Process for making gamma-branched alcohol

Patent metadata

Field	Value
Publication number	US-10604462-B2
Application number	US-201815988604-A
Country	US
Kind code	B2
Filing date	May 24, 2018
Priority date	Aug 28, 2017
Publication date	Mar 31, 2020
Grant date	Mar 31, 2020

Abstract

This disclosure relates to a process for making an alcohol product comprising a gamma-branched alcohol from a vinylidene olefin by hydroformylation.

First claim

What is claimed is:

1. A process for making an alcohol product comprising a gamma-branched alcohol having a formula (F-I) below:

where each R 1 group, the same or different, is independently a C2 to C28 linear or branched alkyl group, the process comprising the following steps:
(I) providing a vinylidene feed comprising a vinylidene olefin having a formula (F-II) below:

where the R 1 groups correspond to the R 1 groups in formula (F-I) above;
(II) contacting the vinylidene olefin with carbon monoxide and hydrogen in the presence of a carbonylation catalyst system comprising a rhodium-containing compound and a phosphine compound to obtain a carbonylation product mixture;
wherein the contacting with the carbonylation catalyst occurs at a pressure of at least 510 psig, and
(III) contacting the carbonylation product mixture with hydrogen in the presence of a hydrogenation catalyst to produce an alcohol product comprising the gamma-branched alcohol, wherein:
steps (II) and (III) combined have a selectivity of the vinylidene olefin toward the gamma-branched alcohol of at least 97%.

2. The process of claim 1 , wherein the rhodium-containing compound is selected from rhodium oxides, inorganic salts of rhodium, rhodium salts of carboxylic acids, rhodium carbonyl compounds, and mixtures thereof.

3. The process of claim 1 , wherein the phosphine compound is selected from triphenyl phosphine, tri-(n-butyl) phosphine; tri-(tert-butyl) phosphine; tri-(n-pentyl) phosphine; tri-(n-hexyl) phosphine; tri(n-heptyl) phosphine; tri-(n-octyl) phosphine; tri(n-nonyl) phosphine; tri-(n-decyl) phosphine; and any mixture of two or more thereof.

4. The process of claim 1 , wherein in step (II), the molar ratio of carbon monoxide to hydrogen is 1:1.

5. The process of claim 1 , wherein steps (II) and (III) combined have a selectivity of the vinylidene olefin toward the gamma-branched alcohol of at least 99%.

6. The process of claim 1 , wherein each R 1 group, the same or different, is independently a linear alkyl group.

7. The process of claim 6 , wherein each R 1 group, the same or different, is independently selected from ethyl, n-propyl, n-butyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, n-icosyl, n-docosyl, n-tetracosyl, n-hexacosyl, and n-octacosyl.

8. The process of claim 6 , wherein each R 1 group, the same or different, is independently selected from ethyl, n-propyl, n-butyl, n-hexyl, n-octyl, n-decyl, and n-dodecyl, n-tetradecyl, n-hexadecyl, and n-octadecyl.

9. The process of claim 1 , wherein the two R 1 groups are identical.

10. The process of claim 1 , wherein in step (I), the vinylidene feed consists essentially of a single vinylidene olefin having a formula (F-II).

11. The process of claim 1 , wherein in step (I), the vinylidene feed comprises multiple vinylidene olefins each having a different formula (F-II).

12. The process of claim 11 , wherein the multiple vinylidene olefins differ in terms of molecular weight thereof by no more than 150 grams per mole.

13. The process of claim 1 , wherein step (I) comprises the following steps:
(Ia) providing a monomer feed comprising a terminal olefin having a formula (F-III) below:
R 1 —CH═CH 2   (F-III),

where R 1 corresponds to one of the two R 1 groups in formula (F-II);
(Ib) oligomerizing the monomer feed in an oligomerization reactor in the presence of a catalyst system comprising a metallocene compound to obtain an oligomerization product mixture; and
(Ic) obtaining the vinylidene feed from the oligomerization product mixture.

14. The process of claim 13 , wherein in step (Ia), the monomer feed comprises a single terminal olefin having a formula (F-III).

15. The process of claim 13 , wherein in step (Ia), the monomer feed comprises multiple terminal olefins having differing formula (F-III).

16. The process of claim 15 , wherein in step (Ia), the multiple terminal olefins differ in terms of molecular weight thereof by no more than 100 grams per mole.

17. The process of claim 13 , wherein:
in step (Ib), the metallocene compound has a formula Cp(Bg) n MX 2 Cp′, wherein M is selected from Hf and Zr; each X is independently a halogen or a hydrocarbyl group; Cp and Cp′, the same or different, independently represents a cyclopentadienyl, alkyl-substituted cyclopentadienyl, indenyl, alkyl-substituted indenyl, 4,5,6,7-tetrahydro-2H-indenyl, alkyl-substituted 4,5,6,7-tetrahydro-2H-indenyl, 9H-fluorenyl, and alkyl-substituted 9H-fluorenyl; each Bg is a bridging group covalently linking Cp and Cp′; and n is 0, 1, or 2; and the catalyst system further comprises an alumoxane.

18. The process of claim 17 , wherein:
step (Ib) is carried out in a continuous process at a temperature in the range from 50 to 90° C.; and in step (Ib):
the metallocene compound is fed into the oligomerization reactor at a feeding rate of R(mc) moles per hour, the alumoxane is fed into the oligomerization reactor at a feeding rate of R(Al) moles per hour, the monomer is fed into the oligomerization reactor at a feeding rate of R(to) moles per hour, 350≤R(to)/R(mc)≤750, 2≤R(Al)/R(mc)≤10, an oligomer mixture comprising the vinylidene olefin and a trimer of the terminal olefin is produced, and the selectivity toward the trimer is less than 5%.

19. The process of claim 18 , wherein in the metallocene compound, M is Zr.

20. The process of claim 18 , wherein X is Cl.

21. The process of claim 18 , wherein the alumoxane is methyl alumoxane.

22. The process of claim 18 , wherein at least one of the following conditions is met:
600≤R( to )/R( mc )≤750; and

2≤R(Al)/R( mc )≤5.

23. The process of claim 18 , wherein step (Ib) has a conversion of the terminal olefin of no less than 40%.

24. The process of claim 18 , wherein step (Ib) has a selectivity of the terminal olefin toward the vinylidene olefin of at least 95%.

25. The process of claim 24 , wherein step (Ic) does not include a step of removing a trimer of the terminal olefin from the oligomer mixture.

Assignees

• Exxonmobil Chemical Patents Inc

Inventors

• Chen Patrick C
• Lewis Kyle G

Classifications

• C07C2531/14

  of aluminium or boron · CPC title

• C07C29/141 Primary

  with hydrogen or hydrogen-containing gases · CPC title

• C07C2531/22

  Organic complexes · CPC title

• C07C45/50

  by oxo-reactions · CPC title

• C07C2/34

  Metal-hydrocarbon complexes · CPC title