Process for transitioning between incompatible catalysts

• US 9,944,727 B2
• Filed: 12/22/2015
• Issued: 04/17/2018
• Est. Priority Date: 12/22/2014
• Status: Active Grant

• Current Assignee: SABIC Global Technologies BV (Government of Saudi Arabia)
• Original Assignee: SABIC Global Technologies BV (Government of Saudi Arabia)
• Inventors: Banat, Yahya, Al-Humydi, Abdulaziz Hamad, Fellahi, Said
• Primary Examiner(s): Teskin, Fred M
• Application Number:
  US15/537,997
• Publication Number:
  US 20170342174A1
• Time in Patent Office: 847 Days
• Field of Search: 526 83
• CPC Class Codes: B01J 2208/00752 Feeding
• CPC Class Codes: B01J 8/0015 Feeding of the particles in the reactor; Evacuation of the particles out of the reactor
• CPC Class Codes: B01J 8/24 according to "fluidised-bed" technique B01J8/20 takes precedence
• CPC Class Codes: C08F 10/00 Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
• CPC Class Codes: C08F 10/02 Ethene
• CPC Class Codes: C08F 2/34 Polymerisation in gaseous state
• CPC Class Codes: C08F 2/42 using short-stopping agents

Abstract

The invention relates to a process for transitioning from a first continuous polymerization reaction in a gas phase reactor conducted in the presence of a first catalyst to a second polymerization reaction conducted in the presence of a second catalyst in the gas phase reactor wherein the first and second catalysts are incompatible, the process comprising: (a) discontinuing the introduction of the first catalyst into the gas phase reactor; (b) introducing an effective amount of cyclohexylamine into the reactor to at least partially deactivate the first catalyst; (c) introducing an organometallic compound into the reactor and reacting the organometallic compound with cyclohexylamine; (d) introducing a gas composition into the reactor for the second polymerization reaction and (e) introducing the second catalyst into the reactor.

Claims

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

(a) discontinuing the introduction of the first catalyst into the gas phase reactor;

(b) introducing an effective amount of cyclohexylamine into the reactor to at least partially deactivate the first catalyst;

(c) introducing an organometallic compound into the reactor and reacting the organometallic compound with cyclohexylamine;

(d) introducing a gas composition into the reactor for the second polymerization reaction and

(e) introducing the second catalyst into the reactor.

2. The process according to claim 1, wherein the organometallic compound is a trialkylaluminum compound.

3. The process according to claim 1, further comprising the step (d2) after step (d) and before step (e), wherein step (d2) comprises introducing a reaction product of an aluminum compound of general formula (1)

4. The process according to claim 3, wherein the compound (1) is tri-isobutylaluminum and the compound (2) is cyclohexylamine or octadecylamine or cyclohexylamine, octadecylamine, 2-ethylhexylamine, ethylhexylamine, bis(4-amino cyclohexyl)methane, hexamethylenediamine, 1,3-benzenedimethanamine, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, 6-amino-1,3-dimethyluracil or a mixture thereof.

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

6. The process according to claim 1, wherein the second catalyst is a metallocene catalyst composition comprising a support containing a metallocene catalyst, a catalyst activator and an optional modifier.

7. The process according to claim 6, wherein the modifier is a reaction product of compound (1) being tri-isobutylaluminum and compound (2) being cyclohexylamine.

8. The process according to claim 6, wherein the metallocene catalyst is selected from the group consisting of:

[ortho-bis(4-phenyl-2-indenyl)-benzene]zirconiumdichloride, [ortho-bis(5-phenyl-2-indenyl)-benzene]zirconiumdichloride, [ortho-bis(2-indenyl)benzene]zirconiumdichloride, [ortho-bis(2-indenyl)benzene]hafniumdichloride, [ortho-bis(1-methyl-2-indenyl)-benzene]zirconiumdichloride, [2.2′

-(1.2-phenyldiyl)-1.1′

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

-(1,2-phenyldiyl)-1, 1′

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

-(1.2-phenyldiyl)-1.1′

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

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

-bis(2-indenyl)biphenyl]hafniumdichloride.

9. The process according to claim 1, wherein the first catalyst is introduced from a first catalyst feeding system and the second catalyst is introduced from a second catalyst feeding system separate from the first catalyst feeding system.

