US4665143A
Expired / Lapsed
US
⏱️ 0.0 years remaining
Co-catalyst dispersion method
Assignee: USI CHEMICALS Co Inc
•
Filing: 1985-04-12
•
Granted: 1987-05-12
•
Expires: 2005-04-12
Abstract
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.
Inventors
- 👤 Mohinder S. Ahluwalia
- 👤 Michael L. Junker
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-31 19:17
CPC Classifications
B; B01; B01J; B01J8/00; B01J8/0015; C; C08; C08F; C08F10/00; C08F10/02; Y; Y10; Y10S; Y10S526/00; Y10S526/901
Claims Analysis
Total Claims: 66
Claim 1
Independent Claim
263 words
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.
Claim 2
Independent Claim
263 words
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.
Claim 3
Independent Claim
148 words
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.
Claim 4
Independent Claim
148 words
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.
Claim 5
Independent Claim
145 words
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.
Claim 6
Independent Claim
145 words
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.
Claim 7
Independent Claim
318 words
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 C 3 to C 8 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/cm 2 ); (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.
Claim 8
Independent Claim
318 words
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 C 3 to C 8 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/cm 2 ); (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.
Claim 9
Dependent Claim
19 words
The method of claim 1 additionally comprising mixing the co-catalyst with the liquid olefin prior to said step (b).
Claim 10
Dependent Claim
19 words
The method of claim 2 additionally comprising mixing the co-catalyst with the liquid olefin prior to said step (b).
Claim 11
Dependent Claim
19 words
The method of claim 3 additionally comprising mixing the co-catalyst with the liquid olefin prior to said step (b).
Claim 12
Dependent Claim
14 words
The method of claim 1 wherein said liquid olefin is a vaporizable, polymerizable olefin.
Claim 13
Dependent Claim
14 words
The method of claim 2 wherein said liquid olefin is a vaporizable, polymerizable olefin.
Claim 14
Dependent Claim
14 words
The method of claim 3 wherein said liquid olefin is a vaporizable, polymerizable olefin.
Claim 15
Dependent Claim
11 words
The method of claim 1 wherein said Ziegler catalyst is vanadium-based.
Claim 16
Dependent Claim
11 words
The method of claim 2 wherein said Ziegler catalyst is vanadium-based.
Claim 17
Dependent Claim
11 words
The method of claim 3 wherein said Ziegler catalyst is vanadium-based.
Claim 18
Dependent Claim
21 words
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.
Claim 19
Dependent Claim
21 words
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.
Claim 20
Dependent Claim
21 words
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.
Claim 21
Dependent Claim
24 words
The method of claim 1 wherein the vertical reactor temperature varies from about 122° F. (50° C.) to about 248° F. (120 ° C.).
Claim 22
Dependent Claim
23 words
The method of claim 2 wherein the vertical reactor temperature varies from about 122° F. (50° C.) to about 248° F. (120° C.).
Claim 23
Dependent Claim
23 words
The method of claim 3 wherein the vertical reactor temperature varies from about 122° F. (50° C.) to about 248° F. (120° C.)
Claim 24
Dependent Claim
27 words
The method of claim 1 wherein the vertical reactor pressure varies from about 100 psi (7.0 kg/cm 2 ) to about 600 psi (42.2 kg/cm 2 ).
Claim 25
Dependent Claim
23 words
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).
Claim 26
Dependent Claim
27 words
The method of claim 3 wherein the vertical reactor pressure varies from about 100 psi (7.0 kg/cm 2 ) to about 600 psi (42.2 kg/cm 2 ).
Claim 27
Dependent Claim
23 words
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.
Claim 28
Dependent Claim
23 words
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.
Claim 29
Dependent Claim
23 words
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.
Claim 30
Dependent Claim
28 words
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.
Claim 31
Dependent Claim
28 words
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.
Claim 32
Dependent Claim
138 words
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.
Claim 33
Dependent Claim
138 words
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.
Claim 34
Dependent Claim
14 words
The process of claim 28 wherein said gas-phase, vertical polymerization reactor includes a fluidized-bed.
Claim 35
Dependent Claim
23 words
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.
Claim 36
Dependent Claim
12 words
The process of claim 28 wherein the Ziegler catalyst is vanadium based.
Claim 37
Dependent Claim
21 words
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.
Claim 38
Dependent Claim
19 words
The method of claim 28 wherein the vertical reactor temperature varies from about 122° F. to about 248° F.
Claim 39
Dependent Claim
19 words
The method of claim 28 wherein the vertical reactor pressure varies from about 100 psi to about 600 psi.
Claim 40
Dependent Claim
28 words
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.
Claim 41
Dependent Claim
32 words
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.
Claim 42
Dependent Claim
32 words
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.
Claim 43
Dependent Claim
37 words
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.
Claim 44
Dependent Claim
32 words
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.
Claim 45
Dependent Claim
32 words
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.
Claim 46
Dependent Claim
55 words
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.
Claim 47
Dependent Claim
32 words
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.
Claim 48
Dependent Claim
32 words
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.
Claim 49
Dependent Claim
37 words
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.
Claim 50
Dependent Claim
32 words
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.
Claim 51
Dependent Claim
32 words
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.
Claim 52
Dependent Claim
37 words
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.
Claim 53
Dependent Claim
32 words
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.
Claim 54
Dependent Claim
32 words
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.
Claim 55
Dependent Claim
37 words
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.
Claim 56
Dependent Claim
14 words
The method of claim 11 wherein said vanadium-based Ziegler catalyst comprises VOCl 3 .
Claim 57
Dependent Claim
14 words
The method of claim 12 wherein said vanadium-based Ziegler catalyst comprises VOCl 3 .
Claim 58
Dependent Claim
14 words
The method of claim 13 wherein said vanadium-based Ziegler catalyst comprises VOCl 3 .
Claim 59
Independent Claim
157 words
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.
Claim 60
Independent Claim
157 words
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.
Claim 61
Independent Claim
356 words
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 C 3 to C 8 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 VOCl 3 , VCl 4 , 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 C 3 to C 8 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.
Claim 62
Independent Claim
356 words
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 C 3 to C 8 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 VOCl 3 , VCl 4 , 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 C 3 to C 8 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.
Claim 63
Dependent Claim
23 words
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.
Claim 64
Independent Claim
324 words
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 VOCl 3 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.
Claim 65
Independent Claim
324 words
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 VOCl 3 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.
Claim 66
Dependent Claim
18 words
The method of claim 57 wherein said fluidized bed comprises said Ziegler catalyst, said co-catalyst, and ethylene polymer.
References Cited (Backward Citations)
US4287327A
Cited
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| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1990-05-11 | 1990-11-10 | 1991-05-12 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1994-05-11 | 1994-11-10 | 1995-05-12 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1998-05-11 | 1998-11-10 | 1999-05-12 | $7700.00 | Window Closed / Lapsed |