Co-catalyst dispersion method

• US 4,665,143 A
• Filed: 04/12/1985
• Issued: 05/12/1987
• Est. Priority Date: 07/12/1982
• Status: Expired due to Term

• Current Assignee: Equistar Chemicals LP (Lyondellbasell Industries NV)
• Original Assignee: Cities Service Oil & Gas Corp.
• Inventors: Ahluwalia, Mohinder S., Junker, Michael L.
• Primary Examiner(s): Michl, Paul R.
• Application Number:
  US06/722,633
• Time in Patent Office: 760 Days
• Field of Search: 526/86, 526/87, 526/88
• US Class Current: 526/88
• CPC Class Codes: B01J 8/0015 Feeding of the particles in the reactor; Evacuation of the particles out of the reactor
• CPC Class Codes: C08F 10/02 Ethene
• CPC Class Codes: C08F 2/34 Polymerisation in gaseous state
• CPC Class Codes: Y10S 526/901 Monomer polymerized in vapor state in presence of transition metal containing catalyst

Abstract

In a gas-phase fluidized-bed polyethylene reactor using a Ziegler catalyst under operating conditions, a co-catalyst, such as triethyl aluminum, is added to the reactor by mixing the TEA with some of the feed ethylene and pumping the solution into the reactor.

Claims

1. A method for polymerizing olefins in a gas-phase, fluidized-bed, vertical polymerization reactor which is under operating conditions for polymerizing olefins using a polymerizing composition having at least one polymerizable olefin, said method comprising the steps of:

(a) introducing a Ziegler catalyst as a dry powder at a first injection point into the gas-phase, fluidized-bed, vertical polymerization reactor that contains a polymerizable composition comprising hydrogen, at least one polymerizable olefin, and a co-monomer olefin; and

(b) introducing, simultaneously with the introduction of the dry Ziegler catalyst, a mixture comprising a co-catalyst and a liquid olefin at a reaction-sustaining rate into said gas-phase, fluidized bed, vertical polymerization reactor at a second injection point located at least about two mixing distances away from the first injection point, wherein one mixing distance is the distance from an injection point beyond which only an equilibrium concentration of the catalyst or co-catalyst will be found, and whereby a polymerized olefin product is obtained with a decrease in the formation of polymerized olefin lumps in the gas-phase, fluidized-bed, vertical polymerization reactor, while simultaneously having an increase in the yield of the polymerized olefin product with respect to the amount of the co-catalyst used and a reduction in the formation of oil in the gas-phase, fluidized-bed, vertical polymerization reactor, when compared to a process not employing a dry Ziegler catalyst in a vertical reactor and not introducing the dry Ziegler catalyst, simultaneously with the introducing of the co-catalyst/liquid olefin mixture, at an injection point located at least about two mixing distances away from the injection point of the co-catalyst/liquid olefin mixture.

5. The method of claim 1 additionally comprising mixing the co-catalyst with the liquid olefin prior to said step (b).

8. The method of claim 1 wherein said liquid olefin is a vaporizable, polymerizable olefin.

11. The method of claim 1 wherein said Ziegler catalyst is vanadium-based.

14. The method of claim 1 wherein the olefin/co-catalyst weight ratio in the olefin/co-catalyst mixture varies from about 10/1 to about 100,000/1.

17. The method of claim 1 wherein the vertical reactor temperature varies from about 122°

F. (50°

C.) to about 248°

F. (120 °

C.).

20. The method of claim 1 wherein the vertical reactor pressure varies from about 100 psi (7.0 kg/cm²) to about 600 psi (42.2 kg/cm²).

23. The method of claim 1 wherein the liquid olefin/co-catalyst mixture comprises liquid ethylene as the liquid olefin and triethyl aluminum as the co-catalyst.

26. The method of claim 23 wherein the polymer yield by weight based on the weight of aluminum in the triethyl aluminum co-catalyst used is greater than about 15,000.

36. The process of claim 1 comprising two or more first injection points wherein the second injection point is located at least about two mixing distances away from any particular first injection point.

37. The process of claim 1 comprising two or more second injection points wherein the first injection point is located at least about two mixing distances away from any particular second injection point.

38. The process of claim 1 comprising two or more first injection points and two or more second injection points, wherein any particular first injection point is located at least two mixing distances from any second injection point.

