WO2021091725A1 - Procédé de réglage d'activité de réacteur en phase gazeuse - Google Patents

Procédé de réglage d'activité de réacteur en phase gazeuse Download PDF

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WO2021091725A1
WO2021091725A1 PCT/US2020/057485 US2020057485W WO2021091725A1 WO 2021091725 A1 WO2021091725 A1 WO 2021091725A1 US 2020057485 W US2020057485 W US 2020057485W WO 2021091725 A1 WO2021091725 A1 WO 2021091725A1
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polymerization
stage
intermediate composition
polymer resin
monomer
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PCT/US2020/057485
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English (en)
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Kevin W. Lawson
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Exxonmobil Chemical Patents Inc.
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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
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/04—Monomers containing three or four carbon atoms
    • C08F210/06—Propene
    • 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
    • B01J19/18—Stationary reactors having moving elements inside
    • B01J19/1812—Tubular reactors
    • B01J19/1837—Loop-type reactors
    • 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
    • B01J19/18—Stationary reactors having moving elements inside
    • B01J19/1862—Stationary reactors having moving elements inside placed in series
    • 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
    • B01J19/2435—Loop-type reactors
    • 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
    • B01J8/08—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with moving particles
    • 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
    • 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
    • B01J8/1872—Details of the fluidised bed reactor
    • 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
    • B01J8/24—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique
    • 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
    • B01J8/24—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique
    • B01J8/26—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique with two or more fluidised beds, e.g. reactor and regeneration installations
    • 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
    • B01J8/24—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique
    • B01J8/36—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique with fluidised bed through which there is an essentially horizontal flow of particles
    • 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
    • B01J8/24—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique
    • B01J8/38—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique with fluidised bed containing a rotatable device or being subject to rotation or to a circulatory movement, i.e. leaving a vessel and subsequently re-entering it
    • 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
    • B01J2219/00087—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements outside the reactor
    • B01J2219/00094—Jackets

Definitions

  • the present invention relates to the production of heterophasic or impact copolymers in series reactors and control of reactor or stage conditions, and in particular to gas phase reactor polymerization processes.
  • GPR gas phase reactor
  • the methods and systems here may be used to alter catalytic activity of a polymerization catalyst in the absence (or reduced presence) of a catalyst poison and without adjusting the temperature of the GPR.
  • One example of a particularly useful of the methods and systems disclosed herein is in generating a heterophasic copolymer of ethylene and propylene.
  • Heterophasic copolymers of ethylene and propylene are made of a dispersed amorphous rubber phase in a semi-crystalline propylene polymer matrix. The addition of the amorphous rubber phase improves the impact performance as compared to propylene homopolymers, especially at low temperatures.
  • Heterophasic propylene-ethylene copolymers have found wide applications, for example, in packaging, houseware, film, and pipe applications, as well as in the automotive and electrical segments, and are transformed by different processing technologies such as injection molding, blow molding, film, fiber, sheet extrusion, and thermoforming.
  • a heterophasic copolymer resin may be prepared by combining a crystalline matrix of a first monomer (e.g., propylene), produced in a first polymerization stage, with embedded particles of ethylene-propylene rubber (EPR) and polyethylene (PE), produced in a subsequent polymerization stage.
  • the polymerization reaction may be aided by a polymerization catalyst, such as a Zeigler-Natta catalyst, which are well known in the art.
  • the output stream of the first polymerization stage containing the matrix of the first monomer may be conveyed to the second polymerization phase along with unreacted first monomer and polymerization catalyst where further polymerization effectively incorporates a second polymer phase into the first polymer matrix.
  • Adjusting process conditions (e.g., temperature) in the second polymerization stage affects catalyst activity, and thus allows for tuning of the properties of the emerging heterophasic copolymer.
  • the properties of the emerging copolymer may also be tuned by adding anti-static agents and catalyst poisoning agents to the reaction stream.
