Renewable alkene production engaging metathesis

Patent metadata

Field	Value
Publication number	US-11795124-B2
Application number	US-202017762893-A
Country	US
Kind code	B2
Filing date	Sep 25, 2020
Priority date	Sep 26, 2019
Publication date	Oct 24, 2023
Grant date	Oct 24, 2023

Abstract

Herein is provided a process for producing renewable products, such as alkenes, from a feedstock of biological origin. The process includes subjecting a feedstock including fatty acid glycerides and optionally free fatty acids, wherein at least one hydrocarbon chain is unsaturated, to esterification reaction in the presence of an alcohol. The ester stream thereby obtained is then fractionated and a fraction including esters of unsaturated C18 fatty acids is subjected to metathesis conditions in the presence of an alkene to obtain metathesis products. Fractionation of the metathesis products includes recovery of at least renewable 1-decene, and unsaturated C10-C15 fatty acid esters.

First claim

The invention claimed is:

1. A process for combined renewable alkene and renewable chemical production from a glyceride containing feedstock, the process comprising:
a) providing the glyceride containing feedstock containing free fatty acids, fatty acid glycerides selected from monoglycerides, diglycerides and triglycerides of fatty acids, and/or a mixture thereof, wherein the feedstock contains a compound having at least one carbon-carbon double bond;
b) subjecting the feedstock to esterification reaction in a presence of a C1-C4 monoalcohol, to yield a product having a fatty acid ester stream;
c) subjecting the product from step b) to fractional distillation to provide at least three fractions of: a gas fraction containing water and C1-C4 alcohols; a fraction containing fatty acid esters up to C16 for producing renewable base oil meeting API group III specifications; and a fraction containing alkyl esters of unsaturated C18 fatty acids;
d) subjecting the fraction containing alkyl esters of unsaturated C18 fatty acids to metathesis reaction conditions in a presence of a C2-C4 alkene to obtain metathesis products containing renewable alkenes, and fatty acid derived esters; and
e) recovery of at least one renewable alkene containing 1-decene, and at least one fatty acid derived ester containing alkyl-9-decenoate, from the products of step d).

2. The process according to claim 1 , wherein the fractional distillation in step c) provides:
at least one fraction containing water and C1-C4 monoalcohol, in a cumulative amount of at least 80%-wt of a total fraction weight;
at least one fraction containing saturated fatty acid esters having carbon chain length from C12 to C16 in a cumulative amount of at least 80%-wt and/or at least 90% wt of the total fraction weight;
at least one fraction containing alkyl esters of unsaturated C18 fatty acids; and
an optional bottom product from the fractional distillation containing >C18 fatty acid esters and glycerol.

3. The process according to claim 2 , wherein the fraction containing alkyl esters of unsaturated C18 fatty acids comprises:
fatty acid esters having a carbon chain length of C18, in a cumulative amount of at least 80%-wt of a total fraction weight.

4. The process according to claim 3 , wherein step e) comprises:
metathesis product separation steps selected from evaporation, distillation or combinations thereof.

5. The process according to claim 4 , wherein step e) comprises:
i) an evaporation, wherefrom the C2-C4 alkenes are recovered as an evaporation overheads product, and recycled back to a metathesis reaction, and a distillation of an evaporation bottom, wherefrom renewable C5-C9 alkenes are recovered as a distillation overheads product and the bottom product is obtained.

6. The process according to claim 5 , wherein step e) comprises:
ii) a distillation of the bottom product from distillation i), wherefrom 1-decene is recovered as a product distillation overheads product.

7. The process according to claim 6 , wherein step e) comprises:
iii) a second distillation of the bottom product from distillation ii), wherefrom alkyl-9-decenoate and/or ethyl-9-decenoate, is recovered as an overheads product.

8. The process according to claim 7 , wherein step e) comprises:
iv) hydrotreatment of the bottom product from second distillation iii), by hydrodeoxygenation and hydroisomerisation into at least one component selected from renewable diesel, renewable naphtha, renewable aviation fuel, and renewable gasoline.

9. The process according to claim 1 , wherein the metathesis reaction conditions in step d) comprise:
a temperature from 20 to 120° C., a pressure from 0.1 to 3 MPa and a metathesis catalyst.

10. The process according to claim 1 , wherein the C1-C4 monoalcohol used in step b) is selected from at least one or more of methanol, ethanol, 1-propanol, 2-propanol, 1-butanol and 2-butanol, and/or a mixture thereof and/or from bio based monoalcohols, and/or from bio based ethanol.

11. The process according to claim 1 , wherein the C2-C4 alkene is ethene.

12. The process according to claim 2 , comprising:
subjecting the fraction containing fatty acid esters up to C16, or the fraction containing saturated fatty acid esters having carbon chain length from C12 to C16, to ketonisation and hydrotreatment to produce renewable base oil meeting the API group III specifications.

13. The process according to claim 12 , wherein the monoalcohol used in step b) is ethanol, the ketonisation releases ethene, and the ethene thereby produced is recycled back to metathesis reaction in step d).

14. The process according to claim 1 , wherein the metathesis products comprise:
ethyl-9-decenoate.

15. The process according to claim 1 , comprising:
hydrotreatment of the bottom product containing >C18 fatty acid esters from separation in step c).

16. Process for providing a metathesis reaction, the process comprising:
conducting the fractional distillation of claim 1 as pretreatment for the metathesis reaction of fatty acid esters according to the process of claim 1 .

17. Process according to claim 16 , in a combined renewable base oil and renewable alkene production.

18. Process according to claim 17 , comprising:
producing a renewable fuel.

19. The process according to claim 1 , wherein the fractional distillation in step c) provides:
the bottom product from the fractional distillation containing >C18 fatty acid esters and glycerol.

20. The process according to claim 2 , wherein the fraction containing saturated fatty acid esters having carbon chain length from C12 to C16 comprises:
saturated fatty acid esters having a carbon chain length from C12 to C16 in a cumulative amount of at least 90%-wt of the total fraction weight.

21. The process according to claim 2 , wherein the fraction containing alkyl esters of unsaturated C18 fatty acids comprises:
fatty acid esters having a carbon chain length of C18 in a cumulative amount of at least 90%-wt of a total fraction weight.

Assignees

• Neste Oyj

Inventors

• Hietala Jukka
• Leminen Anja
• Rämö Virpi
• Räsänen Jukka

Classifications

• C07C6/04 Primary

  at a carbon-to-carbon double bond · CPC title

• C07C67/02 Primary

  by interreacting ester groups, i.e. transesterification · CPC title

• C07C67/333

  by isomerisation; by change of size of the carbon skeleton (introduction or elimination of carboxyl groups C07C67/313, C07C67/32) · CPC title

• C07C67/54

  by distillation · CPC title

• C10G7/00 Primary

  Distillation of hydrocarbon oils · CPC title