51. The method of claim 11 wherein said vanadium-based Ziegler catalyst comprises VOCl₃.

2. A method for polymerizing olefins in a gas-phase, fluidized-bed, vertical polymerization reactor which is under operating conditions for polymerizing olefins using a polymerizing composition having at least one polymerizable olefin, said method comprising the step of:

(a) introducing a Ziegler catalyst as a dry powder at a first injection point into the gas-phase, fluidized-bed, vertical polymerization reactor that contains a polymerizable composition comprising hydrogen, at least one polymerizable olefin, and a co-monomer olefin; and

(b) introducing, simultaneously with the introduction of the dry Ziegler catalyst, a mixture comprising a co-catalyst and a liquid olefin at a reaction-sustaining rate into said gas-phase, fluidized-bed, vertical polymerization reactor at a second injection point located at least about two mixing distances away from the first injection point, wherein one mixing distance is the distance from an injection point beyond which only an equilibrium concentration of the catalyst or co-catalyst will be found.

6. The method of claim 2 additionally comprising mixing the co-catalyst with the liquid olefin prior to said step (b).

9. The method of claim 2 wherein said liquid olefin is a vaporizable, polymerizable olefin.

12. The method of claim 2 wherein said Ziegler catalyst is vanadium-based.

15. The method of claim 2 wherein the olefin/co-catalyst weight ratio in the olefin/co-catalyst mixture varies from about 10/1 to about 100,000/1.

18. The method of claim 2 wherein the vertical reactor temperature varies from about 122°

F. (50°

C.) to about 248°

F. (120°

C.).

21. The method of claim 2 wherein the vertical reactor pressure varies from about 100 psi (7.0 kg/cm) to about 600 psi (42.2 kg/cm).

24. The method of claim 2 wherein the liquid olefin/co-catalyst mixture comprises liquid ethylene as the liquid olefin and triethyl aluminum as the co-catalyst.

27. The method of claim 24 wherein the polymer yield by weight based on the weight of aluminum in the triethyl aluminum co-catalyst used is greater than about 15,000.

39. The process of claim 2 comprising two or more first injection points wherein the second injection point is located at least about two mixing distances away from any particular first injection point.

40. The process of claim 2 comprising two or more second injection points wherein the first injection point is located at least about two mixing distances away from any particular second injection point.

41. The process of claim 2 comprising two or more first injection points and two or more second injection points, wherein any particular first injection point is located at least two mixing distances from any second injection point, and any particular second injection point is located at least two mixing distances from any first injection point.

52. The method of claim 12 wherein said vanadium-based Ziegler catalyst comprises VOCl₃.

3. A method for polymerizing olefins in a gas-phase, vertical polymerization reactor which is under operating conditions for polymerizing olefins using a polymerizing composition having at least one polymerizable olefin, said method comprising the steps of:

(a) introducing a Ziegler catalyst as a dry powder at a first injection point into the gas-phase, vertical polymerization reactor that contains a polymerizable composition comprising hydrogen, at least one polymerizable olefin, and a co-monomer olefin; and

(b) introducing, simultaneously with the introduction of the dry Ziegler catalyst, a mixture comprising a co-catalyst and a liquid olefin at a reaction-sustaining rate into said gas-phase, vertical polymerization reactor at a second injection point located at least about two mixing distances away from the first injection point, wherein one mixing distance is the distance from an injection point beyond which only an equilibrium concentration of the catalyst or co-catalyst will be found.

7. The method of claim 3 additionally comprising mixing the co-catalyst with the liquid olefin prior to said step (b).

10. The method of claim 3 wherein said liquid olefin is a vaporizable, polymerizable olefin.

13. The method of claim 3 wherein said Ziegler catalyst is vanadium-based.

16. The method of claim 3 wherein the olefin/co-catalyst weight ratio in the olefin/co-catalyst mixture varies from about 10/1 to about 100,000/1.

19. The method of claim 3 wherein the vertical reactor temperature varies from about 122°

F. (50°

C.) to about 248°

F. (120°

C.)

22. The method of claim 3 wherein the vertical reactor pressure varies from about 100 psi (7.0 kg/cm²) to about 600 psi (42.2 kg/cm²).

25. The method of claim 3 wherein the liquid olefin/co-catalyst mixture comprises liquid ethylene as the liquid olefin and triethyl aluminum as the co-catalyst.

42. The process of claim 3 comprising two or more first injection points wherein the second injection point is located at least about two mixing distances away from any particular first injection point.

43. The process of claim 3 comprising two or more second injection points wherein the first injection point is located at least about two mixing distances away from any particular second injection point.

44. The process of claim 3 comprising two or more first injection points and two or more second injection points, wherein any particular first injection point is located at least two mixing distances from any second injection point.