  • introduction of additives complicates the polymerization reaction, the manufacturing process (and required equipment therefore), and costs more.
  • the industry would benefit from systems and methods that effectively manufacture heterophasic copolymer resins while minimizing the use of additive materials.
  • Disclosed herein are methods and systems for controlling catalytic activity of a polymerization catalyst in a gas phase reactor.
  • the methods and systems here may be used to alter catalytic activity of a polymerization catalyst in the absence (or reduced presence) of a catalyst poison and without adjusting the temperature of the GPR.
  • One example of a particularly useful of the methods and systems disclosed herein is in generating a heterophasic copolymer of ethylene and propylene.
  • catalytic activity of a polymerization catalyst may be carried out according to a method comprising contacting a first monomer with a polymerization catalyst having a first catalytic activity to form an intermediate composition comprising a first polymeric resin and the polymerization catalyst; heating the intermediate composition to a temperature sufficient to alter the first catalytic activity to a second catalytic activity, thereby forming a heated intermediate composition; and contacting the heated intermediate composition with a second monomer under conditions effective to generate a product polymer resin.
  • the method may be carried out on a system comprising a first polymerization stage configured to be operated under a first set of conditions effective to impart upon a polymerization catalyst a first desired catalytic activity and generate an intermediate composition comprising the polymerization catalyst and a first polymer resin; a heating stage downstream of the first polymerization stage, the heating stage configured to heat the intermediate composition to a temperature of at least 60°C thereby generating a heated intermediate composition; and a second polymerization stage downstream of the heating stage configured to operate under a second set of conditions effective to introduce a second monomer into the heated intermediate composition, thus generating a product polymer resin.
  • FIG. 1 relates to the effect of temperature on the activity of one example of a Zeigler-Natta catalyst suitable for use in the systems and methods disclosed herein
  • FIG. 2 illustrates a system that may be used to generate heterophasic copolymers according to the methods disclosed herein.
  • GPR gas phase reactor
  • the methods and systems here may be used to alter catalytic activity of a polymerization catalyst in the absence (or reduced presence) of a catalyst poison and without adjusting the temperature of the GPR.
  • the temperature of an intermediate stream comprising a polymerization catalyst may be adjusted to control the catalytic activity of a polymerization catalyst therein being fed as it is fed into a GPR.
  • One example of a particularly useful of the methods and systems disclosed herein is in creating a heterophasic copolymer of ethylene and propylene.
  • upstream refers to a component located before the reference component.
  • downstream refers to a compound located after the reference component.
  • a system suitable for employing the methods disclosed herein may include a first polymerization stage, a heating stage, and a second polymerization stage.
  • the first polymerization stage comprises a first polymerization reactor that is configured to be operated at a first set of conditions effective to impart upon a polymerization catalyst a desired catalytic activity, thereby generating a first polymer resin comprising a first monomer.
  • the first polymerization reactor may include an inlet that is configured and arranged to convey a first feed into the reactor.
  • the first polymerization stage may include more than one reactors, for example, two or more reactors in series.
  • a first polymerization stage may include one or more of the following reactor types: loop reactor, horizontal stirred bed, sub-fluidized stirred bed, multi-zone reactor, continuous stirred tank reactor (CSTR), plug flow reactor (PFR, sometimes called a “tubular” reactor), and the like.
  • CSTR continuous stirred tank reactor
  • PFR plug flow reactor
  • a first polymerization reactor may include apparatus to control temperature within the reactor, for example, to remove heat from the reactor.
  • a first polymerization reactor may include a second inlet, configured and arranged to receive one or more of an unreacted monomer and hydrogen. Any inlet may include a valve to control flow through the inlet.
  • At least one reactor in the first polymerization stage includes an outlet arranged and configured to convey a first polymerization stage output to a downstream heating stage fluidly coupled to the first polymerization stage.
