquid fuels. The process involves the conversion of water soluble oxygenated hydrocarbons to oxygenates, such as alcohols, furans, ketones, aldehydes, carboxylic acids, diols, triols, and/or other polyols, followed by the subsequent conversion of the oxygenates to paraffins by dehydration and alkylation. The oxygenated hydrocarbons may originate from any source, but are preferably derived from biomass.

Claims

1. A method of making C₆₊ paraffins comprising:

catalytically reacting hydrogen, water and water soluble oxygenated hydrocarbons comprising C₂₊O₁₊ hydrocarbons in the presence of a deoxygenation catalyst at a deoxygenation temperature and deoxygenation pressure to produce an oxygenate comprising C₂₊O_1-3 hydrocarbons;

catalytically reacting the C₂₊O_1-3 hydrocarbons in the presence of a dehydration catalyst at a dehydration temperature and dehydration pressure to produce a reaction stream comprising C₂₊ olefins; and

reacting the C₂₊ olefins with a stream of C₄₊ isoparaffins in the presence of an alkylation catalyst at an alkylation temperature and alkylation pressure to produce a product stream comprising C₆₊ paraffins.

2. The method of claim 1, wherein the C₂₊O₁₊ hydrocarbon comprises a member selected from the group consisting of a sugar alcohol, sugar, monosaccharide, disaccharide, alditol, cellulosic derivative, lignocellulosic derivative, glucose, fructose, sucrose, maltose, lactose, mannose, xylose, arabitol, erythritol, glycerol, isomalt, lactitol, malitol, mannitol, sorbitol, xylitol, and a mixture of any two or more of the foregoing.

3. The method of claim 1, wherein the C₂₊O_1-3 hydrocarbon comprises a member selected from the group consisting of an alcohol, ketone, aldehyde, furan, diol, triol, hydroxy carboxylic acid, carboxylic acid, and a mixture of any two or more of the foregoing.

4. The method of claim 1, wherein the C₆₊ paraffin comprises a member selected from the group consisting of branched C_6-10 alkane, a branched C₆ alkane, a branched C₇ alkane, a branched C₈ alkane, a branched C₉ alkane, a branched C₁₀ alkane, or a mixture of any two or more of the foregoing.

5. The method of claim 1, wherein the deoxygenation catalyst comprises a support and a member selected from the group consisting of Re, Cu, Fe, Ru, Ir, Co, Rh, Pt, Pd, Ni, W, Os, Mo, Ag, Au, an alloy of any two or more of the foregoing, or a combination of any two or more of the foregoing.

6. The method of claim 5, wherein the deoxygenation catalyst further comprises a member selected from the group consisting of Mn, Cr, Mo, W, V, Nb, Ta, Ti, Zr, V, La, Sc, Zn, Cd, Ag, Au, Sn, Ge, P, Al, Ga, In, Tl, and a combination of any two or more of the foregoing.

7. The method of claim 5, wherein the support comprises a member selected from group consisting of a nitride, carbon, silica, alumina, zirconia, titania, vanadia, ceria, boron nitride, heteropolyacid, kieselguhr, hydroxyapatite, zinc oxide, chromia, and mixtures of any two or more of the foregoing.

8. The method of claim 7, wherein the support comprises a member selected from the group consisting of carbon nanotubes, carbon fullerenes, and zeolites.

9. The method of claim 1, wherein the dehydration catalyst comprises a member selected from the group consisting of an acidic alumina, aluminum phosphate, silica-alumina phosphate, amorphous silica-alumina, aluminosilicate, zirconia, sulfated zirconia, tungstated zirconia, tungsten carbide, molybdenum carbide, titania, sulfated carbon, phosphated carbon, phosphated silica, phosphated alumina, acidic resin, heteropolyacid, inorganic acid, and a combination of any two or more of the foregoing.

10. The method of claim 9, wherein the dehydration catalyst further comprises a Modifier selected from the group consisting of Ce, Y, Sc, La, Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, P, B, Bi, and a combination of any two or more of the foregoing.

11. The method of claim 9, wherein the dehydration catalyst further comprises an oxide of an element, the element selected from the group consisting of Ti, Zr, V, Nb, Ta, Mo, Cr, W, Mn, Re, Al, Ga, In, Fe, Co, Ir, Ni, Si, Cu, Zn, Sn, Cd, P, and a combination of any two or more of the foregoing.

