CA2500674A1 - Apparatus for preparing polyolefin products and methodology for using the same - Google Patents
Apparatus for preparing polyolefin products and methodology for using the same Download PDFInfo
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- CA2500674A1 CA2500674A1 CA002500674A CA2500674A CA2500674A1 CA 2500674 A1 CA2500674 A1 CA 2500674A1 CA 002500674 A CA002500674 A CA 002500674A CA 2500674 A CA2500674 A CA 2500674A CA 2500674 A1 CA2500674 A1 CA 2500674A1
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- zone
- catalyst
- olefin polymerization
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- 229920000098 polyolefin Polymers 0.000 title claims abstract 42
- 238000000034 method Methods 0.000 title claims 27
- 239000003054 catalyst Substances 0.000 claims abstract 74
- 238000006116 polymerization reaction Methods 0.000 claims abstract 51
- 150000001336 alkenes Chemical class 0.000 claims abstract 49
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract 49
- 239000000203 mixture Substances 0.000 claims abstract 41
- 239000011541 reaction mixture Substances 0.000 claims abstract 30
- 239000003607 modifier Substances 0.000 claims abstract 12
- 239000003139 biocide Substances 0.000 claims abstract 7
- 239000000047 product Substances 0.000 claims 61
- 238000006243 chemical reaction Methods 0.000 claims 40
- 239000012071 phase Substances 0.000 claims 32
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims 30
- 239000012530 fluid Substances 0.000 claims 18
- 239000012736 aqueous medium Substances 0.000 claims 16
- 239000008346 aqueous phase Substances 0.000 claims 15
- 238000011144 upstream manufacturing Methods 0.000 claims 13
- 230000005484 gravity Effects 0.000 claims 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims 11
- 230000003134 recirculating effect Effects 0.000 claims 10
- 229920002367 Polyisobutene Polymers 0.000 claims 8
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims 6
- 238000010936 aqueous wash Methods 0.000 claims 6
- 239000008139 complexing agent Substances 0.000 claims 3
- 239000003795 chemical substances by application Substances 0.000 claims 2
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 claims 2
- 150000003839 salts Chemical class 0.000 claims 2
- 239000002351 wastewater Substances 0.000 claims 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims 1
- 235000011114 ammonium hydroxide Nutrition 0.000 claims 1
- 239000012043 crude product Substances 0.000 claims 1
- 239000007791 liquid phase Substances 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/24—Stationary reactors without moving elements inside
- B01J19/2415—Tubular reactors
- B01J19/2425—Tubular reactors in parallel
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/01—Processes of polymerisation characterised by special features of the polymerisation apparatus used
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/24—Stationary reactors without moving elements inside
- B01J19/2405—Stationary reactors without moving elements inside provoking a turbulent flow of the reactants, such as in cyclones, or having a high Reynolds-number
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/24—Stationary reactors without moving elements inside
- B01J19/2455—Stationary reactors without moving elements inside provoking a loop type movement of the reactants
- B01J19/2465—Stationary reactors without moving elements inside provoking a loop type movement of the reactants externally, i.e. the mixture leaving the vessel and subsequently re-entering it
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/005—Separating solid material from the gas/liquid stream
- B01J8/007—Separating solid material from the gas/liquid stream by sedimentation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
- B01J8/20—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with liquid as a fluidising medium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F6/00—Post-polymerisation treatments
- C08F6/02—Neutralisation of the polymerisation mass, e.g. killing the catalyst also removal of catalyst residues
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00008—Controlling the process
- B01J2208/00017—Controlling the temperature
- B01J2208/00106—Controlling the temperature by indirect heat exchange
- B01J2208/00168—Controlling the temperature by indirect heat exchange with heat exchange elements outside the bed of solid particles
- B01J2208/00212—Plates; Jackets; Cylinders
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00008—Controlling the process
- B01J2208/00017—Controlling the temperature
- B01J2208/00106—Controlling the temperature by indirect heat exchange
- B01J2208/00265—Part of all of the reactants being heated or cooled outside the reactor while recycling
- B01J2208/00283—Part of all of the reactants being heated or cooled outside the reactor while recycling involving reactant liquids
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00002—Chemical plants
- B01J2219/00004—Scale aspects
- B01J2219/00006—Large-scale industrial plants
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00002—Chemical plants
- B01J2219/00027—Process aspects
- B01J2219/00038—Processes in parallel
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00051—Controlling the temperature
- B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
- B01J2219/00076—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements inside the reactor
- B01J2219/00085—Plates; Jackets; Cylinders
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00051—Controlling the temperature
- B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
- B01J2219/00105—Controlling the temperature by indirect heating or cooling employing heat exchange fluids part or all of the reactants being heated or cooled outside the reactor while recycling
