Method and systems for making distillate fuels from biomass

Patent metadata

Field	Value
Publication number	US-10619106-B2
Application number	US-201213368023-A
Country	US
Kind code	B2
Filing date	Feb 7, 2012
Priority date	Feb 7, 2011
Publication date	Apr 14, 2020
Grant date	Apr 14, 2020

Abstract

The present invention provides methods, reactor systems and catalysts for converting biomass and biomass-derived feedstocks to C8+ hydrocarbons using heterogenous catalysts. The product stream may be separated and further processed for use in chemical applications, or as a neat fuel or a blending component in jet fuel and diesel fuel, or as heavy oils for lubricant and/or fuel oil applications.

First claim

We claim:

1. A method of making C 8+ compounds comprising:
(i) providing a first reactant stream comprising molecules having a general formula C x H y O z and a first reactant stream average oxygen to carbon ratio of between 0.2 and 1.0 and wherein x=2-12 carbon atoms and z=1-12 oxygen atoms;
(ii) adding to the first reactant stream a distinct second reactant stream to create a combined reactant stream that comprises carbon atoms from the first and second reactant streams, the second reactant stream comprising molecules having a general formula C p H r O s and a second reactant stream average oxygen to carbon ratio of 0.2 or less, and wherein p=2-7 carbon atoms and s=0-1 oxygen atoms and the second reactant stream comprises a plurality of C 7− compounds selected from the group consisting of alkanes, alkenes, cycloalkanes, cycloalkenes, and aryls,
wherein, of the total number of carbon atoms in the combined reactant stream, greater than 10% are from the first reactant stream, and greater than 10% are from the second reactant stream,
wherein the average oxygen to carbon ratio of the first reactant stream is higher than the average oxygen to carbon ratio of the second reactant stream; and
(iii) catalytically reacting the combined reactant stream with hydrogen in the presence of an acid condensation catalyst to produce a product stream comprising water and a plurality of C 8+ compounds selected from the group consisting of C 8+ alkanes, C 8+ alkenes, C 8+ cycloalkanes, C 8+ cycloalkenes, C 8+ alcohols, C 8+ ketones, an aryl, a fused aryl, an oxygenated aryl, an oxygenated fused aryl, and a mixture thereof, wherein the acid condensation catalyst comprises an acidic support or a heterogeneous acid catalyst comprising a metal selected from the group consisting of Pd, Pt, Cu, Co, Ru, Cr, Ni, Ag, an alloy thereof, and a combination thereof,
wherein, after the catalytic reaction of step (iii), percent yield of the C 8+ compounds in the product stream is greater than percent yield of C 8+ compounds in a product stream produced when either the first or the second reactant stream alone is catalytically reacted with hydrogen in the presence of the acid condensation catalyst.

2. The method of claim 1 , wherein the acidic support is selected from the group consisting of an aluminosilicate, a tungstated aluminosilicate, a silica-alumina phosphate, an aluminum phosphate, an amorphous silica alumina, an acidic alumina, a phosphate alumina, a tungstated alumina, a zirconia, a tungstated zirconia, a tungstated silica, a tungstated titania, a tungstated phosphate, niobia, an acid modified resin, a zeolite, a heteropolyacid, a tungstated heteropolyacid, and combinations thereof.

3. The method of claim 1 , wherein the heterogeneous acidic catalyst further comprises a support selected from the group consisting of carbon, silica, alumina, zirconia, titania, vanadia, kieselguhr, hydroxyapatite, chromia, niobia, mixtures thereof, and combinations thereof.

4. The method of claim 1 , wherein the acid condensation catalyst further comprises a modifier selected from the group consisting of Cu, Ag, Au, Ru, Pd, Ni, Co, Ga, In, Cr, Mo, W, Sn, Nb, Ti, Zr, Ge, P, Al, alloys thereof, and combinations thereof.

5. The method of claim 1 , wherein the acid condensation catalyst comprises ZSM-5 or tungstated zirconia.

6. The method of claim 5 , wherein the acid condensation catalyst further comprises Pd or Cu.

7. The method of claim 1 , wherein the second reactant stream has an average oxygen to molecule ratio of 1 to 4 and the first reactant stream has an average oxygen to molecule ratio of 1.5 or less.