12. The method of claim 9, wherein the dehydration catalyst further comprises a metal selected from the group consisting of Cu, Ag, Au, Pt, Ni, Fe, Co, Ru, Zn, Cd, Ga, In, Rh, Pd, Ir, Re, Mn, Cr, Mo, W, Sn, Os, an alloy of any two or more of the foregoing, and a combination of any two or more of the foregoing.

13. The method of claim 9, wherein the dehydration catalyst comprises an aluminosilicate zeolite.

14. The method of claim 13, wherein the dehydration catalyst further comprises a modifier selected from the group consisting of Ga, In, Zn, Fe, Mo, Ag, Au, Ni, P, Sc, Y, Ta, a lanthanide, and a combination of any two or more of the foregoing.

15. The method of claim 13, wherein the dehydration catalyst further comprises a metal selected from the group consisting of Cu, Ag, Au, Pt, Ni, Fe, Co, Ru, Zn, Cd, Ga, In, Rh, Pd, Ir, Re, Mn, Cr, Mo, W, Sn, Os, an alloy of any two or more of the foregoing, and a combination of any two or more of the foregoing.

16. The method of claim 1, wherein the alkylation catalyst comprises a member selected from the group consisting of sulfuric acid, hydrofluoric acid, aluminum chloride, boron trifluoride, solid phosphoric acid, chlorided alumina, acidic alumina, aluminum phosphate, silica-alumina phosphate, amorphous silica-alumina, aluminosilicate, aluminosilicate zeolite, zirconia, sulfated zirconia, tungstated zirconia, tungsten carbide, molybdenum carbide, titania, sulfated carbon, phosphated carbon, phosphated silica, phosphated alumina, acidic resin, heteropolyacid, inorganic acid, a mixture of a mineral acid and a Friedel-Crafts metal halide, and a combination of any two or more of the foregoing.

17. The method of claim 16, wherein the alkylation catalyst further comprises a modifier selected from the group consisting of Ga, In, Zn, Fe, Mo, Ag, Au, Ni, P, Sc, Y, Ta, a lanthanide, and a combination of any two or more of the foregoing.

18. The method of claim 16, wherein the alkylation catalyst further comprises a metal selected from the group consisting of Cu, Ag, Au, Pt, Ni, Fe, Co, Ru, Zn, Cd, Ga, In, Rh, Pd, Ir, Re, Mn, Cr, Mo, W, Sn, Os, an alloy of any two or more of the foregoing, and a combination of any two or more of the foregoing.

19. The method of claim 1, wherein the dehydration catalyst and the alkylation catalyst are atomically identical.

20. The method of claim 1, wherein at least a portion of the hydrogen is an APR hydrogen produced by a method comprising catalytically reacting a first portion of the water and the water soluble oxygenated hydrocarbon in the presence of an APR catalyst at a reforming temperature and a reforming pressure to produce the APR hydrogen.

21. The method of claim 20, wherein the APR catalyst comprises a support and a member selected from the group consisting of Fe, Ru, Os, Ir, Co, Rh, Pt, Pd, Ni, an alloy of any two or more of the foregoing, and a combination of any two or more of the foregoing.

22. The method of claim 21, wherein the APR catalyst further comprises a member selected from the group consisting of Cu, B, Mn, Re, Cr, Mo, Bi, W, V, Nb, Ta, Ti, Zr, V, La, Sc, Zn, Cd, Ag, Au, Sn, Ge, P, Al, Ga, In, Tl, an alloy of any two or more of the foregoing, and a combination of any two or more of the foregoing.

23. The method of claim 21, wherein the support comprises a member selected from group consisting of a nitride, carbon, silica, alumina, zirconia, titania, vanadia, ceria, boron nitride, heteropolyacid, kieselguhr, hydroxyapatite, zinc oxide, chromia, and mixtures of any two or more of the foregoing.

24. The method of claim 21, wherein the support comprises a member selected from the group consisting of carbon nanotubes, carbon fullerenes, and zeolites.

25. The method of claim 20, wherein one or more of the APR catalyst, deoxygenation catalyst, and dehydration catalyst are atomically identical.

