Method for converting carboxylic acids and esters into base oil hydrocarbons

Patent metadata

Field	Value
Publication number	US-11149206-B2
Application number	US-201816623210-A
Country	US
Kind code	B2
Filing date	Jun 15, 2018
Priority date	Jun 19, 2017
Publication date	Oct 19, 2021
Grant date	Oct 19, 2021

Abstract

A number of different branched hydrocarbon compounds (formula I) having a star-like configuration (S) are prepared from renewable oils containing fatty acids or derivatives containing fatty acids. The branched hydrocarbon compounds may be isolated individually or in mixtures, and may be used as part of base oils, such as renewable base oils (RBOs). A process for preparing the branched hydrocarbon compounds of formula I involve conditions that favour a trimerisation reaction followed by hydrotreating conditions. The compounds of formula I may be made by catalytically treating renewable material in a process, and the compounds have desirable qualities relating to lubrication, cold flow as well as having a low Noack volatility.

First claim

The invention claimed is:

1. A compound of a formula I, wherein n, m and p are each, independently of each other, an odd numbered integer value between 9 and 41, and where a total carbon number of formula I is between 31 and 65, with a proviso that when n and m are both 9, then p is not 9 or 11, and with the proviso that n, m and p are not all 11

2. The compound according to claim 1 , wherein n is 13 or 15; m and p are, independently of each other, either 15 or 17.

3. A process for obtaining isomerised star-shaped compounds containing any of between 1 to 5 methyl branches, the process comprising:
subjecting one or more compounds of formula I:

wherein n, m and p are each, independently of each other, an odd numbered integer value between 9 and 41, and where a total carbon number of formula I is between 31 and 65, with a proviso that when n and m are both 9, then p is not 9 or 11, and with a proviso that n, m and p are not all 11, to an isomerisation step; and
conducting the isomerisation step in a presence of hydrogen and an isomerisation catalyst at a temperature in a range of 250 to 400° C., a pressure in a range from 10 to 60 barg a WHSV in a range of 0.1-5 h −1 , and a H 2 flow of 100-800 nl H 2 /l feed.

4. A compound of a formula II, wherein n is 13; m and p are both 15:

5. A base oil mixture comprising:
one or more compound(s) of formula I, wherein n, m and p are each, independently of each other, an odd numbered integer value between 9 and 41, and where a total carbon number of formula I is between 31 and 65:

6. The base oil mixture according to claim 5 , comprising:
one or more compound(s) of formula I, wherein n is 13 or 15; m and p are each, independently of each other, either 15 or 17.

7. The base oil mixture according to claim 5 , wherein the base oil mixture is selected to have a boiling point of 380° C. or more, 450° C. or more, 460° C. or more, or 470° C. or more.

8. The base oil mixture according to claim 5 , wherein the base oil mixture comprises:
at least 2% or more of the one or more compound(s) of formula I.

9. A process for base oil production, comprising:
a) trimerising a feed containing at least one fatty acid to provide a trimerisation product where a mixture of fatty acid trimers is obtained; and
b) hydrotreating at least a portion of the trimerisation product to provide a base oil product having a pour point lower than 5° C.;
where the hydrotreated base oil product includes one or more compound(s) of formula I,
wherein n, m and p are each, independently of each other, an integer value between 9 and 41, and where a total carbon number of formula I is between 31 and 65;

where carbon atoms of one or more compound(s) of formula I exclusively come from monocarboxylic fatty acids; and
where the trimerising is carried out at a conversion level of at least 99.5% of the at least one fatty acid of the feed.

10. The process for base oil production according to claim 9 , wherein step a) comprises:
contacting the at least one fatty acid with a trimerisation catalyst in a trimerisation zone under trimerisation conditions to provide the mixture of fatty acid trimers; and step b) comprises:
contacting the mixture of fatty acid trimers with a hydrotreating catalyst in a presence of hydrogen gas in a hydrotreating zone under hydrotreating conditions to provide the base oil product.

11. The process for base oil production according to claim 10 , wherein the trimerisation conditions comprise:
a temperature in a range from 300 to 400° C., a pressure in a range from 5 to 100 barg and a WHSV in a range from 0.1-5 h −1 , and the trimerisation catalyst comprises:
a metal oxide catalyst.

12. The process for base oil production according to claim 9 , wherein the trimerisation catalyst comprises at least one of:
a catalyst containing metal selected from one or more of a list consisting of: metal oxides containing Ti, Mn, Mg, and Ca; and
TiO 2 and one or more alkali metal oxides, where the one or more alkali metal oxides are selected from one or more of a list consisting of: metal oxides containing Li, Na, and K.

13. The process for base oil production according to claim 9 , wherein the trimerising comprises:
formation of a ketone from a reaction between two fatty acids followed by a condensation reaction between the ketone and another fatty acid to produce an alpha-substituted and alpha-unsaturated ketone.

14. The process for base oil production according to claim 9 , wherein the at least one fatty acid is selected from a C 9 to C 22 fatty acid.

15. The process for base oil production according to claim 9 , the feed comprising at least one of:
at least one fatty acid selected from one or more of the list consisting of: palm oil, canola oil, rapeseed oil, olive oil, sunflower oil, beef fat, lard, coconut oil, corn oil, soybean oil, jatropha oil, tall oil, crude tall oil, tall oil pitch, tall oil heads and tall oil fatty acids; and
at least one fatty acid diluted with a stream of hydrocarbons, or where the trimerisation product is diluted with a stream of hydrocarbons.

16. The process for base oil production according to claim 10 , wherein the feed comprises:
at least one fatty acid diluted with a stream of product withdrawn from the process, for example or withdrawn from the trimerisation zone or from the hydrotreatment zone.

17. The process for base oil production according to claim 10 , wherein in the trimerisation zone a gas feed is present, the gas being selected from the list consisting of: nitrogen, carbon dioxide, water vapour, methane and hydrogen.

18. The process for base oil production according to claim 9 , wherein the trimerisation product is isolated in a fraction having a boiling point of more than 450° C.

19. The process for base oil production according to claim 9 , comprising:
c) isomerising the hydrotreated base oil product.

20. The base oil composition obtained by the process of claim 9 .

21. A process according to claim 9 , comprising:
improving the lubricating properties of base oil with the hydrotreated base oil product.

22. A process for obtaining isomerised star-shaped compounds containing between 1 to 5 methyl branches, the method comprising:
a feed containing at least 80 wt % hydrocarbons and at least 2 wt %, of one or more compounds of formula I:

 wherein n, m and p are each, independently of each other, an odd numbered integer value between 9 and 41, and where a total carbon number of formula I is between 31 and 65, with a proviso that when n and m are both 9, then p is not 9 or 11, and with a proviso that n, m and p are not all 11 to an isomerisation step; and
conducting the isomerisation step in a presence of hydrogen and an isomerisation catalyst at a temperature in a range of 250 to 400° C., a pressure in a range from 10 to 60 barg a WHSV in a range of 0.1-5

Assignees

• Neste Oyj

Inventors

• Myllyoja Jukka
• Kettunen Mika
• Piilola Rami

Classifications

• C11C1/10

  by distillation · CPC title

• C11C1/04

  by hydrolysis · CPC title

• C10N2030/74

  Noack Volatility · CPC title

• C10N2030/43

  Sulfur free or low sulfur content compositions · CPC title

• C10N2030/16

  Antiseptic; {(micro)} biocidal {or bactericidal} · CPC title