Process for producing renewable products

Patent metadata

Field	Value
Publication number	US-11279665-B2
Application number	US-201917419885-A
Country	US
Kind code	B2
Filing date	Dec 17, 2019
Priority date	Dec 31, 2018
Publication date	Mar 22, 2022
Grant date	Mar 22, 2022

Abstract

The present disclosure relates to a method for producing renewable ketones, paraffin waxes, base oil components and alkenes from a feedstock of biological origin, wherein the method includes ketonisation of esters of fatty acids and monohydric alcohols wherein the alcohols have carbon chain length of two or more.

First claim

The invention claimed is:

1. A method for producing simultaneously renewable ketones and renewable alkenes from a feedstock of biological origin, the method comprising steps of:
a) providing a feedstock of biological origin containing fatty acids and/or fatty acid esters;
b) subjecting the feedstock to esterification reaction in a presence of a monohydric alcohol, wherein the monohydric alcohol has a carbon chain length of two or more, yielding esters of the fatty acids and the monohydric alcohol, in proviso that when the feedstock includes esters of fatty acids and a monohydric alcohol, wherein the monohydric alcohol has a carbon chain length of two or more, step b) is optional;
c) subjecting the esters of the fatty acid and the monohydric alcohol to ketonisation reaction in a presence of a metal oxide ketonisation catalyst, yielding an intermediate product stream containing ketones, alkenes and carbon dioxide; and
d) separating the alkenes from the intermediate product stream yielding an alkene depleted intermediate product stream and the separated alkenes.

2. The method according to claim 1 , comprising:
subjecting the feedstock to prehydrogenation reaction in a presence of hydrogenation catalyst prior to step b).

3. The method according to claim 1 , comprising:
purifying the feedstock prior to step b).

4. The method according to claim 1 , comprising,
purifying the ester of fatty acid and the monohydric alcohol prior to step c).

5. The method according to claim 1 , comprising:
subjecting the ester of fatty acid and the monohydric alcohol to prehydrogenation reaction in a presence of hydrogenation catalyst prior to step c).

6. The method according to claim 1 , wherein the ketonisation catalyst comprises:
TiO 2 as active catalyst material.

7. The method according to claim 1 , comprising:
performing the ketonisation reaction of step c) at least partially in liquid phase.

8. The method according to claim 1 , wherein the ketonisation reaction of step c) is at a temperature in a range from 100 to 500° C., and at a pressure in a range from atmospheric pressure to 10 MPa, in a presence of a ketonisation catalyst.

9. The method according to claim 1 , wherein the ketonisation reaction of step c) is performed in a presence of a CO 2 flow of 0.5-1.0 kg CO 2 /kg ester feed.

10. The method according to claim 1 , wherein step c) comprises:
adding a monohydric alcohol having a carbon chain length of two or more to the ketonisation reaction.

11. The method according to claim 1 , comprising:
separating the carbon dioxide from the intermediate product stream.

12. A method for producing renewable wax, the method comprising:
producing an alkene depleted intermediate product stream according to claim 1 ; and
subjecting the alkene depleted intermediate product stream to hydrodeoxygenation reaction to yield renewable wax.

13. A method for producing renewable base oil fulfilling API Group Ill base oil specifications having ≥90 wt % saturated hydrocarbons, ≤0.03 wt-% sulfur and a viscosity index of ≥120, the method comprising:
producing an alkene depleted intermediate product stream according to claim 1 ; and
subjecting the alkene depleted intermediate product stream to both hydrodeoxygenation reaction and to hydroisomerisation reaction, simultaneously or in sequence, to yield a deoxygenated and isomerized product stream containing renewable base oil components.

14. The method according to claim 12 , wherein the hydrodeoxygenation reaction is performed at a temperature in a range from 100 to 500° C.; a pressure in a range from atmospheric pressure to 20 MPa; a WHSV in a range from 0.5 to 3 h- -1 , and a H 2 flow of 350-900 nl H 2 /l feed, in a presence of a hydrodeoxygenation catalyst.

15. The method according to claim 13 , wherein subjecting to hydrodeoxygenation and to hydroisomerisation is made in sequence, and wherein the method comprises:
separating liquids from gases between hydrodeoxygenation and hydroisomerisation.

16. The method according to claim 13 , wherein the hydroisomerisation reaction is performed at a temperature in range from 200 to 450° C.; a pressure in a range from 1 to 15 MPa; a WHSV in a range from 0.5-3 h -1 , and a H 2 flow of 100-800 nl H 2 /l feed, in a presence of a hydroisomerisation catalyst comprising a Group VIII metal and a molecular sieve, optionally on an alumina and/or silica support.

17. The method according to claim 13 , wherein the method comprises:
distilling the deoxygenated and isomerized product stream comprising the renewable base oil to obtain distilled renewable base oil and one or more of liquified petroleum gas, naphtha and diesel/jet fuel.

18. The method according to claim 1 , wherein the monohydric alcohol has a carbon chain length from 2 to 20.

19. The method according to claim 1 , wherein the monohydric alcohol.

20. The method according to claim 8 , wherein the ketonisation reaction of step c) is at a temperature in a range from 300 to 400° C., and at a pressure in a range from atmospheric pressure from 0.5 to 3 MPa, in a presence of a ketonisation catalyst.

21. The method according to claim 12 , wherein the hydrodeoxygenation reaction is performed at a temperature in the range from 250 to 400° C.; a pressure in a range from atmospheric pressure from 0.2 to 8 MPa; a WHSV in a range from 0.5 to 3 h -1 , and a H 2 flow of 350-900 nl H 2 /l feed, in a presence of a hydrodeoxygenation catalyst.

22. The method according to claim 13 , wherein the hydroisomerisation reaction is performed at a temperature in a range from 250 to 400° C.; a pressure in a range from 1 to 6 MPa; a WHSV in a range from 0.5-3 h -1 , and a H 2 flow of 100-800 nl H 2 /l feed, in a presence of a hydroisomerisation catalyst comprising a Group VIII metal and a molecular sieve, optionally on an alumina and/or silica support.

23. The method according to claim 1 , wherein the monohydric alcohol has a carbon chain length from 2 to 10.

24. The method according to claim 1 , wherein the monohydric alcohol is renewable ethanol.

25. The method according to claim 13 , wherein the hydrodeoxygenation reaction is performed at a temperature in a range from 100 to 500° C.; a pressure in a range from atmospheric pressure to 20 MPa; a WHSV in a range from 0.5 to 3 h -1 , and a H2 flow of 350-900 nl H 2 /l feed, in a presence of a hydrodeoxygenation catalyst.

26. The method according to claim 25 , wherein subjecting to hydrodeoxygenation and to hydroisomerisation is made in sequence, and wherein the method comprises:
separating liquids from gases between hydrodeoxygenation and hydroisomerisation.

27. The method according to claim 26 , wherein the hydroisomerisation reaction is performed at a temperature in range from 200 to 450° C.; a pressure in a range from 1 to 15 MPa a WHSV in a range from 0.5-3 h -1 , and a H 2 flow of 100-800 nl H 2 /l feed, in a presence of a hydroisomerisation catalyst containing a Group VIII metal and a molecular sieve, optionally on an alumina and/or silica support.

Assignees

• Neste Oyj

Inventors

• Myllyoja Jukka
• Silvonen Petro

Classifications

• Y02P30/20

  using bio-feedstock · CPC title

• C10G2400/20

  C2-C4 olefins · CPC title

• C10G2300/1018

  of animal origin · CPC title

• C10G2300/1014

  of vegetal origin · CPC title

• Y02P20/52

  using catalysts, e.g. selective catalysts · CPC title