26. The method of claim 20, wherein the APR catalyst and deoxygenation catalyst comprise Pt alloyed or admixed with a member selected from the group consisting of Ni, Ru, Cu, Fe, Rh, Re, alloys of any two or more of the foregoing, and a combination of any two or more of the foregoing.

27. The method of claim 20, wherein the APR catalyst and deoxygenation catalyst comprise Ru alloyed or admixed with a member selected from the group consisting of Ge, Bi, B, Ni, Sn, Cu, Fe, Rh, Pt, alloys of any two or more of the foregoing, and a combination of any two or more of the foregoing.

28. The method of claim 20, wherein the APR catalyst comprises Ni alloyed or admixed with a member selected from the group consisting of Sn, Ge, Bi, B, Cu, Re, Ru, Fe, alloys of any two or more of the foregoing, and a combination of any two or more of the foregoing.

29. The method of claim 1 further comprising the step of providing an aqueous solution comprising water and a polysaccharide, disaccharide, monosaccharide, sugar, furfural, carboxylic acid, ketone, furan, or a combination of any two or more of the foregoing, and catalytically reacting the polysaccharide, disaccharide, monosaccharide, sugar, furfural, carboxylic acid, ketone, furan, or combination, with hydrogen in the presence of a hydrogenation catalyst at a hydrogenation temperature and hydrogenation pressure to produce the water soluble oxygenated hydrocarbon.

30. The method of claim 29, wherein the hydrogenation catalyst comprises a support and a member selected from the group consisting of Fe, Ru, Os, Ir, Co, Rh, Pt, Pd, Ni, Re, Cu, alloys of any two or more of the foregoing, and a combination of any two or more of the foregoing.

31. The method of claim 30, wherein the hydrogenation catalyst further comprises a member selected from the group consisting of Ag, Au, Cr, Zn, Mn, Sn, Bi, Mo, W, B, P, alloys of any two or more of the foregoing, and a combination of any two or more of the foregoing.

32. The method of claim 1 further comprising the step of providing an aqueous solution comprising water and a polysaccharide, disaccharide, monosaccharide, polyhydric alcohol, sugar, sugar alcohol, or a combination of any two or more of the foregoing, and catalytically reacting the sugar, sugar alcohol, polysaccharide, disaccharide, monosaccharide, polyhydric alcohol, or combination, with hydrogen in the presence of a hydrogenolysis catalyst at a hydrogenolysis temperature and hydrogenolysis pressure to produce the water soluble oxygenated hydrocarbon.

33. The method of claim 32, wherein the hydrogenolysis catalyst comprises a member selected from the group consisting of phosphate, Cr, Mo, W, Re, Mn, Cu, Cd, Fe, Ru, Os, Ir, Co, Rh, Pt, Pd, Ni, alloys of any two or more of the foregoing, and a combination of any two or more of the foregoing.

34. The method of claim 33, wherein the hydrogenolysis catalyst further comprises a member selected from the group consisting of Au, Ag, Zn, Sn, Bi, B, Cr, Mn, O, alloys of any two or more of the foregoing, and a combination of any two or more of the foregoing.

35. The method of claim 33, wherein the hydrogenolysis catalyst further comprises an alkaline earth metal oxide.

36. The method of claim 1 wherein the step of catalytically reacting hydrogen, water and water soluble oxygenated hydrocarbons in the presence of a deoxygenation catalyst is performed in either a liquid phase, a vapor phase, or a combination of the foregoing.

37. A method of making a C₆₊ paraffins comprising:

catalytically reacting hydrogen, water and water soluble oxygenated hydrocarbons comprising C₂₊O₁₊ hydrocarbons in the presence of a deoxygenation catalyst at a deoxygenation temperature and deoxygenation pressure to produce an oxygenate comprising C₂₊O_1-3 hydrocarbons;

catalytically reacting a portion of the C₂₊O_1-3 hydrocarbons with hydrogen in the presence of a first hydrogenation catalyst at a hydrogenation temperature and hydrogenation pressure to produce a C₂₊ hydroxyl compound;

catalytically reacting a portion of the C₂₊ hydroxyl compound in the presence of a dehydration catalyst at a dehydration temperature and dehydration pressure to produce C₂₊ olefins; and

catalytically reacting the C₂₊ olefins with a stream of C₄₊ isoparaffins in the presence of an alkylation catalyst at an alkylation temperature and alkylation pressure to produce a product stream comprising C₆₊ paraffins.

