Olefin trimerization

Patent metadata

Field	Value
Publication number	US-11535577-B2
Application number	US-202117524800-A
Country	US
Kind code	B2
Filing date	Nov 12, 2021
Priority date	Nov 12, 2020
Publication date	Dec 27, 2022
Grant date	Dec 27, 2022

Abstract

The present disclosure relates to a process and a production unit that are used to catalytically manufacture olefin trimers from olefin monomers, and wherein olefin dimers are recycled after dimerization reaction, and reacted with olefin monomers in an addition reaction.

First claim

The invention claimed is:

1. A process for manufacturing olefin trimers comprising:
feeding into a reactor containing a dimerization catalyst: olefin monomer feed and at least one oxygen-containing moderator;
operating the reactor at a temperature selected from a range of 40-140° C. and at a pressure selected from a range of 10-40 bar for carrying out catalytic dimerization reactions between olefin monomers and olefin monomers, and addition reactions between olefin monomers and olefin dimers;
withdrawing a reactor outlet stream from the reactor; and
distilling the reactor outlet stream to separate at least one lighter product containing olefin dimers, and a heavier bottom product containing olefin trimers; wherein
at least a portion of the at least one lighter product is recycled into the reactor for providing a recycle feed,
olefin monomers are fed into the reactor predominantly as a fresh olefin monomer feed,
amounts of the fresh olefin monomer feed and the recycle feed fed into the reactor are controlled such that a mass ratio of olefin monomers to olefin dimers entering the reactor is selected from a range of 1:8-1:15,
and wherein catalytic reactions of the reactor are carried out at operational conditions wherein olefins remain in liquid phase.

2. The process of claim 1 , wherein the fresh olefin monomers fed into the reactor comprise:
olefins having four carbon atoms, and/or isobutene.

3. The process of claim 1 , wherein the olefin monomer feed comprises:
at least one of the following: C4 olefins, C5 olefins, a mixed feed of C4 and C5 olefins, isobutene, 1-butene, cis-2-butene, trans-2-butene; and optionally inerts, n-butane, i-butane, butadiene, distillation fraction, or any mixture thereof.

4. The process of claim 1 , wherein olefin dimers are recycled into the reactor by mixing the recycle feed with fresh olefin monomers as a combined feed that is fed into the reactor.

5. The method of claim 1 , wherein the mass ratio of olefin monomers to olefin dimers is selected from a range 1:8-1:10.

6. The process of claim 1 , wherein a selectivity for olefin trimer production is selected to be one or more of at least 85%, and/or at least 90%, expressed as a weight-% based on the olefin monomers.

7. The process of claim 1 , wherein a once-through conversion rate of olefin monomers is selected to be one or more of at least 60%, at least 70%, at least 80%, at least 90%, at least 95% and/or at least 96%.

8. The process of claim 1 , wherein the dimerization catalyst is selected to be one or more of an acid catalyst, an acidic ion exchange resin catalyst, and/or a macroreticular acid ion exchange resin catalyst.

9. The process of claim 1 , wherein the oxygen-containing moderator contains water, demiwater, alcohol, tert-butyl alcohol, or any combination thereof.

10. The process of claim 9 , wherein an amount of the oxygen-containing moderator is selected from one or more of a range 0.01-0.5 wt-% of total feed to the reactor, a range 0.1-0.4 wt-% of total feed to the reactor, and/or from a range 0.2-0.3 wt-% of total feed to the reactor.

11. The process of claim 1 , wherein an operating temperature of the reactor is selected from one or more of a range 50-130° C., and/or a range 60-120° C.

12. The process of claim 1 , wherein an operating pressure of the reactor is selected from one or more of a range 15-35 bar, and/or from a range 20-30 bar.

13. The process of claim 1 , wherein a residence time of feed passing through the reactor is one or more of a 0.25-2 1/h expressed as weight hourly space velocity (WHSV), and/or 0.25-0.4 1/h.

14. The process of claim 1 , wherein the distilling is carried out at a pressure selected from a range of 1.8-2 bar, and at a T max of 250° C.

15. The process of claim 1 , wherein the recycle feed contains at least 95 wt-% olefin dimers.

16. A production unit configured for manufacturing olefin trimers, the production unit comprising:
a. at least one reactor unit configured to receive an acid catalyst;
b. at least one distillation column configured to separate isooctene from isododecene;
c. at least one reactor feed line in fluid connection with the reactor unit and a reservoir for olefin monomers;
d. at least one reactor outlet stream line in fluid connection with the reactor unit and the distillation column;
e. at least one recycle line in fluid connection with the at least one distillation column and the at least one reactor unit; and
f. a bottom product line in fluid connection with the at least one distillation column and a bottom product reservoir;
wherein the production unit comprises:
a first recycle line configured to recycle at least one of olefin monomers, diluent, and modifier through a first recycle line into the at least one reactor unit; and
a second recycle line configured to recycle olefin dimers to the at least one reactor unit.

17. The production unit of claim 16 , wherein the reactor unit comprises:
a plurality of reactor vessels, and wherein each reactor vessel downstream of a preceding upstream reactor vessel contains a larger amount of acid catalyst than a preceding upstream reactor vessel.

18. The production unit of claim 17 , comprising:
at least one heat exchange unit configured to recover heat from at least one line from the at least one distillation column.

19. The process of claim 2 , wherein the olefin monomer feed comprises:
at least one of the following: C4 olefins, C5 olefins, a mixed feed of C4 and C5 olefins, isobutene, 1-butene, cis-2-butene, trans-2-butene; and optionally inerts, n-butane, i-butane, butadiene, distillation fraction, or any mixture thereof.

Assignees

• Neste Oyj

Inventors

• Pyhälahti Antti
• Kanervo Jaana

Classifications

• C07C7/04

  by distillation · CPC title

• C07C2/28 Primary

  with ion-exchange resins · CPC title

• C07C2531/08

  Ion-exchange resins · CPC title

• C07C7/20

  Use of additives, e.g. for stabilisation · CPC title

• B01J31/08

  Ion-exchange resins · CPC title