Mitigation of catalyst inhibition in olefin polymerization

Patent metadata

Field	Value
Publication number	US-9382344-B2
Application number	US-201414311171-A
Country	US
Kind code	B2
Filing date	Jun 20, 2014
Priority date	Jun 25, 2013
Publication date	Jul 5, 2016
Grant date	Jul 5, 2016

Abstract

This disclosure relates to a process for polymerization comprising providing a recycle stream, wherein the recycle stream comprises one or more C 6 to C 12 conjugated or non-conjugated diene monomers and one or more C 1 to C 40 oxygenates. The recycle stream is contacted with an adsorbent bed to produce a treated recycle stream; wherein the adsorbent bed comprises at least two adsorbents to remove quenching agent and C 1 to C 40 oxygenates.

First claim

The invention claimed is:

1. A process for polymerization comprising:
(i) providing a polyolefin product stream, wherein the polyolefin product stream comprises polyolefin product and unreacted monomer;
(ii) quenching the polyolefin product stream with a quenching agent selected from water, a C 1 to C 8 alcohol, and mixtures thereof, to produce a quenched polyolefin stream,
(iii) separating the quenched polyolefin stream into polyolefin product and a recycle stream; and
(iv) contacting at least a portion of the recycle stream with an adsorbent bed to produce a treated recycle stream, wherein the recycle stream comprises quenching agent, one or more C 6 to C 12 conjugated or non-conjugated diene monomers, and one or more C 1 to C 40 oxygenates, and wherein the adsorbent bed comprises at least two adsorbents to remove the quenching agent and/or the C 1 to C 40 oxygenates.

2. The process of claim 1 , wherein the adsorbent bed comprises at least one adsorbent to remove water and at least one other adsorbent to remove C 8 to C 40 oxygenates.

3. The process of claim 1 , wherein at least one adsorbent is a zeolitic molecular sieve and at least one adsorbent is a hybrid zeolite in alumina.

4. The process of claim 3 , wherein the hybrid zeolite in alumina adsorbent removes C 8 to C 40 oxygenates.

5. The process of claim 3 , wherein the adsorbent bed further comprises an alumina adsorbent.

6. The process of claim 3 , wherein the adsorbent bed further comprises at least one silica adsorbent.

7. The process of claim 3 , wherein the zeolitic molecular sieve comprises material selected from the group consisting of zeolite X, zeolite Y, zeolite A, faujasite, mordenite, ferrierite, and mixtures thereof.

8. The process of claim 3 , wherein the zeolitic molecular sieve is binderless.

9. The process of claim 1 , wherein the one or more C 6 to C 12 non-conjugated diene monomers are selected from the group consisting of: 2-methyl-1,4-pentadiene, 3-methyl-1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 2-methyl-1,5-hexadiene 3-methyl-1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 1,5-heptadiene, 1,6-heptadiene, norbornadiene, 3,3-dimethyl-1,3-hexadiene, 4-ethyl-1,4-hexadiene, 5-methyl-1,4-heptadiene, 6-methyl-1,4-heptadiene, 1-vinylcyclohexene, 5-methylene-2-norbornene, 1,6-octadiene, 1,7-octadiene, 1,9-octadiene, 1,7-nondiene, 1,8-nonadiene, 5-vinyl-2-norbornene, 5-ethylidene-2-norbornene, 5-ethyl-1,4-heptadiene, 5-ethyl-1,5-heptadiene, 4-methyl-1,4-octadiene, 5-methyl-1,4-octadiene, 5-methyl-1,5-octadiene, 6-methyl-1,5-octadiene, 6-methyl-1,6-octadiene, 7-methyl-1,6-octadiene, 1,8-decadiene, 1,9-decadiene, 1,4-divinylcyclohexane, 1,3-divinylcyclohexane, dicyclopentadiene, 3,7-dimethyl-1,6-octadiene, 5,7-dimethyl-1,6-octadiene, 4-ethyl-1,4-octadiene, 5-ethyl-1,4-octadiene, 5-ethyl-1,5-octadiene, 6-ethyl-1,5-octadiene, 6-ethyl-1,6-octadiene, 4-methyl-1,4-nonadiene, 5-methyl-1,4-nonadiene, 5-methyl-1,5-nonadiene, 6-methyl-1,5-nonadiene, 6-methyl-1,6-nonadiene, 7-methyl-1,6-nonadiene, 7-methyl-1,7-nonadiene, 5-allyl-2-norbornene, 1,10-undecadiene, 6-propyl-1,6-octadiene, 4-ethyl-1,4-nonadiene, 5-ethyl-1,4-nonadiene, 5-ethyl-1,5-nonadiene, 6-ethyl-1,5-nonadiene, 6-ethyl-1,6-nonadiene, 7-ethyl-1,6-nonadiene, 5-methyl-1,4-decadiene, 5-methyl-1,5-decadiene, 6-methyl-1,5-decadiene, 6-methyl-1,6-decadiene, 7-methyl-1,6-decadiene, 7-methyl-1,7-decadiene, 8-methyl-1,7-decadiene, 8-methyl-1,8-decadiene, 9-methyl-1,8-decadiene, 1,11-dodecadiene, 6-butyl-1,6-octadiene, 5-ethyl-1,4-decadiene, 5-ethyl-1,5-decadiene, 6-ethyl-1,5-decadiene, 6-ethyl-1,6-decadiene, 7-ethyl-1,6-decadiene, 7-ethyl-1,7-decadiene, 8-ethyl-1,7-decadiene, 8-ethyl-1,8-decadiene, 6-methyl-1,6-undecadiene, 8-methyl-1,6-undecadiene, and combinations thereof.