38. The method of claim 37, wherein at least a portion of the hydrogen is an APR hydrogen produced by a method comprising catalytically reacting a first portion of the water and the water soluble oxygenated hydrocarbon in the presence of an APR catalyst at a reforming temperature and a reforming pressure to produce the APR hydrogen.

39. The method of claim 37 further comprising the step of providing an aqueous solution comprising water and a polysaccharide, disaccharide, monosaccharide, sugar, furfural, carboxylic acid, ketone, furan, or a combination of any two or more of the foregoing, and catalytically reacting the polysaccharide, disaccharide, monosaccharide, sugar, furfural, carboxylic acid, ketone, furan, or combination of any two or more of the foregoing, with hydrogen in the presence of a second hydrogenation catalyst at a hydrogenation temperature and hydrogenation pressure to produce the water soluble oxygenated hydrocarbon.

40. The method of claim 37 further comprising the step of providing an aqueous solution comprising water and a polysaccharide, disaccharide, monosaccharide, polyhydric alcohol, sugar, sugar alcohol, or a combination of any two or more of the foregoing, and catalytically reacting the sugar, sugar alcohol, polysaccharide, disaccharide, monosaccharide, polyhydric alcohol, or combination of any two or more of the foregoing, with hydrogen in the presence of a hydrogenolysis catalyst at a hydrogenolysis temperature and hydrogenolysis pressure to produce the water soluble oxygenated hydrocarbon.

41. A method of making a C₆₊ paraffins comprising:

catalytically reacting hydrogen, water and water soluble oxygenated hydrocarbons comprising C₂₊O₁₊ hydrocarbons in the presence of a deoxygenation catalyst at a deoxygenation temperature and deoxygenation pressure to produce an oxygenate comprising C₂₊O_1-3 hydrocarbons and one or more C₄₊ normal paraffins, aromatics and/or naphthenes;

collecting a portion of the C₄₊ normal paraffins, aromatics and/or naphthenes and catalytically reacting the C₄₊ normal paraffins, aromatics and/or naphthenes in the presence of an isomerization catalyst to produce a stream of C₄₊ isoparaffins;

catalytically reacting the C₂₊O_1-3 hydrocarbons in the presence of a dehydration catalyst at a dehydration temperature and dehydration pressure to produce a reaction stream comprising C₂₊ olefins; and

catalytically reacting the C₂₊ olefins with the C₄₊ isoparaffins in the presence of an alkylation catalyst at an alkylation temperature and alkylation pressure to produce a product stream comprising C₆₊ paraffins.

42. The method of claim 41, wherein at least a portion of the hydrogen is an APR hydrogen produced by a method comprising catalytically reacting a first portion of the water and the water soluble oxygenated hydrocarbon in the presence of an APR catalyst at a reforming temperature and a reforming pressure to produce the APR hydrogen.

43. The method of claim 41 further comprising the step of providing an aqueous solution comprising water and a polysaccharide, disaccharide, monosaccharide, sugar, furfural, carboxylic acid, ketone, furan, or a combination of any two or more of the foregoing, and catalytically reacting the polysaccharide, disaccharide, monosaccharide, sugar, furfural, carboxylic acid, ketone, furan, or combination of any two or more of the foregoing, with hydrogen in the presence of a second hydrogenation catalyst at a hydrogenation temperature and hydrogenation pressure to produce the water soluble oxygenated hydrocarbon.

44. The method of claim 41 further comprising the step of providing an aqueous solution comprising water and a polysaccharide, disaccharide, monosaccharide, polyhydric alcohol, sugar, sugar alcohol, or a combination of any two or more of the foregoing, and catalytically reacting the sugar, sugar alcohol, polysaccharide, disaccharide, monosaccharide, polyhydric alcohol, or combination of any two or more of the foregoing, with hydrogen in the presence of a hydrogenolysis catalyst at a hydrogenolysis temperature and hydrogenolysis pressure to produce the water soluble oxygenated hydrocarbon.

45. The method of claim 41, wherein the isomerization catalyst comprises a member selected from the group consisting of a zeolite, zirconia, sulfated zirconia, tungstated zirconia, alumina, silica-alumina, zinc aluminate, chlorided alumina, phosphoric acid, and combinations of any two or more of the foregoing.

