Processes to produce poly alpha-olefin trimer and apparatus therefor

Patent metadata

Field	Value
Publication number	US-11028197-B2
Application number	US-201916537381-A
Country	US
Kind code	B2
Filing date	Aug 9, 2019
Priority date	Feb 12, 2018
Publication date	Jun 8, 2021
Grant date	Jun 8, 2021

Abstract

In at least one embodiment, a process to produce a poly alpha-olefin (PAO) includes introducing a first alpha-olefin to a first catalyst system comprising activator and a metallocene compound into a continuous stirred tank reactor or a continuous tubular reactor under first reactor conditions to form a first reactor effluent. The first alpha-olefin is introduced to the reactor at a flow rate of about 100 g/hr or more. The first reactor effluent includes at least 60 wt % of PAO dimer and 40 wt % or less of higher oligomers, where the higher oligomers are oligomers that have a degree of polymerization of 3 or more. The process includes introducing the first reactor effluent and a second alpha-olefin to a second catalyst composition including an acid catalyst in a second reactor to form a second reactor effluent comprising PAO trimer.

First claim

What is claimed is:

1. A process to produce a poly alpha-olefin (PAO), comprising:
a) introducing a first alpha-olefin to a first catalyst system comprising activator and a metallocene compound into a continuous stirred tank reactor or a continuous tubular reactor under first reactor conditions, wherein the first alpha-olefin is introduced to the reactor at a flow rate of about 100 g/hr or more, to form a first reactor effluent comprising at least 60 wt % of PAO dimer and 40 wt % or less of higher oligomers, where the higher oligomers are oligomers that have a degree of polymerization of 3 or more; and
b) introducing the first reactor effluent and a second alpha-olefin to a second catalyst composition comprising an acid catalyst in a second reactor to form a second reactor effluent comprising PAO trimer,
wherein the higher oligomers in the first reactor effluent are not separated from the first effluent stream prior to introduction into the second reactor.

2. The process of claim 1 , wherein the first reactor effluent is not transferred to a separation unit prior to introduction into the second reactor unit.

3. The process of claim 1 , further comprising:
introducing the second reactor effluent to a first distillation unit to form a first distillation effluent; and
introducing the first distillation effluent to a hydrogenation unit and hydrogenating the first distillation effluent to form a hydrogenated effluent.

4. The process of claim, further comprising:
introducing the hydrogenated effluent to a second distillation unit to form a second distillation effluent; and
introducing the second distillation effluent to a third distillation unit to form PAO effluents having a viscosity of from 3 cSt to about 10 cSt.

5. The process of claim 1 , wherein the acid catalyst is a Lewis acid.

6. The process of claim 1 , wherein the acid catalyst is present in the second reactor at an acid catalyst loading of from about 5 mmolCat/100gLAO to about 15 mmolCat/100gLAO.

7. The process of claim 1 , wherein the second reactor comprises a temperature of from about 10° C. to about 40° C.

8. The process of claim 1 , wherein the acid catalyst is BF 3 .

9. The process of claim 1 , wherein the first reactor effluent includes 50 wt % or less of higher oligomers, based on a total weight percent of the first reactor effluent.

10. The process of claim 1 , wherein the first reactor effluent includes 10 wt % or less of higher oligomers of alpha-olefin, based on a total weight percent of the first reactor effluent.

11. The process of claim 1 , wherein the first alpha-olefin and the second alpha-olefin are different.

12. The process of claim 1 , wherein the second reactor effluent comprises 50 wt % or more of the PAO trimer based on a total weight percent of the second reactor effluent.

13. The process of claim 1 , wherein the second reactor effluent comprises 65 wt % or more of the PAO trimer based on a total weight percent of the second reactor effluent.

14. The process of claim 1 , wherein the second reactor effluent comprises 75 wt % or more of the PAO trimer, based on a total weight percent of the second reactor effluent.

15. The process of claim 1 , wherein the second reactor conditions include a second reactor temperature of less than 60° C.

16. The process of claim 1 , wherein the second catalyst composition further comprises an alcohol and an alkyl acetate.

17. The process of claim 1 , wherein,
the PAO dimer of the first product effluent comprises 96 mol % or more of vinylidene, and 4 mol % or less of disubstituted vinylene and trisubstituted vinylene, based on total moles of vinylidene, disubstituted vinylene, and trisubstituted vinylene in the PAO dimer of the first product effluent.

