Process for the production of olefinic compounds and a hydrocarbon fuel or a fraction thereof

Patent metadata

Field	Value
Publication number	US-11021416-B2
Application number	US-201415028780-A
Country	US
Kind code	B2
Filing date	Dec 24, 2014
Priority date	Dec 30, 2013
Publication date	Jun 1, 2021
Grant date	Jun 1, 2021

Abstract

The present invention relates to a process for the production of olefinic compounds that can be used for the production of detergents, additives, lubricants and/or plastic materials, or components which can be used in the field of oil explorations and productions, and a hydrocarbon fuel or a fraction thereof, which comprises subjecting a mixture of glycerides having at least one unsaturated hydrocarbon chain, to metathesis reaction and, after separating the olefinic mixture obtained, effecting a hydrodeoxygenation and subsequently hydroisomerization process, so as to obtain the hydrocarbon fuel or a fraction thereof.

First claim

The invention claimed is:

1. A process for producing olefinic compounds and a hydrocarbon fuel or a fraction thereof, the process comprising:
(a) subjecting to metathesis reaction a mixture of glycerides having at least one unsaturated hydrocarbon chain with at least one C 2 -C 6 monoolefin in the presence of a metathesis catalyst, to obtain a mixture of glycerides having at least one unsaturated hydrocarbon chain with a carbon length less than an initial carbon length, and a mixture of C 6 -C 18 olefins;
(b) separating the mixture of C 6 -C 18 olefins from the mixture of glycerides obtained by step (a);
(c) subjecting the mixture of glycerides obtained by step (b) to a transesterification reaction with an alcohol selected from the group consisting of methanol, ethanol and mixtures thereof, to obtain a mixture of methyl esters, ethyl esters, or both, and glycerol;
(c′) separating the glycerol from the mixture of methyl esters, ethyl esters, or both; and then
(c″) separating methyl esters, ethyl esters, or both, having an unsaturated hydrocarbon chain from methyl esters, ethyl esters, or both, having a saturated hydrocarbon chain in the mixture; and
(d) hydrodeoxygenating a stream consisting essentially of the methyl esters, ethyl esters, or both, having a saturated hydrocarbon chain, obtained by step (c″) to produce an effluent and then hydroisomerizing the effluent to obtain the hydrocarbon fuel or a fraction thereof.

2. The process of claim 1 , wherein the hydrocarbon fuel is selected from the group consisting of a diesel fuel, a naphtha fuel, an aviation petrol, and mixtures thereof.

3. The process of claim 1 , wherein the glycerides having at least one unsaturated hydrocarbon chain in the mixture in step (a) are glycerides of vegetable or animal origin or of microbial origin.

4. The process of claim 3 , wherein the glycerides of vegetable or animal origin or of microbial origin are mono or polyunsaturated glycerides of fatty acids having at least one C 12 -C 24 hydrocarbon chain.

5. The process of claim 3 , wherein the glycerides are in the form of a vegetable oil, a recycled oil from a food industry, a recycled fat from a food industry, a lipid from a seaweed, an animal oil, an animal or mixtures thereof.

6. The process of claim 1 , wherein the at least one C 2 -C 6 monoolefin is selected from the group consisting of ethylene, propene, 1-butene, but-2-ene, 2-methyl-propene, and mixtures thereof.

7. The process of claim 1 , wherein, in step (a), a molar ratio of double bonds of the mixture of glycerides having at least one unsaturated hydrocarbon chain and double bonds of the at least one C 2 -C 6 monoolefin ranges from 1:0.1 to 1:20.

8. The process of claim 1 , wherein step (a) occurs at a temperature from 20 to 120° C., for a period of time from 0.5 to 6 hours.

9. The process of claim 1 , wherein step (a) occurs at a pressure of between 1 and 30 bars.

10. The process of claim 1 , wherein the metathesis catalyst is a carbene complex of a transition metal of Group 8.

11. The process of claim 1 , wherein separation in step (b) occurs by distillation.

12. The process of claim 1 , wherein said hydrodeoxygenating in step (d) occurs with hydrogen in the presence of a hydrodeoxygenation catalyst.

13. The process of claim 12 , wherein the hydrodeoxygenation catalyst comprises at least one metal of group VIII or of group VIB.

14. The process of claim 12 , wherein the hydrodeoxygenation catalyst is supported on at least one metallic oxide.

15. The process of claim 1 , wherein the said hydroisomerizing in step (d) occurs with hydrogen in the presence of a hydroisomerization catalyst.

16. The process of claim 15 , wherein the hydroisomerization catalyst comprises at least one metal of group VIII and an acid-containing support.

17. The process of claim 1 , wherein the glycerides are triglycerides.

18. The process of claim 1 , wherein the at least one C 2 -C 6 monoolefin is a C 2 -C 4 monoolefin.

19. The process of claim 1 , wherein the glycerides are in the form of a vegetable oil and said vegetable oil is selected from the group consisting of sunflower, rapeseed, canola, palm, soya bean, hemp, olive, linseed, mustard, peanut, castor, coconut and tall oil.

20. The process of claim 1 , wherein the glycerides are in the form of a fat and said fat is selected from the group consisting of lard, lard cream, tallow, and milk fat.

21. A process for producing olefinic compounds and a hydrocarbon fuel or a fraction thereof, the process comprising:
(a) subjecting to metathesis reaction a mixture of glycerides having at least one unsaturated hydrocarbon chain with at least one C 2 -C 6 monoolefin in the presence of a metathesis catalyst, to obtain a mixture of glycerides having at least one unsaturated hydrocarbon chain with a carbon length less than an initial carbon length, and a mixture of C 6 -C 18 olefins;
(b) separating the mixture of C 6 -C 18 olefins from the mixture of glycerides obtained by step (a);
(c) subjecting the mixture of glycerides obtained by step (b) to a transesterification reaction with an alcohol selected from the group consisting of methanol, ethanol and mixtures thereof, to obtain a mixture of methyl esters, ethyl esters, or both, and glycerol;
(c′) separating the glycerol from the mixture of methyl esters, ethyl esters, or both; and then
(c″) separating methyl esters, ethyl esters, or both, having an unsaturated hydrocarbon chain from methyl esters, ethyl esters, or both, having a saturated hydrocarbon chain in the mixture; and
(d) hydrodeoxygenating a stream consisting of the methyl esters, ethyl esters, or both, having a saturated hydrocarbon chain, obtained by step (c″) to produce an effluent and then hydroisomerizing the effluent to obtain the hydrocarbon fuel or a fraction thereof.

Assignees

• Versalis Spa

Inventors

• Bosetti Aldo
• Lombardini Sergio Francantonio
• Girotti Gianni

Classifications

• C07C67/333 Primary

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

• C11C3/003

  by esterification of fatty acids with alcohols (C11C3/02 takes precedence) · CPC title

• C11C3/14

  by isomerisation {(isomerisation induced by hydrogenation C11C3/12)} · CPC title

• C10G3/50 Primary

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

• C10G3/45

  containing iron group metals or compounds thereof · CPC title