- B01J2219/0011—Controlling the temperature by indirect heating or cooling employing heat exchange fluids part or all of the reactants being heated or cooled outside the reactor while recycling involving reactant liquids
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00245—Avoiding undesirable reactions or side-effects
- B01J2219/00272—Addition of reaction inhibitor
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
Abstract
~Apparatus (202) for olefin polymerization includes a plurality of shell and tube olefin polymerization reactors (202a, 202b), each of which has an olefin polymerization reaction mixture inlet connection and a crude polyolefin product outlet connection (55a, 55b). Each reactor (202a, 202b) is equipped with a recirculation system including a pump (25a, 25b) arranged to circulate a reaction mixture through the tube side of the reactor (202a, 202b) independently of the introduction of olefin polymerization reaction mixture into the reactor (202a, 202b). The apparatus (202) also includes an inlet reaction mixture distribution manifold (215, 15a, 15b) and an outlet polymerization reaction mixture collection manifold (255, 55a, 55b) interconnecting the reactors (202a, 202b) for operation in parallel. The apparatus (202) also includes catalyst composition and catalyst modifier inlets (16a, 16b, 30a, 30b) for each reactor (202a, 202b) arranged such that a catalyst modifier to may be introduced into each reactor (202a, 202b) at a rate which is independent of the introduction of catalyst composition. The apparatus (202) further incorporates a crude polyolefin product catalyst removal and wash system including a plurality of settler vessels (302, 306, 308), associated piping and an inlet (318) for a catalyst killing agent. This crude polyolefin product catalyst removal and wash system operates to receive crude polyolefin product from the crude polyolefin product outlet (255) and remove residual catalyst therefrom.
Claims (38)
1. Apparatus for olefin polymerization comprising:
an olefin containing feedstock distribution assembly including a feedstock inlet and a plurality of feedstock outlets, said distribution assembly being adapted and arranged to receive feedstock via said feedstock inlet, divide said feedstock into a plurality of separate streams and deliver each of said streams to a respective one of said outlets;
a plurality of reactors, each of said reactors comprising (1) structure defining a reaction zone, said structure being adapted and arranged to facilitate the conduct of an exothermic olefin polymerization reaction on an olefin polymerization reaction mixture in said zone, said structure comprising inlet and outlet connections arranged in fluid communication with said zone, and (2) a recirculation system including a pump arranged and adapted to circulate said reaction mixture in said zone, each said feedstock outlet being connected in fluid communication with the inlet connection of a respective reactor, each said recirculation system being adapted and arranged to circulate reaction mixture in its respective zone independently of the introduction of feedstock into said zone via a respective inlet connection;
a crude polyolefin product collection assembly including a plurality of crude polyolefin product inlets and a crude polyolefin product outlet, each said crude polyolefin product inlet being connected in fluid communication with the outlet connection of a respective reactor.
an olefin containing feedstock distribution assembly including a feedstock inlet and a plurality of feedstock outlets, said distribution assembly being adapted and arranged to receive feedstock via said feedstock inlet, divide said feedstock into a plurality of separate streams and deliver each of said streams to a respective one of said outlets;
a plurality of reactors, each of said reactors comprising (1) structure defining a reaction zone, said structure being adapted and arranged to facilitate the conduct of an exothermic olefin polymerization reaction on an olefin polymerization reaction mixture in said zone, said structure comprising inlet and outlet connections arranged in fluid communication with said zone, and (2) a recirculation system including a pump arranged and adapted to circulate said reaction mixture in said zone, each said feedstock outlet being connected in fluid communication with the inlet connection of a respective reactor, each said recirculation system being adapted and arranged to circulate reaction mixture in its respective zone independently of the introduction of feedstock into said zone via a respective inlet connection;
a crude polyolefin product collection assembly including a plurality of crude polyolefin product inlets and a crude polyolefin product outlet, each said crude polyolefin product inlet being connected in fluid communication with the outlet connection of a respective reactor.
2. Apparatus for olefin polymerization as set forth in claim 1, comprising two of said reactors.
3. Apparatus for olefin polymerization as set forth in claim 1, comprising at least three of said reactors.
4. Apparatus for olefin polymerization as set forth in claim 1, comprising a respective catalyst composition inlet in fluid communication with each reaction zone, each said catalyst composition inlet being adapted and arranged to introduce catalyst composition into said recirculating olefin polymerization reaction mixture in said zone, and a respective catalyst modifier inlet in fluid communication with each said reaction zone, each said catalyst modifier inlet being adapted and arranged to introduce catalyst modifier into said recirculating olefin polymerization reaction mixture at a rate which is independent of the rate of introduction of the catalyst composition.