  • a heating stage downstream of the first polymerization stage may be arranged to accept a first polymerization stage output stream and heat said stream.
  • a heating stage may be configured to heat a first polymerization stage output stream to a temperature of about 80°C to about 140°C.
  • a heating stage may include one or more conduits including at least one heating element configured and arranged to transfer heat contents conveyed therethrough.
  • a heating stage may include one or more separate heating units which may be the same or different from each other and may be in series or in parallel with respect to each other. Any known method of heating may be used, for example, steam, or electricity.
  • a suitable heating stage is configured to adjust the temperature of the first polymerization stage output stream before it enters a second polymerization stage in a manner effective to adjust the catalytic activity, at least in part, of a polymerization catalyst therein.
  • a second polymerization stage may comprise a second polymerization reactor that is fluidly coupled to the heating stage via an inlet for receiving a heating stage output stream.
  • a second reactor may be configured to be operated at a second set of conditions.
  • a second polymerization stage may comprise more than one reactor, for example two or more reactors in series.
  • At least one reactor in the second polymerization stage includes an outlet, configured and arranged to convey a product stream out of the second polymerization stage.
  • a reactor in the second polymerization stage may include apparatus to control temperature within the reactor, for example, to remove heat therefrom.
  • a reactor may include an inlet, configured and arranged to receive one or more of an unreacted monomer and hydrogen.
  • Any inlet may include a valve to control flow therethrough.
  • At least one reactor in the second polymerization stage includes a product stream outlet arranged and configured to convey a product stream exiting the second polymerization stage to a downstream separation stage fluidly coupled to the second polymerization stage.
  • a product separation stage may be configured to isolate one or more of solid, gas, and liquid components of a product stream.
  • a product separation stage may be fluidly coupled to an upstream location (e.g., a reactor) via a conduit arranged and configured to convey a gas component of a product stream to the upstream location.
  • the conduit may include one or more of a heat exchanger, compressor, and condenser.
  • a suitable system may include one or more intermediate separation stages downstream of a heating stage (and fluidly coupled thereto) and upstream of a second polymerization stage (and fluidly coupled thereto).
  • An intermediate separation stage may be arranged and configured to remove one or more of solid fines, unreacted monomer, and hydrogen from a first polymerization stage output stream.
  • An intermediate separation stage may include a high-pressure separator, such as a dust collector. Additionally or alternatively, an intermediate stage may comprise a cyclone, filtration medium, and/or the like.
  • an intermediate separation stage may be fluidly coupled to an upstream location via a recycle conduit, configured to convey a gas component of a first polymerization stage output stream to the upstream location.
  • an intermediate separation stage may include apparatus for controlling the temperature thereof.
  • a system may include a second heating stage downstream of an intermediate separation stage (and fluidly coupled thereto) and upstream of a second polymerization stage (and fluidly coupled thereto).
  • a first polymerization stage 201 includes two loop reactors 202a, 202b in series.
  • the first loop reactor 202a has a first feed inlet 203 and a hydrogen inlet 205a fluidly coupled to a first recycle conduit 204, which is fluidly connected to and feeds into the first loop reactor 202a.
  • the first loop reactor 202a is fluidly connected to a second loop reactor 202b through an inter-reactor conduit 206.
  • the first recycle conduit 204 further fed by a hydrogen inlet 205b, is also fluidly coupled to the second loop reactor 202b.
  • a heating stage 210 is fluidly coupled to the first polymerization stage 201 via a conduit 211 that conveys the first polymer resin out of the first polymerization stage.
  • the heating stage 210 includes the conduit 211 and two heating elements 212.
  • the heating stage 210 is fluidly coupled to an intermediate separation stage 220, depicted in FIG. 2 as a dust collector.
  • the intermediate separation stage has an outlet 221 for receiving and condensing a gas (e.g., unreacted monomer, hydrogen) exiting the intermediate separation stage 220.
  • the outlet 221 is fluidly connected via a first recycle conduit 204.
