Process for transitioning between incompatible catalysts

• US 10,494,454 B2
• Filed: 03/24/2016
• Issued: 12/03/2019
• Est. Priority Date: 03/24/2015
• Status: Active Grant

• Current Assignee: SABIC Global Technologies BV (Government of Saudi Arabia)
• Original Assignee: SABIC Global Technologies BV (Government of Saudi Arabia)
• Inventors: Althukair, Mohammed
• Primary Examiner(s): Branch, Catherine S
• Application Number:
  US15/560,785
• Publication Number:
  US 20180051102A1
• Time in Patent Office: 1,349 Days
• Field of Search: None
• CPC Class Codes: B01J 8/24 according to "fluidised-bed" technique B01J8/20 takes precedence
• CPC Class Codes: C08F 2/001 Multistage polymerisation processes characterised by a change in reactor conditions without deactivating the intermediate polymer C08F295/00, C08F297/00 take precedence
• CPC Class Codes: C08F 2/34 Polymerisation in gaseous state
• CPC Class Codes: C08F 2/42 using short-stopping agents
• CPC Class Codes: C08F 210/14 Monomers containing five or more carbon atoms
• CPC Class Codes: C08F 210/16 Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
• CPC Class Codes: C08F 2410/01 Additive used together with the catalyst, excluding compounds containing Al or B
• CPC Class Codes: C08F 2410/05 Transitioning, i.e. transition from one catalyst to another with use of a deactivating agent
• CPC Class Codes: C08F 2410/08 Presence of a deactivator
• CPC Class Codes: C08F 2420/09 Cyclic bridge, i.e. Cp or analog where the bridging unit linking the two Cps or analogs is part of a cyclic group
• CPC Class Codes: C08F 4/022 Magnesium halide as support anhydrous or hydrated or complexed by means of a Lewis base for Ziegler-type catalysts
• CPC Class Codes: C08F 4/025 Metal oxides
• CPC Class Codes: C08F 4/22 of chromium, molybdenum or tungsten
• CPC Class Codes: C08F 4/6192 containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
• CPC Class Codes: C08F 4/6557 and metals of C08F4/64 or compounds thereof
• CPC Class Codes: C08F 4/65912 in combination with an organoaluminium compound
• CPC Class Codes: C08F 4/65916 supported on a carrier, e.g. silica, MgCl2, polymer
• CPC Class Codes: C08F 4/65927 two cyclopentadienyl rings being mutually bridged
• CPC Class Codes: C08F 4/69 Chromium, molybdenum, tungsten or compounds thereof

Abstract

The invention relates to a process for transitioning from a first continuous polymerization reaction in a reactor, for example a gas-phase reactor conducted in the presence of a first catalyst to a second continuous polymerization reaction in the reactor conducted in the presence of a second catalyst, wherein the first and second catalysts are incompatible, the process comprising: (a) discontinuing the introduction of the first catalyst from a catalyst feeding system into a reactor and emptying the catalyst feeding system of the first catalyst; (b) introducing a first catalyst killer to the reactor to substantially deactivate the first catalyst in the reactor; (c) introducing a second catalyst killer to the catalyst feeding system to substantially deactivate the first catalyst in the catalyst feeding system; (d) introducing a second catalyst to the catalyst feeding system and (e) introducing the second catalyst to the reactor from the catalyst feeding system, wherein the second catalyst killer is the same as or different from the first catalyst killer.

Claims

1. A process for transitioning from a first continuous polymerization reaction, in a reactor, conducted in the presence of a first catalyst to a second continuous polymerization reaction in the reactor conducted in the presence of a second catalyst, wherein the first and second catalysts are incompatible, the process comprising:

(a) discontinuing the introduction of the first catalyst from a catalyst feeding system into a reactor and emptying the catalyst feeding system of the first catalyst;

(b) introducing a first catalyst killer to the reactor to substantially deactivate the first catalyst in the reactor;

(c) introducing a second catalyst killer to the catalyst feeding system to substantially deactivate the first catalyst in the catalyst feeding system;

(c2) introducing a first portion of a second catalyst to the catalyst feeding system to remove any remaining second catalyst killer by the reaction of the second catalyst and the second catalyst killer;

(c3) removing a reaction product from the reaction of the second catalyst with the second catalyst killer from the catalyst feeding system;

(d) introducing a second portion of the second catalyst to the catalyst feeding system and

(e) introducing the second catalyst to the reactor from the catalyst feeding system,

wherein the second catalyst killer is the same as or different from the first catalyst killer.

2. The process according to claim 1, wherein the first catalyst is a Ziegler-Natta catalyst and the second catalyst is a metallocene catalyst or wherein the first catalyst is a chromium catalyst and the second catalyst is a metallocene catalyst.

3. The process according to claim 1, wherein the second catalyst is a metallocene catalyst selected from the group consisting of:

[ortho-bis(4-phenyl-2-indenyl)-benzene]zirconium dichloride, [ortho-bis(5-phenyl-2-indenyl)-benzene]zirconium dichloride, [ortho-bis(2-indenyl)benzene]zirconium dichloride, [ortho-bis(2-indenyl)benzene]hafnium dichloride, [ortho-bis(1-methyl-2-indenyl)-benzene]zirconium dichloride, [2.2′

-(1.2-phenyldiyl)-1.1′

-dimethylsilyl-bis(indene)]zirconiumdichloride, [2,2′

-(1 ,2-phenyldiyl)-1, 1′

-diphenylsilyl-bis(indene)]zirconium dichloride, [2,2′

-(1.2-phenyldiyl)-1.1 ′

-(1.2-ethanediyl)-bis(indene)]zirconium dichloride, [2.2′

-bis(2-indenyl)biphenyl]zirconium dichloride and [2,2′

-bis(2-indenyl)biphenyl]hafnium dichloride.