5. Apparatus for olefin polymerization as set forth in claim 4, wherein each said catalyst modifier inlet is spaced from its corresponding catalyst composition inlet.
6. Apparatus for olefin polymerization as set forth in claim 1 or claim 4, and a crude polyolefin product catalyst removal and wash system including a plurality of settler vessels, associated piping and an inlet for a catalyst billing agent, said crude polyolefin product catalyst removal and wash system being adapted and arranged to receive crude polyolefin product from said crude polyolefin product outlet and remove residual catalyst therefrom.
7. Apparatus for olefin polymerization as set forth in claim 6, wherein said crude polyolefin product catalyst removal and wash system comprises:
an upstream settler vessel defining an internal settlement chamber adapted and arranged for receiving a mixture of a crude polyolefin product and an aqueous wash media and allowing said product and said media to separate therein under the influence of gravity;
a crude, catalyst containing olefin polymerization product inlet line connected to said crude polyolefin product outlet and arranged in fluid communication with the chamber of said upstream settler vessel;
a catalyst billing agent inlet conduit in fluid communication with the chamber of said upstream settler vessel;
a first make-up water inlet passageway in fluid communication with the chamber of said upstream settler vessel;
a downstream settler system including at least one downstream settler vessel defining an internal settlement chamber adapted and arranged for receiving a mixture of a partially washed crude polyolefin product and an aqueous wash media and allowing said product and said media to separate therein under the influence of gravity;
an overhead, partially washed polyolefin product line intercommunicating the chamber of said upstream settler vessel with said downstream settler system;
a washed crude olefin polymerization product outlet line in fluid communication with said downstream settler system;
a second make-up water inlet passageway in fluid communication with said downstream settler system;
a first drain line interconnecting the chamber of said upstream settler vessel with an inlet connection to a waste water receiving system; and a second drain line interconnecting said downstream settler system with said inlet connection.
an upstream settler vessel defining an internal settlement chamber adapted and arranged for receiving a mixture of a crude polyolefin product and an aqueous wash media and allowing said product and said media to separate therein under the influence of gravity;
a crude, catalyst containing olefin polymerization product inlet line connected to said crude polyolefin product outlet and arranged in fluid communication with the chamber of said upstream settler vessel;
a catalyst billing agent inlet conduit in fluid communication with the chamber of said upstream settler vessel;
a first make-up water inlet passageway in fluid communication with the chamber of said upstream settler vessel;
a downstream settler system including at least one downstream settler vessel defining an internal settlement chamber adapted and arranged for receiving a mixture of a partially washed crude polyolefin product and an aqueous wash media and allowing said product and said media to separate therein under the influence of gravity;
an overhead, partially washed polyolefin product line intercommunicating the chamber of said upstream settler vessel with said downstream settler system;
a washed crude olefin polymerization product outlet line in fluid communication with said downstream settler system;
a second make-up water inlet passageway in fluid communication with said downstream settler system;
a first drain line interconnecting the chamber of said upstream settler vessel with an inlet connection to a waste water receiving system; and a second drain line interconnecting said downstream settler system with said inlet connection.
8. Apparatus for olefin polymerization as set forth in claim 1, wherein each said reactor comprises a shell and tube heat exchanger configured and arranged so that said reaction zone is on the tube side thereof.
9. A method for olefin polymerization comprising:
providing a reactor system including a plurality of reactors, each said reactor defining an internal reaction zone;
conducting an exothermic olefin polymerization reaction on an olefin polymerization reaction mixture in each reaction zone;
supplying an olefin containing feedstock and dividing the same into a plurality of separate feedstock streams;
introducing a separate one of said olefin containing feedstock streams into the reaction zone of each reactor;
separately circulating the reaction mixture in each reactor at a flow rate that is independent of the rate of introduction of the respective stream of feedstock into the reaction zone;
removing a crude polyolefin product stream from each of said reactors; and combining said crude polyolefin product streams to form a single crude product stream.
providing a reactor system including a plurality of reactors, each said reactor defining an internal reaction zone;
conducting an exothermic olefin polymerization reaction on an olefin polymerization reaction mixture in each reaction zone;
supplying an olefin containing feedstock and dividing the same into a plurality of separate feedstock streams;
introducing a separate one of said olefin containing feedstock streams into the reaction zone of each reactor;
separately circulating the reaction mixture in each reactor at a flow rate that is independent of the rate of introduction of the respective stream of feedstock into the reaction zone;
removing a crude polyolefin product stream from each of said reactors; and combining said crude polyolefin product streams to form a single crude product stream.
10. A method as set forth in claim 9, wherein said system includes two of said reactors and said olefin polymerization reaction mixture is divided into two separate streams.
11. A method as set forth in claim 9, wherein said system includes at least three of said reactors and said olefin polymerization reaction mixture is divided into at least three separate streams.
