Process Improvements In Selective Ethylene Oligomerizations

Patent metadata

Field	Value
Publication number	US-2017342000-A1
Application number	US-201615166991-A
Country	US
Kind code	A1
Filing date	May 27, 2016
Priority date	May 27, 2016
Publication date	Nov 30, 2017
Grant date	—

Abstract

Disclosed are processes, systems, and reaction systems for the oligomerization of ethylene to form an oligomer product in a reaction zone using a catalyst system having i) a chromium component comprising an N 2 -phosphinyl amidine chromium compound complex, an N 2 -phosphinyl formamidine chromium compound complex, an N 2 -phosphinyl guanidine chromium compound complex, or any combination thereof, and ii) an aluminoxane. Ethylene can be contacted with an organic reaction medium to form an ethylene feedstock mixture prior to contact with the catalyst system. The ethylene feedstock mixture can be contacted with the catalyst system inside or outside of the reaction zone.

First claim

1 . A process comprising:
contacting 1) ethylene, 2) a catalyst system comprising i) a chromium component comprising an N 2 -phosphinyl amidine chromium compound complex, an N 2 -phosphinyl formamidine chromium compound complex, an N 2 -phosphinyl guanidine chromium compound complex, or any combination thereof, and ii) an aluminoxane, 3) an organic reaction medium, and optionally 4) hydrogen; and forming an oligomer product in a reaction zone, wherein the ethylene is contacted with at least a portion of the organic reaction medium to form an ethylene feedstock mixture prior to contacting ethylene with the catalyst system.

2 . The process of claim 1 , wherein the ethylene and the organic reaction medium are dispersed in the ethylene feedstock mixture prior to contact of the ethylene feedstock mixture with the catalyst system.

3 . The process of claim 1 , wherein the catalyst system and the ethylene feedstock mixture are contacted prior to entering the reaction zone.

4 . The process of claim 1 , wherein the catalyst system is introduced into the reaction zone separately from the ethylene feedstock mixture.

5 . The process of claim 1 , wherein the oligomer product comprises hexenes and/or octenes.

6 . The process of claim 1 , wherein the ethylene feedstock mixture, the catalyst system, and optionally, hydrogen are periodically or continuously introduced into the reaction zone and a reaction zone effluent comprising the oligomer product is periodically or continuously removed from the reaction zone.

7 . The process of claim 1 , wherein a mass of polymer per mass of oligomer in the reaction zone is less than a mass of polymer per mass of oligomer in the reaction zone of an otherwise similar process which does not: i) contact ethylene with the at least a portion of the organic reaction medium prior to contact of ethylene with the catalyst system, and/or ii) introduce or feed the ethylene feedstock mixture into the reaction zone separately from the catalyst system.

8 . The process of claim 1 , having a productivity greater than a productivity in an otherwise similar process which does not: i) contact ethylene with the at least a portion of the organic reaction medium prior to contact of ethylene with the catalyst system, and/or ii) introduce or feed the ethylene feedstock mixture into the reaction zone separately from the catalyst system.

9 . A process comprising:
introducing a catalyst system to a reaction zone, the catalyst system comprising i) a chromium component comprising an N-phosphinyl amidine chromium compound complex, an N 2 -phosphinyl formamidine chromium compound complex, an N 2 -phosphinyl guanidine chromium compound complex, or any combination thereof, and ii) an aluminoxane; introducing an ethylene feedstock mixture to the reaction zone separately from the catalyst system, the ethylene feedstock mixture comprising ethylene and at least a portion of an organic reaction medium used in the process, wherein the ethylene feedstock mixture is substantially free of the catalyst system; optionally introducing hydrogen to the reaction zone; and contacting the catalyst system and the ethylene feedstock mixture in the reaction zone to form an oligomer product.

10 . The process claim 9 , wherein the oligomer product comprises hexenes and/or octenes.

11 . The process of claim 9 , wherein the ethylene feedstock mixture, the catalyst system, and optionally, hydrogen are periodically or continuously introduced into the reaction zone and a reaction zone effluent comprising the oligomer product is periodically or continuously removed from the reaction zone.