18. The process of claim 1 , wherein,
the PAO dimer of the first product effluent comprises 98 mol % or more of vinylidene, and 2 mol % or less of disubstituted vinylene and trisubstituted vinylene, based on total moles of vinylidene, disubstituted vinylene, and trisubstituted vinylene in the PAO dimer of the first product effluent.

19. The process of claim 1 , wherein the metallocene compound is represented by the formula:

wherein:
each of R 1 , R 2 , and R 3 is independently hydrogen, a substituted or unsubstituted linear, branched, or cyclic C1-C20 hydrocarbyl group, wherein at least one of R 1 , R 2 , and R 3 is not hydrogen and at least one of R 1 , R 2 , and R 3 is hydrogen;
each of R 4 , R 5 , R 6 , and R 7 is independently hydrogen, a substituted or unsubstituted linear, branched, or cyclic C1-C30 hydrocarbyl group, or one or more pair of R 4 and R 5 , R 5 and R 6 , or R 6 and R 7 , taken together with the carbon atoms in the indenyl ring to which they are directly connected, collectively form one or more substituted or unsubstituted rings fused to the indenyl ring;
each of R 8 , R 9 , R 10 , R 11 , and R 12 is independently a substituted or unsubstituted linear, branched, or cyclic C 1 -C 30 hydrocarbyl, silylcarbyl, or germanyl group;
M is a group 3, 4 or 5 transition metal;
each X is independently a halogen, a hydride, an amide, an alkoxide, a sulfide, a phosphide, a diene, an amine, a phosphine, an ether, or a C 1 -C 20 substituted or unsubstituted linear, branched, or cyclic hydrocarbyl group, or optionally two or more X moieties together form a fused ring or ring system; and
m is an integer equal to 1, 2, or 3.

20. The process of claim 1 , wherein the metallocene compound is represented by the formula:

wherein:
each of R 1 , R 2 , and R 3 is independently hydrogen or a substituted or unsubstituted linear, branched, or cyclic C 1 -C 20 hydrocarbyl or silylcarbyl group;
each of R 4 and R 7 is independently hydrogen, a substituted or unsubstituted linear, branched, or cyclic C1-C30 hydrocarbyl or silylcarbyl group;
each of R 8 , R 9 , R 10 , R 11 , and R 12 is independently a hydrogen, or a substituted or unsubstituted linear, branched, or cyclic C 1 -C 20 hydrocarbyl, silylcarbyl, or germanyl group, or optionally at least three of R 8 , R 9 , R 10 , R 11 , and R 12 are not hydrogen;
each of R 13 , R 14 , R 15 , R 16 , R 17 , and R 18 is independently hydrogen or a substituted or unsubstituted linear, branched, or cyclic C 1 -C 20 hydrocarbyl or silylcarbyl group;
M is a group 3, 4 or 5 transition metal;
each X is independently a halogen, a hydride, an amide, an alkoxide, a sulfide, a phosphide, a diene, an amine, a phosphine, an ether, or a C 1 -C 20 substituted or unsubstituted linear, branched, or cyclic hydrocarbyl group, or optionally two or more X moieties together form a fused ring or ring system; and
m is an integer equal to 1, 2, or 3.

21. The process of claim 1 , wherein the wherein the activator comprises one or more of:
N,N-dimethylanilinium tetrakis(perfluorophenyl)borate,
N,N-dimethylanilinium tetrakis(perfluoro-naphthyl)borate,
triphenylcarbonium tetrakis(perfluorophenyl)borate,
triphenylcarbonium tetrakis(perfluoronaphthyl)borate,
N,N-dimethylanilinium tetrakis(perfluorophenyl)aluminate,
N,N-dimethylanilinium tetrakis(perfluoronaphthyl)aluminate,
alumoxane,
a modified alumoxane, and
aluminum alkyl.

22. The p

Assignees

• Exxonmobil Chemical Patents Inc

Inventors

• Chen Patrick C
• Li Mark H
• Rapp Jennifer L
• Nandapurkar Pramod J
• Wahn Brian H
• Lotfizadehdehkordi Babak
• Emett Craig J
• Kuzhiyil Najeeb M
• Yang Jian

Classifications

• C07C17/00

  Preparation of halogenated hydrocarbons · CPC title

• C07C2/32

  as complexes, e.g. acetyl-acetonates {(complexes of salts of acids of halogen C07C2/20)} · CPC title

• C07C2/30

  containing metal-to-carbon bond; Metal hydrides · CPC title

• C08F2420/07

  Heteroatom-substituted Cp, i.e. Cp or analog where at least one of the substituent of the Cp or analog ring is or contains a heteroatom · CPC title

• C08F4/65908

  in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+ · CPC title