53. The method of claim 13 wherein said vanadium-based Ziegler catalyst comprises VOCl₃.

4. A method for polymerizing ethylene in a gas-phase, fluidized-bed, vertical polymerization reactor comprising the steps of:

(a) introducing ethylene, hydrogen, and a co-monomer olefin into the gas-phase, fluidized-bed, vertical polymerization reactor;

(b) adding a vanadium-based Ziegler catalyst as a dry powder into the vertical polymerization reactor, at a first injection point, so as to attain and maintain a concentration in the fluidized-bed of from about 0.1 to about 100 ppm, by weight, of vanadium;

(c) forming a mixture comprising a triethyl aluminum co-catalyst and a liquid ethylene monomer or a liquid co-monomer selected from the group consisting of from C₃ to C₈ alpha olefins, wherein the liquid ethylene monomer or the liquid co-monomer/co-catalyst weight ratio varies from about 10/1 to about 100,000/1;

(d) attaining and maintaining an operating temperature in the vertical reactor of from about 122°

F. (50°

C.) to about 248°

F. (120°

C.);

(e) attaining and maintaining an operating pressure in the vertical reactor of from about 100 psi (7.0 kg/cmz) to about 600 psi (42.2 kg/cm²);

(f) introducing the mixture of step (c) at a reaction-sustaining rate into said gas-phase, fluidized-bed, vertical polymerization reactor at a second injection point located at least two mixing distances away from the first injection point, wherein one mixing distance is the distance from an injection point beyond which only an equilibrium concentration of the catalyst or co-catalyst will be found; and

whereby an ethylene polymer is produced with a reduction in the formation of oil in the gas-phase, fluidized-bed, vertical polymerization reactor, when compared to a process not employing a dry Ziegler catalyst in a vertical reactor and not introducing the dry Ziegler catalyst, simultaneously with the introducing of the co-catalyst/liquid olefin mixture, at an injection point located at least about two mixing distances away from the injection point of the co-catalyst/liquid olefin mixture; and

(g) removing ethylene polymer from the vertical polymerization reactor.

45. The process of claim 4 comprising two or more first injection points wherein the second injection point is located at least about two mixing distances away from any particular first injection point.

46. The process of claim 4 comprising two or more second injection points wherein the first injection point is located at least about two mixing distances away from any particular second injection point.

47. The process of claim 4 comprising two or more first injection points and two or more second injection points, wherein any particular first injection point is located at least two mixing distances from any second injection point.

28. In a process for the polymerization of at least one olefin utilizing a gas-phase, vertical polymerization reactor which is under operating conditions using a polymerizing composition having at least one polymerizable olefin which has been at least partially polymerized by the action of a Zielger catalyst that is introduced as a dry powder into the vertical reactor at a first injection point, the improvement comprising depositing a co-catalyst on the polymerized olefin by introducing a mixture comprising the co-catalyst and a liquid, vaporizable, polymerizable olefin at a reaction-sustaining rate into the gas-phase, vertical polymerization reactor at a second injection point located at least about two mixing distances away from the first injection point, wherein one mixing distance is the distance from an injection point beyond which only an equilibrium concentration of the catalyst or co-catalyst will be found.

29. The process of claim 28 wherein said gas-phase, vertical polymerization reactor includes a fluidized-bed.

30. The process of claim 28 wherein said liquid olefin/co-catalyst mixture comprises liquid ethylene as the liquid olefin and triethyl aluminum as the co-catalyst.

31. The process of claim 28 wherein the Ziegler catalyst is vanadium based.

32. The method of claim 28 wherein the olefin/co-catalyst weight ratio in the olefin/co-catalyst mixture varies from about 10/1 to about 100,000/1.

33. The method of claim 28 wherein the vertical reactor temperature varies from about 122°

F. to about 248°

F.

34. The method of claim 28 wherein the vertical reactor pressure varies from about 100 psi to about 600 psi.

35. The process of claim 30 wherein the polymer yield by weight based on the weight of aluminum in the triethyl aluminum co-catalyst used is greater than about 15,000.

48. The process of claim 28 comprising two or more first injection points wherein the second injection point is located at least about two mixing distances away from any particular first injection point.

49. The process of claim 28 comprising two or more second injection points wherein the first injection point is located at least about two mixing distances away from any particular second injection point.

50. The process of claim 28 comprising two or more first injection points and two or more second injection points, wherein any particular first injection point is located at least two mixing distances from any second injection point.

54. A method for polymerizing olefins in a gas-phase, fluidized-bed, vertical polymerization reactor which is under operating conditions for polymerizing olefins using a polymerizing composition having at least one polymerizable olefin, said method comprising the steps of:

(a) introducing a vanadium-based Ziegler catalyst as a dry powder at a first injection point into the gas-phase, fluidized-bed, vertical polymerization reactor that contains a polymerizable composition comprising hydrogen, at least one polymerizable olefin, and a co-monomer olefin; and

(b) introducing, simultaneously with the introduction of the dry vanadium-based Ziegler catalyst, a mixture comprising a co-catalyst and a liquid olefin at a reaction-sustaining rate into said gas-phase, fluidized bed, vertical polymerization reactor at a second injection point located at least about two mixing distances away from an injection point, wherein one mixing distance is the distance from an injection point beyond which a temperature equilibration within the vertical polymerization reactor exists due to an equilibrium concentration of the catalyst or co-catalyst.

