Olefin Oligomerizations Using Chemically-Treated Solid Oxides

Patent metadata

Field	Value
Publication number	US-2017174584-A1
Application number	US-201514977728-A
Country	US
Kind code	A1
Filing date	Dec 22, 2015
Priority date	Dec 22, 2015
Publication date	Jun 22, 2017
Grant date	—

Abstract

Oligomerization processes include the steps of introducing a monomer containing a C 3 to C 30 olefin and a chemically-treated solid oxide into a reaction zone, and oligomerizing the monomer to form an oligomer product in the reaction zone. Fluorided silica-coated alumina and fluorided-chlorided silica-coated alumina are illustrative chemically-treated solid oxides that can be used in the oligomerization processes.

First claim

1 . A process comprising:
(i) introducing a monomer comprising a C 3 to C 30 olefin and a chemically-treated solid oxide into a reaction zone, the chemically-treated solid oxide comprising a silica-coated alumina treated with an electron-withdrawing anion; and (ii) oligomerizing the monomer to form an oligomer product in the reaction zone; wherein the oligomerizing step is conducted in the substantial absence of organoaluminum compounds and the absence of metallocene compounds; and wherein the oligomer product comprises at least 30 wt. % dimers.

2 . The process of claim 1 , wherein the chemically-treated solid oxide comprises fluorided silica-coated alumina.

3 . The process of claim 2 , wherein a conversion of the monomer to the oligomer product is greater than that of a comparable process using sulfated alumina, under the same oligomerization conditions.

4 . The process of claim 1 , wherein the chemically-treated solid oxide comprises fluorided-chlorided silica-coated alumina.

5 . The process of claim 4 , wherein a conversion of the monomer to the oligomer product is greater than that of a comparable process using sulfated alumina, under the same oligomerization conditions.

6 . The process of claim 1 , wherein:
the silica-coated alumina comprises from 20 to 45 wt. % silica, based on the weight of the silica-coated alumina; and the electron-withdrawing anion comprises sulfate, fluoride, chloride, or any combination thereof.

7 . The process of claim 1 , wherein the monomer comprises at least 75 wt. % C 3 to C 18 alpha olefins.

8 . The process of claim 1 , wherein the monomer comprises propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, or any combination thereof.

9 . The process of claim 1 , wherein the monomer comprises propylene, and wherein the oligomer product comprises at least 40 wt. % trimers and/or a weight ratio of trimers to tetramers in the oligomer product is greater than 1:1.

10 . The process of claim 1 , wherein the monomer comprises 1-butene, 1-pentene, 1-hexene, or any combination thereof and wherein the oligomer product comprises at least 40 wt. % trimers and/or a weight ratio of trimers to dimers in the oligomer product is greater than 1:1.

11 . The process of claim 1 , wherein the monomer comprises 1-octene, 1-decene, 1-dodecene, or any combination thereof, and wherein a weight ratio of dimers to trimers in the oligomer product is greater than 1:1.

12 . A process comprising:
(i) introducing a monomer comprising a C 12 to C 16 olefin and a chemically-treated solid oxide into a reaction zone, the chemically-treated solid oxide comprising sulfated alumina; and (ii) oligomerizing the monomer to form an oligomer product in the reaction zone; wherein the oligomerizing step is conducted in the substantial absence of organoaluminum compounds and the absence of metallocene compounds; and wherein the oligomer product comprises from 30 to 98 wt. % dimers.

13 . The process of claim 12 , wherein a weight ratio of dimers to trimers in the oligomer product is from 2:1 to 6:1.

14 . The process of claim 12 , wherein the oligomer product comprises from 55 to 95 wt. % dimers and/or a weight ratio of dimers to trimers in the oligomer product is from 1.5:1 to 8:1.

15 . The process of claim 1 , wherein the monomer comprises 1-dodecene.

16 - 20 . (canceled)

21 . A process comprising:
(i) introducing a monomer comprising a C 3 to C 8 olefin and a chemically-treated solid oxide into a reaction zone, the chemically-treated solid oxide comprising a silica-coated alumina treated with an electron-withdrawing anion; and (ii) oligomerizing the monomer to form an oligomer product in the reaction zone; wherein the oligomerizing step is conducted in the substantial absence of organoaluminum compounds and the absence of metallocene compounds; and wherein the oligomer product comprises at least 30 wt. % trimers.

22 . The process of claim 21 , wherein the electron-withdrawing anion comprises sulfate, fluoride, chloride, or any combination thereof.

23 . The process of claim 21 , wherein the monomer comprises propylene, and wherein a weight ratio of trimers to tetramers in the oligomer product is in a range from 1.05:1 to 1.6:1.

24 . The process of claim 23 , wherein:
the oligomer product comprises from 35 to 60 wt. % trimers; and the chemically-treated solid oxide comprises fluorided silica-coated alumina and/or fluorided-chlorided silica-coated alumina.

25 . The process of claim 21 , wherein the monomer comprises 1-hexene, and wherein a weight ratio of trimers to dimers in the oligomer product is in a range from 1.02:1 to 2:1.

26 . The process of claim 25 , wherein:
the oligomer product comprises from 35 to 65 wt. % trimers; and the chemically-treated solid oxide comprises fluorided silica-coated alumina and/or fluorided-chlorided silica-coated alumina.

Assignees

• Chevron Phillips Chemical Co Lp

Inventors

• Yang Qing
• Kilgore Uriah J
• Mcdaniel Max P
• Small Brooke L
• Hope Kenneth D
• Baralt Eduardo J

Classifications

• C07C2521/04

  Alumina · CPC title

• C07C2527/10

  Chlorides · CPC title

• C07C2527/12

  Fluorides · CPC title

• C07C2527/06

  Halogens; Compounds thereof · CPC title

• C07C2/10 Primary

  with metal oxides · CPC title