12 . The process of claim 9 , wherein a mass of polymer per mass of oligomer in the reaction zone is less than a mass of polymer per mass of oligomer in the reaction zone of an otherwise similar process which does not: i) contact ethylene with the at least a portion of the organic reaction medium prior to contact of ethylene with the catalyst system, and/or ii) introduce or feed the ethylene feedstock mixture into the reaction zone separately from the catalyst system.

13 . The process of claim 9 , having a productivity greater than a productivity in an otherwise similar process which does not: i) contact ethylene with the at least a portion of the organic reaction medium prior to contact of ethylene with the catalyst system, and/or ii) introduce or feed the ethylene feedstock mixture into the reaction zone separately from the catalyst system.

14 . A reaction system comprising;
a reaction zone; a first reaction zone inlet configured to introduce a catalyst system comprising i) a chromium component comprising an N 2 -phosphinyl amidine chromium compound complex, an N 2 -phosphinyl formamidine chromium compound complex, an N 2 -phosphinyl guanidine chromium compound complex, or any combination thereof, and ii) an aluminoxane to the reaction zone, a second reaction zone inlet configured to introduce an ethylene feedstock mixture comprising ethylene and an organic reaction medium to the reaction zone, wherein the ethylene feedstock mixture is substantially free of the catalyst system, and one or more reaction zone outlets configured to discharge a reaction zone effluent comprising an oligomer product from the reaction zone.

15 . The reaction system of claim 14 , further comprising:
a catalyst system feed line flowing the catalyst system to the first reaction zone inlet; an ethylene feed line comprising the ethylene; an organic reaction medium feed line comprising the organic reaction medium, wherein the organic reaction medium feed line and the ethylene feed line combine to yield the ethylene feedstock mixture which is introduced to the second reaction zone inlet.

16 . The reaction system of claim 15 , further comprising:
a pump in fluid communication with the second reaction zone inlet and which is located upstream of a point where the ethylene feed line and the organic reaction medium feed line join to produce the ethylene feedstock mixture.

17 . The reaction system of claim 15 further comprising;
a mixing device positioned between i) the joining of the ethylene feed line and the organic reaction medium feed line, and ii) the second reaction zone inlet, to disperse the ethylene and the organic reaction medium in the ethylene feedstock mixture prior to the ethylene feedstock mixture entering the reaction zone.

18 . The reaction system of claims 14 , wherein the first reaction zone inlet is configured to periodically or continuously introduce the catalyst system to the reaction zone, the second reaction zone inlet is configured to periodically or continuously introduced the ethylene feedstock mixture to the reaction zone, and the one or more reaction zone outlets is configured to periodically or continuously discharge the reaction zone effluent comprising the oligomer product from the reaction zone.

19 . The process of claim 1 , wherein the reaction zone comprises one or more reactors selected from an autoclave reactor, a continuous stirred tank reactor, a loop reactor, a gas phase reactor, a solution reactor, a tubular reactor, a recycle reactor, a bubble reactor, and any combination thereof.

20 . A reaction system comprising:
a reaction zone having a reaction zone inlet; an ethylene feed line in fluid communication with the reaction zone inlet and comprising ethylene; an organic reaction medium feed line in fluid communication with the reaction zone inlet and comprising an organic reaction medium, wherein the ethylene feed line and the

Assignees

• Chevron Phillips Chemical Co Lp

Inventors

• Bischof Steven M
• Sydora Orson L
• Fern Jared T
• Kilgore Uriah J
• HUTCHISON Steven Ross
• Rios Ray
• Fernandez Eric R

Classifications

• C07F11/005

  compounds without a metal-carbon linkage · CPC title

• C07F9/46

  Phosphinous acids [R2POH], [R2P(= O)H]: Thiophosphinous acids {including[R2PSH]; [R2P(=S)H]; Aminophosphines [R2PNH2]; Derivatives thereof} · CPC title

• C07F9/6561

  containing systems of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring or ring system, with or without other non-condensed hetero rings · CPC title

• C08F4/69068

  PN · CPC title

• C07C2531/24

  Phosphines · CPC title