12. A reactor apparatus for olefin polymerization comprising:
a reactor defining a reaction zone and including an olefin polymerization reaction mixture inlet connection and an olefin polymerization reaction mixture outlet connection, which connections are in fluid communication with said zone, said reactor being adapted and arranged to facilitate the conduct in said zone of an exothermic olefin polymerization reaction on said olefin polymerization reaction mixture in the presence of a catalyst composition comprising a catalyst and a catalyst modifier;
an inlet for introduction of an olefin containing feedstock into the reaction mixture in said zone;
a recirculation system including a pump arranged and adapted to circulate said reaction mixture in said zone at a flow rate that is independent of the rate of introduction of olefin containing feedstock into said zone;
a catalyst composition inlet in fluid communication with said zone for introduction of a catalyst composition into the reaction mixture in said zone;
and at least one catalyst modifier inlet in fluid communication with said zone for introduction of a catalyst modifier into the reaction mixture in said zone at a rate which is independent of the rate of introduction of catalyst composition into the reaction mixture in said zone.
a reactor defining a reaction zone and including an olefin polymerization reaction mixture inlet connection and an olefin polymerization reaction mixture outlet connection, which connections are in fluid communication with said zone, said reactor being adapted and arranged to facilitate the conduct in said zone of an exothermic olefin polymerization reaction on said olefin polymerization reaction mixture in the presence of a catalyst composition comprising a catalyst and a catalyst modifier;
an inlet for introduction of an olefin containing feedstock into the reaction mixture in said zone;
a recirculation system including a pump arranged and adapted to circulate said reaction mixture in said zone at a flow rate that is independent of the rate of introduction of olefin containing feedstock into said zone;
a catalyst composition inlet in fluid communication with said zone for introduction of a catalyst composition into the reaction mixture in said zone;
and at least one catalyst modifier inlet in fluid communication with said zone for introduction of a catalyst modifier into the reaction mixture in said zone at a rate which is independent of the rate of introduction of catalyst composition into the reaction mixture in said zone.
13. A reactor apparatus for olefin polymerization as set forth in claim 12, wherein said catalyst composition inlet is spaced from said catalyst modifier inlet.
14. A reactor apparatus for olefin polymerization as set forth in claim 12, wherein said catalyst composition inlet is connected to a pipe which is part of said recirculation system.
15. A method for conducting an olefin polymerization reaction comprising:
recirculating an olefin polymerization reaction mixture in a reaction zone of an olefin polymerization reactor;
introducing an olefin containing feedstock into said recirculated olefin polymerization reaction mixture, said olefin polymerization reaction mixture being recirculated at a flow rate which is independent of the rate of introduction of said feedstock into said zone;
introducing a catalyst composition comprising a catalyst and a catalyst modifier into said reaction mixture;
subjecting said polymerization reaction mixture to exothermic olefin polymerization reaction conditions in said zone in the presence of said catalyst composition;
and introducing a catalyst modifier into said recirculating olefin polymerization reaction mixture at a rate which is independent of the rate of introduction of said catalyst composition into said zone.
recirculating an olefin polymerization reaction mixture in a reaction zone of an olefin polymerization reactor;
introducing an olefin containing feedstock into said recirculated olefin polymerization reaction mixture, said olefin polymerization reaction mixture being recirculated at a flow rate which is independent of the rate of introduction of said feedstock into said zone;
introducing a catalyst composition comprising a catalyst and a catalyst modifier into said reaction mixture;
subjecting said polymerization reaction mixture to exothermic olefin polymerization reaction conditions in said zone in the presence of said catalyst composition;
and introducing a catalyst modifier into said recirculating olefin polymerization reaction mixture at a rate which is independent of the rate of introduction of said catalyst composition into said zone.
16. A liquid phase polymerization process for preparing polyisobutylene, said process comprising:
providing a feedstock comprising isobutylene;
providing a catalyst composition comprising a complex of BF3 and a complexing agent;
introducing said feedstock and said catalyst composition into a reaction mixture in a reaction zone;
intimately intermixing said reaction mixture, said feedstock and said catalyst composition to present an intimately intermixed reaction admixture in said reaction zone;
maintaining the intimately intermixed reaction admixture in its intimately intermixed condition while the same is in said reaction zone, to thereby cause the isobutylene therein to undergo polymerization to form polyisobutylene;
introducing an additional amount of said complexing agent into said intimately intermixed reaction admixture at a rate which is independent of the rate of introduction of said catalyst composition; 'and withdrawing a product stream comprising polyisobutylene from said reaction zone.
providing a feedstock comprising isobutylene;
providing a catalyst composition comprising a complex of BF3 and a complexing agent;
introducing said feedstock and said catalyst composition into a reaction mixture in a reaction zone;
intimately intermixing said reaction mixture, said feedstock and said catalyst composition to present an intimately intermixed reaction admixture in said reaction zone;
maintaining the intimately intermixed reaction admixture in its intimately intermixed condition while the same is in said reaction zone, to thereby cause the isobutylene therein to undergo polymerization to form polyisobutylene;
introducing an additional amount of said complexing agent into said intimately intermixed reaction admixture at a rate which is independent of the rate of introduction of said catalyst composition; 'and withdrawing a product stream comprising polyisobutylene from said reaction zone.