  • Solid and/or liquid product for further polymerization is conveyed out of the intermediate separation stage 220 through a conduit 222, which is fluidly coupled to a second polymerization stage 230.
  • Second polymerization stage 230 which includes a gas phase reactor (GPR) 231.
  • GPR 231 in FIG. 2 operates as a fluidized bed reactor, and thus includes a fluidized bed region 235.
  • GPR 231 is fluidly coupled to conduit 222 for receiving the portion of the first polymer resin that exits the intermediate separation stage 220 and enters fluidized bed region 235 of the GPR 231.
  • GPR 231 is also fluidly connected to a second recycle conduit 237 at the top of the GPR 231, which is configured to convey fluidizing gas passing through the fluidized bed region 235 back to the bottom of the reactor.
  • the second recycle conduit 237 includes a pump 238 and a heat exchanger 242.
  • a second feed inlet 234 is fluidly coupled to the second recycle conduit 237 to introduce a second feed into the system.
  • the GPR 231 includes a product stream outlet 233 configured to receive the product polymer resin as it exits the second polymerization stage 230 and to convey it to a product separation stage 240 fluidly connected thereto.
  • Product separation stage 240 includes a gas outlet 241 for receiving a gas component (e.g., fluidizing gas, unreacted monomer, hydrogen) isolated from the product polymer resin, which is fluidly coupled to the second recycle conduit 237.
  • the product separation stage 240 also includes outlet 242 configured to output the product polymer resin for conveyance to a collection point 250.
  • a gas component e.g., fluidizing gas, unreacted monomer, hydrogen
  • Methods disclosed herein may be used to generate a heterophasic polymer resin using a polymerization catalyst in the absence (or reduced presence) of a catalyst poison and without relying on the operating temperature of a reactor in the second polymerization stage to control catalytic activity of the polymerization catalyst.
  • Such methods may include employing a first polymerization reactor to react a first feed comprising a first monomer with a polymerization catalyst under conditions effective to impart upon the polymerization catalyst a desired catalytic activity to form an intermediate composition comprising a first polymer resin and polymerization catalyst.
  • a suitable first feed may contain polymerization catalyst and at least one first monomer.
  • a polymerization catalyst may be introduced into the first polymerization stage separately.
  • Suitable polymerization catalysts include material capable of polymerizing a plurality of alkene monomers and whose catalytic activity is temperature- sensitive.
  • the catalytic activity of a suitable polymerization catalyst should be sensitive at temperatures below the decomposition temperature of the first polymer resin to be able to control the catalytic activity of a polymerization catalyst without detriment to the polymer itself.
  • a suitable polymerization catalyst may be a Ziegler-Natta catalyst.
  • ZN type catalysts are well known in the field of polymers and generally, comprise (a) at least a catalyst component formed from a transition metal compound of Group 4 to 6 of the Periodic Table (IUPAC, Nomenclature of Inorganic Chemistry, 1989), a metal compound of Group 1 to 3 of the Periodic Table (IUPAC), and, optionally, a compound of group 13 of the Periodic Table (IUPAC) and/or an internal donor compound.
  • ZN catalyst may also comprise (b) further catalyst component(s), such as a co-catalyst and/or an external donor.
  • Suitable Zeigler-Natta catalysts for use in the methods herein may use titanium tetrachloride as an active ingredient, magnesium chloride as a support, and have any known internal electron donor and/or external electron donor.
  • suitable internal electron donors include amines, amides, esters, ketones, nitriles, ethers, and phosphines.
  • suitable external electron donors include monofunctional or polyfunctional carboxylic acids, carboxylic anhydrides and carboxylic esters, also ketones, ethers, alcohols, lactones and organophosphorus and organosilicon compounds, such as propyltrimethylsiloxane, phenyltriethyoxysilane, diphenyldimethoxysilane, cyclohexylmethyldimethoxysilane, diisobutyldimethoxysilane, diisopropyldimethoxysilane, dicyclopentyldimethoxysilane, isobutylisopropyldimethoxysilane, and an aminosilane.
