Method for catalytic conversion of ketoacids via ketoacid dimer intermediate and hydrotreatment to hydrocarbons

Patent metadata

Field	Value
Publication number	US-9914690-B2
Application number	US-201615010972-A
Country	US
Kind code	B2
Filing date	Jan 29, 2016
Priority date	Jan 30, 2015
Publication date	Mar 13, 2018
Grant date	Mar 13, 2018

Abstract

The present invention relates to catalytic conversion of ketoacids, including methods for increasing the molecular weight of ketoacids. The method can include providing in a reactor a raw material having at least one ketoacid. The raw material is then subjected to one or more C—C-coupling reaction(s) in the presence of an ion exchange resin catalyst to produce at least one ketocid dimer. The method can include providing in a reactor a feedstock having the at least one ketoacid dimer and subjecting the feedstock to one or more C—C-coupling reaction(s) at a temperature of at least 200° C.

First claim

The invention claimed is:

1. A method for increasing the molecular weight of a ketoacid, the method comprising:
providing in a reactor a raw material having at least one ketoacid, wherein the ketoacid is an organic molecule that has a keto or aldehyde function and a carboxylic acid or carboxylate function;
subjecting the raw material to first C—C-coupling reaction(s) in a presence of an ion exchange resin catalyst so as to produce at least one ketoacid dimer;
providing in a reactor a feedstock having the at least one ketoacid dimer; and
subjecting the feedstock to second C—C-coupling reaction(s) at a temperature of at least 200° C.

2. The method according to claim 1 , wherein the at least one ketoacid dimer is a dimer of a γ-ketoacid; and/or
wherein the content of the at least one ketoacid dimer in the feedstock is at least 30 wt-%.

3. The method according to claim 1 , wherein the first and second C—C-coupling reaction(s) are conducted in first and second reactors, respectively.

4. The method according to claim 1 , wherein the content of water in the feedstock is less than 15.0 wt-%.

5. The method according to claim 1 , wherein the at least one ketoacid in the raw material is γ-ketoacid; and/or
wherein an average pore diameter of the ion exchange resin catalyst is in the range of 150-300 Å; and/or
wherein the first C—C-coupling reaction(s) are conducted at a temperature in the range of 100-190° C.

6. The method according to claim 1 , wherein the raw material is subjected to the first C—C-coupling reaction(s) in the presence of hydrogen, wherein the ion exchange resin catalyst includes at least one hydrogenating metal selected from Group VIII of the Periodic Table of Elements.

7. The method according to claim 1 , wherein the feedstock is subjected to the second C—C-coupling reactions in the absence of a catalyst.

8. The method according to claim 1 , wherein the feedstock is subjected to the second C—C-coupling reaction(s) in the presence of a solid metal oxide catalyst system having a first metal oxide and a second metal oxide.

9. The method according to claim 8 , wherein the catalyst system has a specific surface area of from 10 to 500 m 2 /g; and/or
wherein the solid catalyst system includes a mixture in which the first metal oxide is supported on the second metal oxide; and/or
wherein the surface density of metal atoms of the first metal oxide supported on the second metal oxide is from 0.5 to 20 metal atoms/nm 2 ; and/or
wherein the first metal oxide includes an oxide of one of K, Li, Be, B, Na, Mg, Al, Si, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Br, Sr, Y, Zr, Nb, Mo, Ba, W, Pb, Bi, La, Ce, Th and the second metal oxide includes one of K, Li, Be B, Na, Mg, Al, Si, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Br, Sr, Y, Zr, Nb, Mo, Ba, W, Pb, Bi, La, Ce, Th, or a combination of these, the first metal oxide not being same as second metal oxide; and/or
wherein the first metal oxide includes an oxide of potassium and the second metal oxide includes an oxide of titanium, or the first metal oxide includes an oxide of tungsten or cerium and the second metal oxide includes an oxide of zirconium, titanium, silicon, vanadium, or chromium, or includes an oxide of zirconium or titanium; and/or
wherein the content of the first metal oxide in the catalyst system is 1.0 to 40.0 wt %, calculated by weight of metal oxide relative to the total mass of the catalyst.

10. The method according to claim 1 , wherein the feedstock comprises:
at least one ketoacid.

11. The method according to claim 10 , wherein the content of the at least one ketoacid in the feedstock is at least 1.0 wt-%; and/or
wherein the weight ratio of the at least one ketoacid content to the at least one ketoacid dimer content in the feedstock [ketoacid:ketoacid dimer] is in the range of 1:5 to 10:1.