17. A process as set forth in claim 16, said reaction zone comprising a loop reactor wherein the reaction admixture is continuously recirculated at a first volumetric flow rate, and said feedstock and said catalyst composition are continuously introduced at a combined second volumetric flow rate.
18. A method as set forth in claim 17, wherein said complexing agent comprises methanol.
19. A method as set forth in claim 18, wherein the product is a highly reactive polyisobutylene and the ratio of BF3 to methanol in said catalyst composition is no less than about 0.59:1.
20. A method as set forth in claim 18, wherein the product is a highly reactive polyisobutylene and the ratio of BF3 to methanol in said catalyst composition is in the range of from about 0.59:1 to about 0.62:1.
21. A method as set forth in claim 19, wherein the product is a highly reactive polyisobutylene and a sufficient amount of methanol is independently introduced to cause the ratio of BF3 to methanol in said intimately intermixed reaction admixture catalyst composition to be maintained in the range of from about 0.59:1 to about 0.60:1 during the course of the reaction.
22. A method as set forth in claim 20, wherein a sufficient amount of methanol is independently introduced to cause the ratio of BF3 to methanol in said intimately intermixed reaction admixture catalyst composition to be maintained at approximately 0.59:1 to about 0.62:1 during the course of the reaction.
23. A method as set forth in claim 17, wherein said intimately intermixed reaction admixture catalyst composition is maintained at a temperature of at least about 0°
while the same is in said reaction zone.
while the same is in said reaction zone.
24. A method as set forth in claim 17, including controlling the introduction of said feedstock into said reaction zone and the withdrawal of said product stream from the reaction zone such that the residence time of the isobutylene undergoing polymerization in the reaction zone is no greater than about 4 minutes.
25. A method as set forth in claim 23, including controlling the introduction of said feedstock into said reaction zone and the withdrawal of said product stream from the reaction zone such that the residence tune of the isobutylene undergoing polymerization in the reaction zone is no greater than about 4 minutes.
26. A method as set forth in claim 24 or claim 25, wherein the introduction of said feedstock into said reaction zone and the withdrawal of said product stream from the reaction zone are controlled such that the residence time of the isobutylene undergoing polymerization in the reaction zone is no greater than about 3 minutes.
27. A method as set forth in claim 24 or claim 25, wherein the introduction of said feedstock into said reaction zone and the withdrawal of said product stream from the reaction zone are controlled such that the residence time of the isobutylene undergoing polymerization in the reaction zone is no greater than about 200 seconds.
28. A crude polyolefin product catalyst removal and wash system comprising:
an upstream settler vessel defining an internal settlement chamber adapted and arranged for receiving a mixture of a crude polyolefin product and an aqueous wash media and allowing said product and said media to separate therein under the influence of gravity;
a crude, catalyst containing olefin polymerization product inlet line in fluid communication with the chamber of said upstream settler vessel;
a catalyst killing agent inlet conduit in fluid communication with the chamber of said upstream settler vessel;
a first make-up water inlet passageway in fluid communication with the chamber of said upstream settler vessel;
a downstream settler system including at least one downstream settler vessel defining an internal settlement chamber adapted and arranged for receiving a mixture of a partially washed crude polyolefin product and an aqueous wash media and allowing said product and said media to separate therein under the influence of gravity;
an overhead, partially washed polyolefin product line intercommunicating the chamber of said upstream settler vessel with said downstream settler system;
a washed crude olefin polymerization product outlet line in fluid communication with said downstream settler system;
a second make-up water inlet passageway in fluid communication with said downstream settler system;
a first drain line interconnecting the chamber of said upstream settler vessel with an inlet connection to a waste water receiving system; and a second drain line interconnecting said downstream settler system with said inlet connection.