  • suitable external electron donors include monofunctional or polyfunctional carboxylic acids, carboxylic anhydrides and carboxylic esters, also ketones, ethers, alcohols, lactones and organophosphorus and organosilicon compounds, such as propyltrimethylsiloxane, phenyltriethyoxys
  • a co-catalyst may optionally be present to activate the catalyst system.
  • suitable co-catalysts for Zeigler-Natta catalysts include, for example, organoaluminum compounds such as methylaluminoxane.
  • a suitable first monomer that may be included in the first feed is propylene.
  • a first feed may contain one or more additional first monomers, for example, a C2- or a C4-C6 alkene.
  • a first polymerization reactor may be operated under conditions effective to polymerize the first monomer via a polymerization reaction, thereby forming an intermediate composition comprising a first polymer resin.
  • the polymerization reaction may be, for example, a gas-phase polymerization, slurry polymerization, or bulk polymerization. Suitable temperatures and pressures will depend on the reactants and properties desired of the first polymer resin.
  • a loop reactor in the first polymerization stage may be operated at temperatures of about 60°C to about 100°C and pressures of about 3 MPa to about 6 MPa.
  • a typical polymerization productivity may have a yield about of 5 tons to about 100 tons of product per kilogram of polymerization catalyst.
  • An intermediate composition may comprise one or more of a first polymer resin, residual polymerization catalyst, and unreacted first monomer in liquid form (e.g., a slurry, if the reactor is a bulk reactor).
  • an intermediate composition may comprise solid particles of a first polymer resin and/or a polymerization catalyst (e.g., powder or granules) entrained in an unreacted gaseous monomer (e.g., if the reactor is a gas phase reactor).
  • An intermediate composition may then be heated to a temperature sufficient to adjust the catalytic activity of a polymerization catalyst therein.
  • the temperature may be chosen such that a polymerization catalyst enters a second polymerization stage with a desired activity, thereby generating a product having desirable properties.
  • an intermediate composition may be heated to a temperature sufficient to reduce the catalytic activity of a polymerization catalyst therein.
  • an intermediate composition may be heated to a temperature and pressure that is greater the vaporization temperature and pressure of the first monomer, for example, to a temperature that is at least about 5°C, at least about 10°C, at least about 20°C, at least about 30°C, at least about 40°C, at least about 50°C, or about 60°C above said vaporization temperature at any given pressure.
  • the first monomer is propylene
  • an intermediate composition comprising unreacted liquid propylene and propylene homopolymer may be heated to a temperature of about 80°C to about 140°C. Heating an intermediate composition may vaporize any liquid unreacted first monomer present therein, which may be optionally conveyed out of the heating stage and recycled back to the first polymerization reactor.
  • the heated intermediate composition may then be conveyed to and reacted in a second polymerization reactor with one or more second monomers under conditions effective to incorporate the second monomer/s into the first polymer resin as a different phase, thereby generating a product stream comprising a product polymer resin.
  • a product stream may also optionally comprise one or more of unreacted monomer, hydrogen, side products, and the like.
  • the second polymerization reactor may be a gas phase reactor and the one or more second monomers may be introduced into the second polymerization reactor through a second feed inlet.
  • a product stream may then be removed from a second polymerization reactor and conveyed downstream to a product separation stage where product polymer resin may be isolated from other components in the product stream.
  • unreacted monomer and hydrogen may be recovered and conveyed back to an upstream location (e.g., first polymerization reactor), optionally passing through one or more of a heat exchanger, a compressor, and a condenser along the way.