10. The process of claim 1 , wherein the recycle stream comprises one or more of C 9 and C 18 oxygenates, before contact with the adsorbent bed.

11. The process of claim 1 , wherein the recycle stream has 50 wt % more C 4 to C 40 oxygenates than the treated recycle stream.

12. The process of claim 11 , wherein the recycle stream has 65 wt % more C 4 to C 40 oxygenates than the treated recycle stream.

13. The process of claim 1 , wherein the quenching agent is water and the oxygenates are C 9 and C 18 oxygenates.

14. The process of claim 1 , wherein the quenching agent is a C m alcohol, where m is an integer equal to the number of carbon atoms in the alcohol, and where the C 1 to C 40 oxygenate is a C m+n , where m is the m from the C m alcohol, and where n is an integer from 6 to 32.

15. The process of claim 1 , wherein the recycle stream, after contact with the adsorbent bed, comprises 10 ppm or less C 4 to C 40 oxygenates.

16. The process of claim 1 , further comprising regenerating the adsorbent bed by heating the adsorbent bed to a temperature in the range of from about 150 to about 290° C.

17. The process of claim 1 , further comprising subjecting the adsorbent bed to a hot diluent wash prior to and/or after regeneration.

18. The process of claim 1 , further comprising sparging the adsorbent bed with hot nitrogen prior to and/or after regeneration.

19. The process of claim 1 , wherein when the recycle stream is in contact with the adsorbent bed, from 70 wt % to 99 wt % of the C 18 oxygenates are absorbed and from 10 wt % to 45 wt % of the non-conjugated dienes are absorbed by the at least two adsorbents.

20. The process of claim 1 , wherein at least one of the adsorbents is a hybrid zeolite in alumina and has a surface area within the range of from 60 m 2 /g to 140 m 2 /g and a pore volume within the range from 0.30 ml/g to 0.54 ml/g.

21. The process of claim 1 , wherein the residence time of the recycle stream with the at least two adsorbents is within the range of from 5 to 20 minutes.

22. The process of claim 1 , wherein the residence time for the recycle stream with each of the adsorbents, individually, is within the range of from 4 to 18 minutes.

23. The process of claim 1 , wherein the oxygenate is the reaction product of a C 6 to C 12 non-conjugated diene monomer, the quenching agent, and an aluminum alkyl adduct or a zeolitic molecular sieve.

24. The process of claim 1 , wherein the quenching agent is water and the recycle stream first contacts the at least one adsorbent provided to remove water, followed by the recycle stream having water removed contacting the at least one other adsorbent provided to remove C 8 to C 40 oxygenates.

Assignees

• Exxonmobil Chem Patents Inc

Inventors

• Ho Suzzy C
• Canich Jo Ann M
• Mertens Machteld M
• Ravishankar Periagaram S
• Byrne Patrick S
• Stefaniak Lisa B V

Classifications

• C08F2/00

  Processes of polymerisation · CPC title

• C08F6/00 Primary

  Post-polymerisation treatments (C08F8/00 takes precedence; of conjugated diene rubbers C08C) · CPC title

• C08F2/01

  characterised by special features of the polymerisation apparatus used · CPC title

• C08F36/04

  conjugated · CPC title

• C08F6/02

  Neutralisation of the polymerisation mass, e.g. killing the catalyst (short-stopping C08F2/42 ){also removal of catalyst residues} · CPC title