an upstream settler vessel defining an internal settlement chamber adapted and arranged for receiving a mixture of a crude polyolefin product and an aqueous wash media and allowing said product and said media to separate therein under the influence of gravity;
a crude, catalyst containing olefin polymerization product inlet line in fluid communication with the chamber of said upstream settler vessel;
a catalyst killing agent inlet conduit in fluid communication with the chamber of said upstream settler vessel;
a first make-up water inlet passageway in fluid communication with the chamber of said upstream settler vessel;
a downstream settler system including at least one downstream settler vessel defining an internal settlement chamber adapted and arranged for receiving a mixture of a partially washed crude polyolefin product and an aqueous wash media and allowing said product and said media to separate therein under the influence of gravity;
an overhead, partially washed polyolefin product line intercommunicating the chamber of said upstream settler vessel with said downstream settler system;
a washed crude olefin polymerization product outlet line in fluid communication with said downstream settler system;
a second make-up water inlet passageway in fluid communication with said downstream settler system;
a first drain line interconnecting the chamber of said upstream settler vessel with an inlet connection to a waste water receiving system; and a second drain line interconnecting said downstream settler system with said inlet connection.
29. A crude polyolefin product catalyst removal and wash system as set forth in claim 28, wherein said downstream settler system includes primary and secondary downstream settler vessels, each of which downstream settler vessels defines a respective internal settlement chamber adapted and arranged for receiving a mixture of a partially washed crude polyolefin product and an aqueous wash media and allowing said product and said media to separate therein under the influence of gravity, wherein said overhead, partially washed polyolefin product line intercommunicates the chamber of said first settler vessel with the chamber of said primary downstream settler vessel, wherein is included a second overhead product line that intercommunicates the chamber of said primary downstream settler vessel with the chamber of said secondary downstream settler vessel, and wherein said second drain line interconnects the chamber of said primary downstream settler vessel with said inlet connection.
30. A crude polyolefin product catalyst removal and wash system as set forth in claim 29, wherein is included a first centrifugal pump located in said crude, catalyst containing olefin polymerization product inlet line, said catalyst killing agent inlet conduit and said first make-up water inlet passageway being connected to said crude, catalyst containing olefin polymerization product inlet line at one or more points that are upstream from a suction side of said pump, and a second centrifugal pump located in said overhead, partially washed polyolefin product line, said pumps being operable to thoroughly mix the crude olefin polymerization product and the aqueous wash media.
31. A method for treating a catalytically formed crude polyolefin product containing residual catalyst to avoid further reaction in the product and remove residual catalyst therefrom, said method comprising:
intimately admixing crude residual catalyst containing polyolefin product and a first aqueous media containing a catalyst killing agent to thereby form a first intimately admixed two phase, gravity separable mixture;
introducing said first two phase mixture into a first settlement zone and allowing the same to settle in said first zone under the influence of gravity to present an upper partially washed crude polyolefin product phase and a first lower aqueous phase containing dissolved catalyst salts;
withdrawing said first lower aqueous phase from said first settlement zone and recirculating a first portion thereof and introducing the same into said first two phase mixture for inclusion as part of said first aqueous media;
directing a second portion of said first lower aqueous phase to a drain for disposal or reclamation;
introducing a first quantity of make-up water into said first two phase mixture for inclusion as part of said first aqueous media;
withdrawing said partially washed crude polyolefin product phase from said first settlement zone and intimately admixing the same with a second aqueous media to thereby form a second intimately admixed two phase, gravity separable mixture;
introducing said second two phase admixture into a second settlement zone and allowing the same to settle in said second zone under the influence of gravity to present an upper more fully washed crude polyolefin product phase and a second lower aqueous phase;
withdrawing said second lower aqueous phase from said second settlement zone and recirculating a first portion thereof and introducing the same into said second two phase mixture for inclusion as part of said second aqueous media;
directing a second portion of said second lower aqueous phase to a drain for disposal or reclamation;
removing said more fully washed crude polyolefin product phase from said second settlement zone; and introducing a second separate quantity of make-up water into said second two phase mixture for inclusion as part of said second aqueous media.
intimately admixing crude residual catalyst containing polyolefin product and a first aqueous media containing a catalyst killing agent to thereby form a first intimately admixed two phase, gravity separable mixture;
introducing said first two phase mixture into a first settlement zone and allowing the same to settle in said first zone under the influence of gravity to present an upper partially washed crude polyolefin product phase and a first lower aqueous phase containing dissolved catalyst salts;
withdrawing said first lower aqueous phase from said first settlement zone and recirculating a first portion thereof and introducing the same into said first two phase mixture for inclusion as part of said first aqueous media;
directing a second portion of said first lower aqueous phase to a drain for disposal or reclamation;
introducing a first quantity of make-up water into said first two phase mixture for inclusion as part of said first aqueous media;
withdrawing said partially washed crude polyolefin product phase from said first settlement zone and intimately admixing the same with a second aqueous media to thereby form a second intimately admixed two phase, gravity separable mixture;
introducing said second two phase admixture into a second settlement zone and allowing the same to settle in said second zone under the influence of gravity to present an upper more fully washed crude polyolefin product phase and a second lower aqueous phase;
withdrawing said second lower aqueous phase from said second settlement zone and recirculating a first portion thereof and introducing the same into said second two phase mixture for inclusion as part of said second aqueous media;
directing a second portion of said second lower aqueous phase to a drain for disposal or reclamation;
removing said more fully washed crude polyolefin product phase from said second settlement zone; and introducing a second separate quantity of make-up water into said second two phase mixture for inclusion as part of said second aqueous media.