  • a method may further include removing one or more of solid fines, hydrogen, and/or unreacted monomer from an intermediate composition exiting a first polymerization reactor. This may be carried out by conveying an intermediate composition through one or more intermediate separation stages, which may be fluidly coupled downstream to the first polymerization reactor. Conveying an intermediate composition through an intermediate separation stage may optionally further include heating the intermediate composition to a temperature. [0033] A heated intermediate composition may then be conveyed to a second polymerization reactor, which may be gas phase reactor. A second feed comprising one or more second monomer/s may be introduced into the second polymerization reactor. The one or more second monomers may independently be any C2-C8 alkene, for example, ethylene.
  • a second feed may include two or more second monomers (e.g., propylene and ethylene; propylene, ethylene and butylene; styrene, ethylene, propylene).
  • the second monomer/s may be the same or different from the first monomer and/or first additional monomers.
  • a second polymerization reactor may be operated under conditions effective to incorporate the second monomer/s into the first polymer resin, thereby generating a product stream comprising a product polymer resin, which is, cumulatively, a product of the first polymer resin and the second monomer/s. Suitable temperatures and pressures will depend on the reactants and properties desired of the product polymer resin. For example, a gas phase reactor may be operated at a temperature of about 50°C to about 100°C and a pressure of about 1 MPa to about 3 MPa.
  • a product polymer resin may comprise one or more second monomer/s dispersed within a first polymer resin.
  • second monomer/s may be present as a copolymer that forms a discontinuous phase dispersed within a continuous phase of the first polymer resin.
  • a product polymer resin may contain a matrix of polypropylene (e.g., as a first polymer resin) with a polypropylene-ethylene copolymer (/. ⁇ ? ., the second monomer/s) dispersed therein.
  • a product polymer resin may be, for example, a heterophasic copolymer.
  • a product polymer resin may comprise from about 5 wt. % to about 45 wt. % of the second monomer/s.
  • a product polymer resin may comprise up to about 40 wt. % of the second monomer/s.
  • a first polymer resin may make up a majority of the balance.
  • a product polymer resin may include from about 60 wt. % to about 98 wt. % of the first polymer resin.
  • compositions and methods can also “consist essentially of’ or “consist of’ the various components and steps. All numbers and ranges disclosed above may vary by some amount. Whenever a numerical range with a lower limit and an upper limit is disclosed, any number and any included range falling within the range is specifically disclosed. In particular, every range of values (of the form, “from about a to about b,” or, equivalently, “from approximately a to b,” or, equivalently, “from approximately a-b”) disclosed herein is to be understood to set forth every number and range encompassed within the broader range of values. Also, the terms in the claims have their plain, ordinary meaning unless otherwise explicitly and clearly defined by the patentee. Moreover, the indefinite articles “a” or “an,” as used in the claims, are defined herein to mean one or more than one of the element that it introduces.
  • One nonlimiting example embodiment of the present disclosure includes a method comprising contacting a first monomer with a polymerization catalyst having a first catalytic activity to form an intermediate composition comprising a first polymeric resin and the polymerization catalyst; heating the intermediate composition to a temperature sufficient to alter the first catalytic activity to a second catalytic activity, thereby forming a heated intermediate composition; and contacting the heated intermediate composition with a second monomer under conditions effective to generate a product polymer resin.
  • this embodiment may further include one or more of the following elements: Element 1: The method wherein the polymerization catalyst comprises a Ziegler-Natta catalyst; Element 2: The method wherein the first monomer comprise propylene; Element 3: The method wherein the first polymer resin is a polypropylene homopolymer; Element 4: The method wherein the second monomer is ethylene; Element 5: Element 1 wherein the Ziegler-Natta catalyst comprises an internal donor comprising one or more of a phthalate, succinate, and diether; Element 6: Element 5 wherein the Ziegler-Natta catalyst further comprises an external donor comprising a silane; Element 7: Element 6 wherein the silane comprises one or more of propyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane, cyclohexylmethyldimethyoxysilane, diisobutyldimethoxysilane diisopropyl
  • Suitable combinations of elements include, but are not limited to, Element 1 (and optionally Element 5) in combination with one or more of Elements 2-4 and 6-16; Element 2 (and optionally Element 6) in combination with one or more of Elements 3-16; Element 3 (and optionally Element 7) in combination with one or more of Elements 4-16; Element 4 in combination with one or more of Elements 5-16; Element 8 in combination with one or more of Elements 9-16; Element 9 (and optionally Element 10) in combination with one or more of Elements 10-16; Element 11 in combination with one or more of Elements 12-16; Element 12 in combination with one or more of Elements 13-16; Element 13 in combination with one or more of Elements 14-16, Element 14 in combination with one or both of Elements 15 and 16; and Element 15 in combination with Element 16.
