Oligomerization process

Patent metadata

Field	Value
Publication number	US-11873263-B2
Application number	US-202017603848-A
Country	US
Kind code	B2
Filing date	Mar 10, 2020
Priority date	Apr 17, 2019
Publication date	Jan 16, 2024
Grant date	Jan 16, 2024

Abstract

The present invention concerns a process for oligomerizing an olefin feedstock to form an oligomerization product, and a method of controlling such an oligomerization process. The process comprises oligomerizing propylene to form a Cn olefin, including contacting a feed stream comprising propylene and a recycle fraction with a solid phosphoric acid oligomerization catalyst under effective oligomerization conditions in an oligomerization reactor to produce an oligomerization effluent; and fractionating the oligomerization effluent to obtain a product fraction and the recycle fraction, the product fraction comprising the Cn olefin and the recycle fraction comprising a Cn-3 olefin; wherein the recycle fraction comprises at least 80 wt % of the Cn-3 olefin, based on the weight of the recycle fraction; and wherein n is 9, or 12.

First claim

The invention claimed is:

1. A process for oligomerizing propylene to form a C n , olefin, wherein the process comprises:
contacting a feed stream comprising X wt % propylene, Y wt % an alkane diluent, and Z wt % a recycle fraction with a solid phosphoric acid oligomerization catalyst under effective oligomerization conditions in an oligomerization reactor to produce an oligomerization effluent; and
fractionating the oligomerization effluent to obtain a product fraction and the recycle fraction, the product fraction comprising the C n , olefin and the recycle fraction comprising a C n-3 olefin;
wherein the recycle fraction comprises at least 80 wt % of the C n-3 olefin, based on the weight of the recycle fraction;
wherein X+Y+Z=100 and X is from 25 to 60, Y is from 5 to 50, and Z is from 20 to 70; and
wherein the process comprises:
at least one period T1 during which n is 9 and X, Y and Z remain constant; and
at least one period T2 during which n is 12 and X, Y, and Z remain constant, wherein at least two of X, Y and Z during period T2 differ by at least 5 from X, Y and Z during period T1.

2. The process according to claim 1 , wherein the recycle fraction comprises at least 90 wt % of a C n-3 olefin, based on the weight of the recycle fraction.

3. The process according to claim 1 , wherein T1 and T2 are each at least 24 hours.

4. The process according to claim 1 , wherein the effective oligomerization conditions include conditions effective for a propylene per pass conversion of at least 90 wt %, based on the weight of propylene fed to the oligomerization reactor.

5. The process according to claim 1 , wherein the effective oligomerization conditions include a temperature of at least 175° C. and a pressure of at least 60 barg.

6. The process according to claim 1 , wherein propylene and the recycle fraction are present in the feed stream at a propylene:recycle fraction ratio of from 10:1 to 1:2, by weight.

7. The process according to claim 1 , wherein X is from 30 to 50.

8. The process according to claim 1 , wherein Y is from from 10 to 50.

9. The process according to claim 1 , wherein the alkane diluent is propane.

10. The process according to claim 1 , wherein Z is from 30 to 50.

11. The process according to claim 1 , wherein wherein the at least two of X, Y and Z during period T2 differ by at least 10 from X, Y and Z during period T1.

12. The process according to claim 1 , wherein T1 and T2 are each at least 24 hours.

13. The process according to claim 1 , wherein all of X, Y and Z during period T2 differ by at least 5, optionally 10, from X, Y and Z during period T1.

14. The process according to claim 1 , wherein the propylene and the recycle fraction are present in the feed stream at a propylene:recycle fraction ratio of from 8:1 to 2:3, by weight.

15. The process according to claim 1 , wherein the propylene and the recycle fraction are present in the feed stream at a propylene:recycle fraction ratio of from 2:1 to 2:3, by weight.

16. The process according to claim 1 , wherein the propylene and the recycle fraction are present in the feed stream at a propylene:recycle fraction ratio of from 5:1 to 1:1, by weight.

17. The process according to claim 1 , wherein:
during one of period T1 and period T2, Y is greater than X and Z; and
during one of period T1 and period T2, Y is less than X and Z.

18. The process according to claim 1 , comprising increasing a selectivity for C9 during the period T1 relative to the period T2 at least in part by differing the at least two of X, Y, Z by at least 5 from X, Y, Z during period T2.

19. The process according to claim 1 , comprising increasing a selectivity for C12 during the period T2 relative to the period T1 at least in part by differing the at least two of X, Y, Z by at least 5 from X, Y, Z during period T1.

20. The process according to claim 1 , wherein the propylene and the recycle fraction are present in the feed stream at a propylene:recycle fraction ratio of 1:1, by weight, during both period T1 and period T2.

Assignees

• Exxonmobil Chemical Patents Inc

Inventors

• Wiersum Andrew
• Hamilton Paul
• Martens Luc
• Garcia Frutos Sara
• Janssen Marcel

Classifications

• C07C2/18 Primary

  Acids of phosphorus; Salts thereof; Phosphorus oxides · CPC title

• B01J31/0257

  Phosphorus acids or phosphorus acid esters · CPC title

• C07C2527/173

  Phosphoric acid or other acids with the formula Hn+2PnO3n+1 · CPC title