32. A method as set forth in claim 31, wherein said catalyst comprises BF3 and said catalyst killing agent comprises NH4OH.
33. A method as set forth in claim 31, wherein said intimately admixing operations are performed using centrifugal pumps.
34. A method as set forth in claim 31, wherein said make-up water comprises demineralized water.
35. A method as set forth in claim 31, wherein said catalyst killing agent is maintained in said first aqueous media at a level which is in excess relative to the amount needed to completely kill the catalyst.
36. A method for washing a crude polyolefin product to remove residual catalyst therefrom, said method comprising:
forming a first intimately admixed two phase admixture comprising a crude olefin polymerization product containing residual catalyst and a first aqueous media containing a catalyst killing agent;
introducing said first two phase admixture into a first settlement zone and causing said first two phase admixture to settle in said zone under the influence of gravity to present an upper partially washed crude polyolefin product phase and a first lower aqueous phase containing dissolved catalyst salts;
removing said first lower aqueous phase from said first settlement zone and recirculating a first portion thereof for inclusion in said first two phase admixture as part of said first aqueous media;
directing a second portion of said first lower aqueous phase to a drain for disposal or reclamation;
removing said partially washed crude polyolefin product phase from said first settlement zone and intimately admixing the same with a second aqueous media to thereby form a second two phase admixture;
introducing said second two phase admixture into a second settlement zone and causing said second two phase admixture to settle therein under the influence of gravity to present an upper intermediately washed crude polyolefin product phase and a second lower aqueous phase;
removing said second lower aqueous phase from said second settlement zone and recirculating a first portion thereof for inclusion in said second two phase admixture as part of said second aqueous media;
directing a second portion of said second lower aqueous phase to a drain for disposal or reclamation;
removing said intermediately washed crude polyolefin product phase from said second settlement zone and admixing the same with a third aqueous media to thereby form a third two phase admixture;
introducing said third two phase admixture into a third settlement zone and causing said third two phase admixture to settle therein under the influence of gravity to present an upper more fully washed crude polyolefin product phase and a third lower aqueous phase;
removing said third lower aqueous phase from said third settlement zone and recirculating a first portion thereof for inclusion in said third two phase admixture as part of said third aqueous media;
recirculating a second portion of said third lower aqueous phase for inclusion in said second intimately admixed two phase admixture as part of said second aqueous media;
introducing a first quantity of make-up water into said first intimately admixed two phase admixture for inclusion therein as part of said first aqueous media;
and introducing a second separate quantity of make-up water into said third intimately admixed two phase admixture for inclusion therein as part of said third aqueous media.
forming a first intimately admixed two phase admixture comprising a crude olefin polymerization product containing residual catalyst and a first aqueous media containing a catalyst killing agent;
introducing said first two phase admixture into a first settlement zone and causing said first two phase admixture to settle in said zone under the influence of gravity to present an upper partially washed crude polyolefin product phase and a first lower aqueous phase containing dissolved catalyst salts;
removing said first lower aqueous phase from said first settlement zone and recirculating a first portion thereof for inclusion in said first two phase admixture as part of said first aqueous media;
directing a second portion of said first lower aqueous phase to a drain for disposal or reclamation;
removing said partially washed crude polyolefin product phase from said first settlement zone and intimately admixing the same with a second aqueous media to thereby form a second two phase admixture;
introducing said second two phase admixture into a second settlement zone and causing said second two phase admixture to settle therein under the influence of gravity to present an upper intermediately washed crude polyolefin product phase and a second lower aqueous phase;
removing said second lower aqueous phase from said second settlement zone and recirculating a first portion thereof for inclusion in said second two phase admixture as part of said second aqueous media;
directing a second portion of said second lower aqueous phase to a drain for disposal or reclamation;
removing said intermediately washed crude polyolefin product phase from said second settlement zone and admixing the same with a third aqueous media to thereby form a third two phase admixture;
introducing said third two phase admixture into a third settlement zone and causing said third two phase admixture to settle therein under the influence of gravity to present an upper more fully washed crude polyolefin product phase and a third lower aqueous phase;
removing said third lower aqueous phase from said third settlement zone and recirculating a first portion thereof for inclusion in said third two phase admixture as part of said third aqueous media;
recirculating a second portion of said third lower aqueous phase for inclusion in said second intimately admixed two phase admixture as part of said second aqueous media;
introducing a first quantity of make-up water into said first intimately admixed two phase admixture for inclusion therein as part of said first aqueous media;
and introducing a second separate quantity of make-up water into said third intimately admixed two phase admixture for inclusion therein as part of said third aqueous media.