8. The method of claim 1 , wherein the second reactant stream has a boiling point of less than 210° C.

9. The method of claim 1 , wherein the product stream further comprises one or more C 7− compounds having 2 to 7 carbon atoms and 0 to 1 oxygen atoms, and wherein a portion of the product stream is recycled to form at least in part the second reactant stream.

10. The method of claim 9 , further comprising the step of removing water from the product stream prior to recycling a portion of the product stream to form in part the second reactant stream.

11. The method of claim 1 further comprising the step of catalytically reacting at least a portion of the product stream in the presence of a finishing catalyst.

12. The method of claim 1 further comprising:
providing hydrogen, water and a water soluble oxygenated hydrocarbon comprising a C 2+ O 1+ hydrocarbon, and
catalytically reacting the oxygenated hydrocarbon with the hydrogen in the presence of a deoxygenation catalyst to produce the first reactant stream.

13. The method of claim 12 , 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 thereof, and a combination thereof.

14. The method of claim 13 , wherein the support comprises a member selected from group consisting of a carbon, silica, alumina, zirconia, titania, vanadia, heteropolyacid, kieselguhr, hydroxyapatite, chromia, zeolite, and mixtures thereof.

15. The method of claim 14 , wherein the support is selected from the group consisting of tungstated zirconia, tungsten modified zirconia, tungsten modified alpha-alumina, or tungsten modified theta alumina.

16. The method of claim 12 , wherein the water soluble oxygenated hydrocarbon is selected from the group consisting of a starch, a carbohydrate, a polysaccharide, a disaccharide, a monosaccharide, a sugar, a sugar alcohol, an aldopentose, an aldohexose, a ketotetrose, a ketopentose, a ketohexose, a hemicellulose, a cellulosic derivative, a lignocellulosic derivative, and a polyol.

17. The method of claim 1 , wherein the combined reactant stream further comprises water.

18. The method of claim 1 , wherein the hydrogen comprises at least one of an in situ-generated H 2 , external H 2 , or recycled H 2 .

19. The method of claim 18 , wherein the hydrogen comprises hydrogen generated in situ by catalytically reacting in a liquid phase or vapor phase an aqueous feedstock solution comprising water and an oxygenated hydrocarbon in the presence of an aqueous phase reforming catalyst at a reforming temperature and reforming pressure.

20. A method of making C 8+ compounds comprising:
(i) providing a first reactant stream comprising water and molecules having a general formula C x H y O z and a first reactant stream average oxygen to carbon ratio of between 0.2 and 1.0 and wherein x=2-12 carbon atoms and z=1-12 oxygen atoms,
(ii) adding to the first reactant stream a distinct second reactant stream to create a combined reactant stream that comprises carbon atoms from the first and second reactant streams, the second reactant stream comprising molecules having a general formula C p H r O s , and a second reactant stream average oxygen to carbon ratio of 0.2 or less, and wherein p=2-7 carbon atoms and s=0-1 oxygen atoms and the second reactant stream comprises a plurality of C 7− compounds selected from the group consisting of alkanes, alkenes, cycloalkanes, cycloalkenes, and aryls; and
wherein, of the total number of carbon atoms in the combined reactant stream, greater than 10% are from the first reactant stream, and greater than 10% are from the second reactant stream; and
wherein the average oxygen to carbon ratio of the first reactant stream is higher than the average oxygen to carbon ratio of the second reactant stream; and
wherein the water concentration of the combined

Assignees

• Dally Brice
• Lyman Warren
• Cortright Randy
• Blommel Paul
• Virent Inc

Inventors

• Dally Brice
• Lyman Warren
• Cortright Randy
• Blommel Paul

Classifications

• C10G3/45

  containing iron group metals or compounds thereof · CPC title

• C10G2300/805

  Water · CPC title

• Y02P30/20

  using bio-feedstock · CPC title

• C10G3/47

  containing platinum group metals or compounds thereof · CPC title

• C10G2300/301

  Boiling range · CPC title