Method for catalytic conversion of ketoacids and hydrotreatment to hydrocarbons

Patent metadata

Field	Value
Publication number	US-10040747-B2
Application number	US-201615010853-A
Country	US
Kind code	B2
Filing date	Jan 29, 2016
Priority date	Jan 30, 2015
Publication date	Aug 7, 2018
Grant date	Aug 7, 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 feedstock comprising at least one ketoacid, water and a base. The feedstock is then subjected to base catalysed condensation reactions.

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 feedstock having at least one ketoacid, water and a base; and subjecting the feedstock to one or more base catalysed condensation reaction(s) to obtain a reaction product,
wherein the base catalysed condensation reaction(s) is/are conducted at a temperature of at least 65° C.,
wherein the base catalysed condensation reaction(s) is/are C-C coupling reaction(s),
wherein a total content of dimerization, trimerization, tetramerization, pentamerization, and hexamerization products of ketoacid present in the reaction product of the one or more base catalysed condensation reaction(s), is more than 40 wt %, based on the reaction product.

2. The method according to claim 1 , wherein the at least one ketoacid is a γ-ketoacid.

3. The method according to claim 1 , wherein the base is a hydroxide, carbonate, or phosphate of an alkaline metal or alkaline earth metal, or a combination of these.

4. The method according to claim 1 , wherein the content of the base in the feedstock is adjusted such that the pH of the feedstock is at least 8.0.

5. The method according to claim 1 , wherein the content of the base in the feedstock is adjusted such that a ratio of the number of proton accepting groups provided by the base to the number of carboxylic acid groups provided by the at least one ketoacid is in the range of 1.00:1.00 to 5.00:1.00.

6. The method according to claim 1 , wherein a molar ratio of the content of the base in the feedstock to the content of the at least one ketoacid in the feedstock is in the range of 1.00:1.00 to 5.00:1.00.

7. The method according to claim 1 , wherein the content of the base in the feedstock is adjusted such that more than 90% (by mole) of the acid groups of the at least one ketoacid in the feedstock are deprotonated.

8. The method according to claim 7 , wherein the acid groups of the at least one ketoacid in the feedstock are converted into carboxylic acid metal salt groups.

9. The method according to claim 1 , wherein the content of the at least one ketoacid in the feedstock is at least 5.0 mol-%; and/or
wherein the content of water in the feedstock is at least 1.0 mol-%.

10. The method according to claim 1 , wherein a mixture of at least two basic compounds is used as the base.

11. The method according to claim 1 , wherein the method further comprises:
preparing the feedstock by mixing the at least one ketoacid, the base and optionally the water prior to subjecting the feedstock to the one or more base catalysed condensation reaction(s) and
wherein the preparing the feedstock is conducted at a temperature in the range of 10° C. to 55° C.

12. The method according to claim 1 , further comprising:
acidifying the reaction product of the condensation reaction(s) by adding an inorganic acid or an organic acid.

13. The method according to claim 12 , further comprising:
purifying the acidified reaction product by extraction, precipitation, crystallization, or liquid-liquid extraction using a solvent.

14. A method of producing hydrocarbons, comprising:
increasing the molecular weight of a ketoacid using the method according to claim 12 to obtain a reaction product, and subjecting the reaction product to a hydrodeoxygenation step and optionally to an isomerization step.

15. The method according to claim 1 , wherein the at least one ketoacid is levulinic acid; and/or
wherein the base catalysed condensation reaction(s) is/are conducted at a temperature in the range of 100 to 120° C.

16. The method according to claim 1 , wherein the base is a hydroxide, carbonate, or phosphate of one of Na, Li, Be, Mg, K, Ca, Sr or Ba, or a combination of these, with the hydroxide being sodium hydroxide, potassium hydroxide or lithium hydroxide or a combination of these.

17. The method according to claim 15 , wherein the content of the base in the feedstock is adjusted such that the pH of the feedstock is at least 12.0.

18. The method according to claim 16 , wherein the content of the base in the feedstock is adjusted such that the ratio of the number of proton accepting groups provided by the base to the number of carboxylic acid groups provided by the at least one ketoacid is in the range of 1.05:1.00 to 2.00:1.00.

19. The method according to claim 17 , wherein the molar ratio of the content of the base the feedstock to the content of the at least one ketoacid in the feedstock is in the range of 1.10:1.00 to 2.00:1.00.

20. The method according to claim 1 , wherein the content of the base in the feedstock is adjusted such that more than 99% (by mole), of the acid groups of the at least one ketoacid in the feedstock are deprotonated.

21. The method according to claim 1 , wherein the content of the at least one ketoacid in the feedstock is at least 20.0 mol-%; and/or
wherein the content of water in the feedstock is at least 30.0 mol-%.

22. The method according to claim 1 , wherein the method further comprises:
preparing the feedstock by mixing the at least one ketoacid, the base and optionally the water prior to subjecting the feedstock to the one or more base catalysed condensation reaction(s) and
wherein the preparing the feedstock is conducted at a temperature in the range of 15° C. to 45° C.

23. The method according to claim 1 , further comprising:
acidifying the reaction product of the condensation reaction(s) by adding a formic acid or acetic acid.

24. The method according to claim 12 , comprising:
purifying the acidified reaction product by liquid-liquid extraction using a solvent.

25. The method according to claim 1 , wherein the base catalysed condensation reaction(s) is/are conducted at a temperature in the range of 100 to 120° C.

26. The method according to claim 1 , wherein the reaction product comprises at least one levulinic acid trimer.

Assignees

• Neste Oyj

Inventors

• Myllyoja Jukka
• Piilola Rami
• Seläntaus Maaria
• Karvinen Esko

Classifications

• C10L1/08

  for compression ignition · CPC title

• C10G3/50

  in the presence of hydrogen, hydrogen donors or hydrogen generating compounds · CPC title

• C07C51/353 Primary

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

• B01J23/26

  Chromium · CPC title

• B01J23/6527

  Tungsten · CPC title