37. A method as set forth in claim 18, wherein the product is a mid-range vinylidene content polyisobutylene and the ratio of BF3 to methanol in said catalyst composition is about 1:1.
38. A method as set forth in claim 19, wherein the product is a mid-range vinylidene content polyisobutylene and a sufficient amount of methanol is independently introduced to cause the ratio of BF3 to methanol in said intimately intermixed reaction admixture catalyst composition to be maintained at approximately 1:1 during the course of the reaction.
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PCT/US2004/011428 WO2004101128A2 (en) | 2003-05-09 | 2004-04-14 | Apparatus for preparing polyolefin products and methodology for using the same |
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US6132827A (en) * | 1997-05-19 | 2000-10-17 | Aep Industries, Inc. | Tacky stretch film and method of making and using the same |
US6407186B1 (en) * | 1997-12-12 | 2002-06-18 | Basf Aktiengesellschaft | Method for producing low-molecular, highly reactive polyisobutylene |
DE19834593A1 (en) * | 1998-07-31 | 2000-02-03 | Basf Ag | Process for the production of halogen-free, reactive polyisobutene |
US6562913B1 (en) * | 1999-09-16 | 2003-05-13 | Texas Petrochemicals Lp | Process for producing high vinylidene polyisobutylene |
DE60045897D1 (en) | 1999-09-16 | 2011-06-09 | Tpc Group Llc | METHOD FOR PRODUCING POLYOLEFINE PRODUCTS |
US7037999B2 (en) * | 2001-03-28 | 2006-05-02 | Texas Petrochemicals Lp | Mid-range vinylidene content polyisobutylene polymer product and process for producing the same |
DE19952031A1 (en) * | 1999-10-28 | 2001-05-03 | Basf Ag | Process for the production of highly reactive polyisobutenes |
DE19952030A1 (en) | 1999-10-28 | 2001-05-03 | Basf Ag | Process for the production of highly reactive polyisobutenes |
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2003
- 2003-05-09 US US10/434,805 patent/US6858188B2/en not_active Expired - Lifetime
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2004
- 2004-01-15 US US10/758,499 patent/US6844401B2/en not_active Expired - Lifetime
- 2004-01-15 US US10/757,748 patent/US6777506B1/en not_active Expired - Lifetime
- 2004-01-15 US US10/758,168 patent/US6844400B2/en not_active Expired - Lifetime
- 2004-04-14 JP JP2006501268A patent/JP4287468B2/en not_active Expired - Lifetime
- 2004-04-14 CA CA2500674A patent/CA2500674C/en not_active Expired - Lifetime
- 2004-04-14 EP EP19000026.5A patent/EP3495039A1/en not_active Withdrawn
- 2004-04-14 KR KR1020057008750A patent/KR100645122B1/en active IP Right Grant
- 2004-04-14 EP EP04760808.8A patent/EP1622710B1/en not_active Expired - Lifetime
- 2004-04-14 MX MXPA05004431A patent/MXPA05004431A/en active IP Right Grant
- 2004-04-14 CN CN2008101782922A patent/CN101412774B/en not_active Expired - Fee Related
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- 2004-04-14 CN CN2008101782918A patent/CN101412773B/en not_active Expired - Fee Related
- 2004-04-14 CN CNB2004800013720A patent/CN100523004C/en not_active Expired - Lifetime
- 2004-04-14 WO PCT/US2004/011428 patent/WO2004101128A2/en active Application Filing
- 2004-04-23 TW TW093111458A patent/TWI262929B/en not_active IP Right Cessation
- 2004-05-03 SA SA07270503A patent/SA07270503B1/en unknown
- 2004-05-03 SA SA07270504A patent/SA07270504B1/en unknown
- 2004-05-03 SA SA04250101A patent/SA04250101B1/en unknown
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- 2004-05-07 MY MYPI20091138A patent/MY143261A/en unknown
- 2004-05-07 MY MYPI20091139A patent/MY143263A/en unknown
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- 2008-09-04 JP JP2008227494A patent/JP2009062536A/en not_active Withdrawn
- 2008-09-04 JP JP2008227499A patent/JP2009052048A/en not_active Withdrawn
- 2008-09-04 JP JP2008227578A patent/JP2009057564A/en not_active Withdrawn
- 2008-09-04 JP JP2008227464A patent/JP2009062535A/en not_active Withdrawn
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