4. The process according to claim 1, wherein the first catalyst is a chromium catalyst.

5. The process according to claim 1, wherein the first catalyst is a Ziegler-Natta catalyst made by a process comprising:

i. contacting a dehydrated support having hydroxyl groups with a magnesium compound having the general formula MgR¹R², wherein R¹ and R² are the same or different and are independently selected from the group consisting of an alkyl group, alkenyl group, alkadienyl group, aryl group, alkaryl group, alkenylaryl group and alkadienylaryl group;

ii. contacting the product obtained in step (i) with modifying compounds (I), (II) and (III), wherein;

(I) is at least one compound selected from the group consisting of carboxylic acid, carboxylic acid ester, ketone, acyl halide, aldehyde and alcohol;

(II) is a compound having the general formula R¹¹_f(R¹²O)_gSiX_h, wherein f, g and h are each integers from 0 to 4 and the sum of f, g and h is equal to 4 with a proviso that when h is equal to 4 then modifying compound (I) is not an alcohol, Si is a silicon atom, O is an oxygen atom, X is a halide atom and R¹¹ and R¹² are the same or different and are independently selected from the group comprising an alkyl group, alkenyl group, alkadienyl group, aryl group, alkaryl group, alkenylaryl group and alkadienylaryl group;

(III) is a compound having the general formula (R¹³O)₄M, wherein M is a titanium atom, a zirconium atom or a vanadium atom, O is an oxygen atom and R¹³ is selected from the group comprising an alkyl group, alkenyl group, alkadienyl group, aryl group, alkaryl group, alkenylaryl group and alkadienylaryl group; and

iii. contacting the product obtained in step (ii) with a titanium halide compound having the general formula TiX₄, wherein Ti is a titanium atom and X is a halide atom.

6. The process according to claim 1, wherein the second catalyst killer is an irreversible catalyst killer.

7. The process according to claim 1, wherein the second catalyst killer is a reversible catalyst killer.

8. The process according to claim 1, further comprising the following step between steps (c) and (c2):

(c1) purging the catalyst feeding system with an inert gas to remove at least a portion of the second catalyst killer.

9. The process according to claim 1, wherein the first polymerization reaction and/or the second polymerization reaction is conducted in a fluidized bed reactor.

10. The process according to claim 1, wherein the first polymerization reaction and/or the second polymerization reaction is a continuous polymerization of one or more α

-olefin monomers of which at least one is ethylene or propylene.

11. The process according to claim 1, wherein the first polymerization and/or the second polymerization produces a polyethylene;

or a polypropylene homopolymer or a propylene random copolymer.

12. A process for transitioning from a first continuous polymerization reaction, in a reactor, conducted in the presence of a first catalyst to a second continuous polymerization reaction in the reactor conducted in the presence of a second catalyst, wherein the first and second catalysts are incompatible, the process comprising:

(a) discontinuing the introduction of the first catalyst from a catalyst feeding system into a reactor and emptying the catalyst feeding system of the first catalyst;

(b) introducing a first catalyst killer to the reactor to substantially deactivate the first catalyst in the reactor;

(c) introducing a second catalyst killer to the catalyst feeding system to substantially deactivate the first catalyst in the catalyst feeding system;

(d) introducing a second catalyst to the catalyst feeding system and

(e) introducing the second catalyst to the reactor from the catalyst feeding system,

wherein the second catalyst killer is the same as or different from the first catalyst killer, and

wherein the first catalyst is a chromium catalyst supported on silica.

13. The process according to claim 12, wherein the second catalyst is a metallocene catalyst.

14. The process according to claim 12, wherein the second catalyst is a metallocene catalyst selected from the group consisting of:

[ortho-bis(4-phenyl-2-indenyl)-benzene]zirconium dichloride, [ortho-bis(5-phenyl-2-indenyl)-benzene]zirconium dichloride, [ortho-bis(2-indenyl)benzene]zirconium dichloride, [ortho-bis(2-indenyl)benzene]hafnium dichloride, [ortho-bis(1-methyl-2-indenyl)-benzene]zirconium dichloride, [2.2′

-(1.2-phenyldiyl)-1.1′

-dimethylsilyl-bis(indene)]zirconiumdichloride, [2,2′

-(1 ,2-phenyldiyl)-1, 1′

-diphenylsilyl-bis(indene)]zirconium dichloride, [2,2′

-(1.2-phenyldiyl)-1.1 ′

-(1.2-ethanediyl)-bis(indene)]zirconium dichloride, [2.2′

-bis(2-indenyl)biphenyl]zirconium dichloride, and [2,2′

-bis(2-indenyl)biphenyl] hafnium dichloride.

15. The process according to claim 12, wherein the second catalyst killer is an irreversible catalyst killer.

16. The process according to claim 12, wherein the second catalyst killer is a reversible catalyst killer.

17. The process according to claim 12, further comprising the following step between steps (c) and (d):

(c1) purging the catalyst feeding system with an inert gas to remove the second catalyst killer.

18. The process according to claim 12, wherein the first polymerization reaction and/or the second polymerization reaction is conducted in a fluidized bed reactor.

19. The process according to claim 12, wherein the first polymerization reaction and/or the second polymerization reaction is a continuous polymerization of one or more α

-olefin monomers of which at least one is ethylene or propylene.

20. The process according to claim 12, wherein the first polymerization and/or the second polymerization produces a polyethylene;

or a polypropylene homopolymer or a propylene random copolymer.