46. The method of claim 45, wherein the isomerization catalyst is an acidic beta, mordenite, or a ZSM-5 zeolite.

47. The method of claim 45, wherein the isomerization catalyst further comprises a metal selected from the group consisting of Y, Pt, Ru, Pd, Ni, Rh, Ir, Fe, Co, Os, Zn, a lanthanide, or an alloy or combination of any two or more of the foregoing.

48. The method of claim 45, wherein the isomerization catalyst comprises a support, the support comprising alumina, sulfated oxide, clay, silica gel, aluminum phosphate, bentonite, kaolin, magnesium silicate, magnesium carbonate, magnesium oxide, aluminum oxide, activated alumina, bauxite, silica, silica-alumina, activated carbon, pumice, zirconia, titania, zirconium, titanium, kieselguhr, or zeolites.

49. The method of claim 48, wherein the isomerization catalyst comprises a support of a sulfated oxide or hydroxide of a Group IVB metal, at least one Group IIIA compound, and a Group VIII metal.

50. The method of claim 49, wherein the Group IVB metal comprises, zirconium, titanium, alloys of the foregoing, or mixtures of the foregoing, and the Group IIIA compound comprises gallium, indium, or mixtures of the foregoing.

51. The method of claim 49, wherein the Group VIII metal comprises Pd, Pt, Ru, Rh, Ir, Os, allows of any two or more of the foregoing, or mixtures of any two or more of the foregoing.

52. The method of claim 45, wherein the isomerization catalyst further includes Fe, Co, Ni, Re, Y, Eu, Tm, Ho, Er, Yb, Tb, or mixtures of any two or more of the foregoing.

53. A method of making a C₆₊ paraffins comprising:

catalytically reacting hydrogen, water and water soluble oxygenated hydrocarbons comprising C₂₊O₁₊ hydrocarbons in the presence of a deoxygenation catalyst at a deoxygenation temperature and deoxygenation pressure to produce an oxygenate comprising C₂₊O_1-3 hydrocarbons;

catalytically reacting the C₂₊O_1-3 hydrocarbons in the presence of a dehydration catalyst at a dehydration temperature and dehydration pressure to produce a reaction stream comprising C₂₊ olefins and one or more C₄₊ normal paraffins, aromatics and/or naphthenes;

collecting a portion of the C₄₊ normal paraffins, aromatics and/or naphthenes and catalytically reacting the C₄₊ normal paraffins, aromatics and/or naphthenes in the presence of an isomerization catalyst to produce a stream of C₄₊ isoparaffins; and

catalytically reacting the C₂₊ olefins with the C₄₊ isoparaffins in the presence of an alkylation catalyst at an alkylation temperature and alkylation pressure to produce a product stream comprising C₆₊ paraffins.

54. The method of claim 53, wherein at least a portion of the hydrogen is an APR hydrogen produced by a method comprising catalytically reacting a first portion of the water and the water soluble oxygenated hydrocarbon in the presence of an APR catalyst at a reforming temperature and a reforming pressure to produce the APR hydrogen.

55. The method of claim 53 further comprising the step of providing an aqueous solution comprising water and a polysaccharide, disaccharide, monosaccharide, sugar, furfural, carboxylic acid, ketone, furan, or a combination of any two or more of the foregoing, and catalytically reacting the polysaccharide, disaccharide, monosaccharide, sugar, furfural, carboxylic acid, ketone, furan, or combination, with hydrogen in the presence of a second hydrogenation catalyst at a hydrogenation temperature and hydrogenation pressure to produce the water soluble oxygenated hydrocarbon.

56. The method of claim 53 further comprising the step of providing an aqueous solution comprising water and a polysaccharide, disaccharide, monosaccharide, polyhydric alcohol, sugar, sugar alcohol, or a combination of any two or more of the foregoing, and catalytically reacting the sugar, sugar alcohol, polysaccharide, disaccharide, monosaccharide, polyhydric alcohol, or combination, with hydrogen in the presence of a hydrogenolysis catalyst at a hydrogenolysis temperature and hydrogenolysis pressure to produce the water soluble oxygenated hydrocarbon.