12. The method according to claim 1 , wherein the feedstock is introduced into the reactor in liquid phase; and/or
wherein the second C—C-coupling reaction(s) are conducted at a temperature in the range of 200-400° C.; and/or
wherein the second C—C-coupling reaction(s) are conducted at a pressure in the range of 0.5-150 bar; and/or
wherein the second C—C-coupling reaction(s) are conducted at a weight hourly space velocity (kg feedstock/kg catalyst*h) in the range of 0.05 h −1 to 2.0 h −1 ; and/or
wherein the feedstock includes at least one of 4-hydroxy-4-methyl-6-oxononanedioic acid, 3-acetyl-4-hydroxy-4-methylheptanedioic acid, 5-(2-methyl-5-oxotetrahydrofuran-2-yl)-4-oxopentanoic acid, (E)-4-methyl-6-oxonon-4-enedioic acid, 4-hydroxy-6-methylnonanedioic acid, (E)-6-hydroxy-4-methylnon-4-enedioic acid, (Z)-3-acetyl-4-methylhept-3-enedioic acid, 3-(3-acetyl-2-methyl-5-oxotetrahydrofuran-2-yl)propanoic acid, (Z)-3-1(1-hydroxyethyl)-4-methylhept-3-enedioic acid, and 3-(1-hydroxyethyl)-4-methylheptanedioic acid.

13. A reaction product of the second C—C-coupling reaction(s) obtained by the method according to claim 1 .

14. A method for producing hydrocarbons, the method comprising:
increasing the molecular weight of a ketoacid using the method according to claim 1 to obtain a reaction product, and subjecting the reaction product to a hydrodeoxygenation step and optionally to an isomerization step.

15. A hydrocarbon composition obtained by the method according to claim 14 , wherein the reaction product comprises a compound selected from the group consisting of a trimer of the ketoacid, a tetramer of the ketoacid, a pentamer of the ketoacid, a hexamer of the ketoacid, and a heptamer of the ketoacid.

16. The method according to claim 1 , wherein the at least one ketoacid dimer is a dimer of levulinic acid; and/or
wherein the content of the at least one ketoacid dimer in the feedstock is at least 60 wt-%.

17. The method according to claim 2 , wherein the first and second C—C-coupling reaction(s) are conducted in first and second reactors, respectively.

18. The method according to claim 1 , wherein the content of water in the feedstock is less than 5.0 wt-%.

19. The method according to claim 17 , wherein the at least one ketoacid in the raw material is levulinic acid; and/or
wherein the average pore diameter of the ion exchange resin catalyst in the range of 200-250 Å; and/or
wherein the first C—C-coupling reaction(s) are conducted at a temperature in the range of 120-140° C.

20. The method according to claim 18 , wherein the raw material is subjected to the first C—C-coupling reaction(s) in the presence of hydrogen, wherein the ion exchange resin catalyst includes at least one hydrogenating metal selected from Group VIII of the Periodic Table of Elements:
Co, Ni, Ru, Rh, Pd, and Pt.

21. The method according to claim 8 , wherein the catalyst system has a specific surface area of from 10 to 500 m 2 /g; and/or
wherein the solid catalyst system includes a mixture in which the first metal oxide is supported on the second metal oxide; and/or
wherein the surface density of metal atoms of the first metal oxide supported on the second metal oxide is from 0.5 to 20 metal atoms/nm 2 ; and/or
wherein the first metal oxide includes an oxide of one of K, Li, Be, B, Na, Mg, Al, Si, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Br, Sr, Y, Zr, Nb, Mo, Ba, W, Pb, Bi, La, Ce, Th and the second metal oxide includes one of K, Li, Be B, Na, Mg, Al, Si, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Br, Sr, Y, Zr, Nb, Mo, Ba, W, Pb, Bi, La, Ce, Th, or a combination of these, the first metal oxide not being same as the second metal oxide; and/or
wh

Assignees

• Neste Oyj

Inventors

• Myllyoja Jukka
• Piilola Rami
• Seläntaus Maaria
• Käldström Mats
• Lindblad Marina
• Ikonen Elias

Classifications

• C07C51/373

  by introduction of functional groups containing oxygen only in doubly bound form · CPC title

• C07C51/353 Primary

  by isomerisation; by change of size of the carbon skeleton · CPC title

• C07D307/33

  in position 2, the oxygen atom being in its keto or unsubstituted enol form · CPC title

• C07C51/367

  by introduction of functional groups containing oxygen only in singly bound form · CPC title

• C07C59/76

  containing keto groups · CPC title