55. A method for polymerizing ethylene in a gas-phase, fluidized-bed, vertical polymerization reactor comprising the steps of:

(a) introducing ethylene, hydrogen, chloroform, and optionally, one or more co-monomers selected from the group consisting of from C₃ to C₈ alpha olefins, into the gas-phase fluidized-bed, vertical polymerization reactor;

(b) adding a Ziegler catalyst as a dry powder into the vertical polymerization reactor, at a first injection point, wherein preparation of the Ziegler catalyst comprises the steps of (i) reacting a dry silica support with triethyl aluminum, (ii) and, subsequently, reacting the triethyl aluminum-dry silica support with a vanadium compound selected from the group consisting of VOCl₃, VCl₄, and mixtures thereof, and whereby the vanadium concentration in the fluidized-bed, vertical polymerization reactor is attained and maintained of from about 1 to about 4 ppm, by weight, of vanadium;

(c) attaining and maintaining an operating temperature in the vertical polymerization reactor of from about 175°

F. (80°

C.) to about 240°

F. (115°

C.);

(d) attaining and maintaining an operating pressure in the vertical polymerization reactor of from about 475 psi to about 525 psi;

(e) introducing a mixture comprising a triethyl aluminum co-catalyst and a liquid ethylene monomer or a liquid co-monomer selected from the group consisting of from C₃ to C₈ alpha olefins;

at a reaction-sustaining rate into said gas-phase, fluidized-bed, vertical polymerization reactor at a second injection point located at least two mixing distances away from the first injection point, wherein one mixing distance is the distance from an injection point beyond which only an equilibrium concentration of the catalyst or co-catalyst will be found, and whereby an ethylene polymer is produced with a reduction in the formation of oil in the gas-phase, fluidized-bed, vertical polymerization reactor, when compared to a process not employing a dry Ziegler catalyst in a vertical reactor and not introducing the dry Ziegler catalyst, simultaneously with the introducing of the co-catalyst/liquid olefin mixture, at an injection point located at least about two mixing distances away from the injection point of the co-catalyst/liquid olefin mixture; and

(f) removing ethylene polymer from the vertical polymerization reactor.

56. The method of claim 55 wherein the liquid ethylene monomer or the liquid co-monomer/co-catalyst weight ratio varies from about 10/1 to about 100,000/1.

57. A method for polymerizing ethylene in a gas-phase, fluidized-bed, vertical polymerization reactor comprising the steps of:

(a) introducing ethylene, hydrogen, chloroform, and propylene into the gas-phase fliudized-bed, vertical polymerization reactor;

(b) adding a Ziegler catalyst as a dry powder into the vertical polymerization reactor, at a first injection point, wherein preparation of the Ziegler catalyst comprises the steps of (i) reacting a dry silica support with triethyl aluminum, (ii) and, subsequently, reacting the triethyl aluminum-dry silica support with VOCl₃ whereby the vanadium concentration in the fluidized-bed, vertical polymerization reactor is attained and maintained at from about 1 to about 4 ppm, by weight, of vanadium;

(c) forming a mixture comprising a triethyl aluminum co-catalyst and a liquid ethylene monomer wherein the liquid ethylene monomer/co-catalyst weight ratio varies from about 30/1 to about 1,000/1;

(d) attaining and maintaining an operating temperature in the vertical polymerization reactor of from about 175°

F. (80°

C.) to about 240°

F. (115°

C.);

(e) attaining and maintaining an operating pressure in the vertical polymerization reactor of from about 475 psi to about 525 psi;

(f) introducing said mixture of step (c) at a reaction-sustaining rate into said gas-phase, fluidized-bed, vertical polymerization reactor at a second injection point located at least two mixing distances away from the first injection point, wherein one mixing distance is the distance from an injection point beyond which only an equilirium concentration of the catalyst or co-catalyst will be found, and whereby an ethylene polymer is produced with a reduction in the formation of oil in the gas-phase, fluidized-bed, vertical polymerization reactor, when compared to a process not employing a dry Ziegler catalyst in a vertical reactor and not introducing the dry Ziegler catalyst, simultaneously with the introducing of the co-catalyst/liquid olefin mixture, at an injection point located at least about two mixing distances away from the injection point of the co-catalyst/liquid olefin mixture; and

(g) removing ethylene polymer from the vertical polymerization reactor.

58. The method of claim 57 wherein said fluidized bed comprises said Ziegler catalyst, said co-catalyst, and ethylene polymer.