10. The process according to claim 1, wherein the polymerization is conducted in a fluidized bed reactor.

11. The process according to claim 1, wherein the first continuous polymerization reaction is operated in a condensed mode in which 5-17.4 wt % of the gas composition entering the gas phase reactor is liquid or a supercondensed mode in which more than 17.4 wt % of the gas composition entering the gas phase reactor is liquid.

12. The process according to claim 1, wherein the gas phase reactor is a multi-zone reactor operable in condensed mode, which multi-zone reactor comprises a first zone, a second zone, a third zone, a fourth zone and a distribution plate,

wherein the first zone is separated from the second zone by the distribution plate, wherein the multi-zone reactor is extended in the vertical direction,

wherein the second zone of the multi-zone reactor is located above the first zone and wherein the third zone of the multi-zone reactor is located above the second zone, and wherein the fourth zone of the multi-zone reactor is located above the third zone,

wherein the second zone contains an inner wall, wherein at least part of the inner wall of the second zone is either in the form of a gradually increasing inner diameter or a continuously opening cone, wherein the diameter or the opening increases in the vertical direction towards the top of the multi-zone reactor,

wherein the third zone contains an inner wall, wherein at least part of the inner wall of the third zone is either in the form of a gradually increasing inner diameter or a continuously opening cone, wherein the diameter or the opening increases in the vertical direction towards the top of the multi-zone reactor, and

wherein the largest diameter of the inner wall of the third zone is larger than the largest diameter of the inner wall of the second zone.

13. The process according to claim 1, wherein a reversible catalyst killer is introduced to render the first catalyst inactive.

14. The process according to claim 1, wherein the organometallic compound is triethylaluminum, trimethylaluminum, tri-isobutylaluminum, or tri-n-hexylaluminum.

15. The process according to claim 1, wherein the organometallic compound is tri-isobutylaluminum.

16. The process according to claim 6, wherein the optional modifier is present and is

[A] a reaction product of an aluminum compound of general formula (1)

17. The process according to claim 7, wherein the metallocene catalyst is selected from the group consisting of:

[ortho-bis(4-phenyl-2-indenyl)-benzene]zirconiumdichloride, [ortho-bis(5-phenyl-2-indenyl)-benzene]zirconiumdichloride, [ortho-bis(2-indenyl)benzene]zirconiumdichloride, [ortho-bis(2-indenyl)benzene]hafniumdichloride, [ortho-bis(1-methyl-2-indenyl)-benzene]zirconiumdichloride, [2.2′

-(1.2-phenyldiyl)-1.1′

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

-(1,2-phenyldiyl)-1,1′

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

-(1.2-phenyldiyl)-1.1′

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

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

-bis(2-indenyl)biphenyl]hafniumdichloride.

18. The process according to claim 13, wherein the reversible catalyst killer is CO.

19. The process according to claim 17,

wherein the first catalyst is introduced from a first catalyst feeding system and the second catalyst is introduced from a second catalyst feeding system separate from the first catalyst feeding system;

wherein the polymerization is conducted in a fluidized bed reactor; and

wherein the first continuous polymerization reaction is operated in a condensed mode in which 5-17.4 wt % of the gas composition entering the gas phase reactor is liquid or a supercondensed mode in which more than 17.4 wt % of the gas composition entering the gas phase reactor is liquid.

20. The process according to claim 19, wherein the gas phase reactor is a multi-zone reactor operable in condensed mode, which multi-zone reactor comprises a first zone, a second zone, a third zone, a fourth zone and a distribution plate,

wherein the first zone is separated from the second zone by the distribution plate, wherein the multi-zone reactor is extended in the vertical direction,

wherein the second zone of the multi-zone reactor is located above the first zone and wherein the third zone of the multi-zone reactor is located above the second zone, and wherein the fourth zone of the multi-zone reactor is located above the third zone,

wherein the second zone contains an inner wall, wherein at least part of the inner wall of the second zone is either in the form of a gradually increasing inner diameter or a continuously opening cone, wherein the diameter or the opening increases in the vertical direction towards the top of the multi-zone reactor,

wherein the third zone contains an inner wall, wherein at least part of the inner wall of the third zone is either in the form of a gradually increasing inner diameter or a continuously opening cone, wherein the diameter or the opening increases in the vertical direction towards the top of the multi-zone reactor, and

wherein the largest diameter of the inner wall of the third zone is larger than the largest diameter of the inner wall of the second zone.