  • Another non-limiting example embodiment includes a system comprising a first polymerization stage configured to be operated under a first set of conditions effective to impart upon a polymerization catalyst a first desired catalytic activity and generate an intermediate composition comprising the polymerization catalyst and a first polymer resin; a heating stage downstream of the first polymerization stage, the heating stage configured to heat the intermediate composition to a temperature of at least 60°C thereby generating a heated intermediate composition; and a second polymerization stage downstream of the heating stage configured to operate under a second set of conditions effective to introduce a second monomer into the heated intermediate composition, thus generating a product polymer resin.
  • Element 17 the system wherein the polymerization catalyst is a Ziegler Natta catalyst
  • Element 18 the system further comprising an intermediate separation stage arranged to receive the intermediate composition
  • Element 19 Element 18 wherein the intermediate separation stage comprises a high-pressure separator
  • Element 20 Element 19 wherein the high-pressure separator is a dust collector
  • Element 21 Element 18 wherein the intermediate separation stage is configured to heat the intermediate composition passing therethrough
  • Element 22 the system wherein the heating stage is heated by steam or electricity
  • Element 23 the system wherein the first polymerization stage comprises one or more slurry loop reactors
  • Element 24 the system wherein the second polymerization stage comprises one or more gas phase reactors.
  • Suitable combinations of elements include, but are not limited to, Element 17 in combination with one or more of Elements 18-24; Element 18 (and optionally Element 19, Elements 19 and 20, or Elements 19-21) in combination with one or more of Elements 22-24; Element 22 in combination with one or both of Elements 23 and 24; and Element 23 in combination with Elements 24. [0041] To facilitate a better understanding of the embodiments of the present invention, the following examples of preferred or representative embodiments are given. In no way should the following examples be read to limit, or to define, the scope of the invention.
  • Example 1 Polymerization Catalyst Activity and Temperature.
  • Catalytic activity of a typical Zeigler-Natta polymerization catalyst (ZN-168 from LyondellBasell, (Rotterdam, Netherlands) in combination with an F external electron donor) was measured at various temperatures. The results, shown in FIG. 1, illustrate the results of the experiment along with simulated data for temperatures above 60°C.
  • ZN-168 is a titanium-based Ziegler-Natta catalyst. The data in FIG. 1 suggests that above about 60°C (0.0030 K 1 ), a Ziegler-Natta polymerization catalyst may begin to lose catalytic activity. While not wishing to be bound by theory, this may be due to increasing secondary reactions at the catalyst active sites.
  • the temperature of the homopolymer exiting the first polymerization stage may be a method useful to control catalytic activity of the residual active catalyst therein before it is conveyed to the GPR to alter catalytic activity of the polymerization catalyst in the GPR without relying on catalyst poisoning or the temperature in the GPR to do so.
  • This type of curve may be constructed with minimal experimentation for any prospective polymerization catalyst to inform one of skill in the art a working temperature range for which the methods and systems disclosed herein may be utilized.

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Abstract

L'invention concerne des procédés et systèmes de production d'une résine de polymère, comprenant : la mise en contact d'un premier monomère avec un catalyseur de polymérisation ayant une première activité catalytique pour former une composition intermédiaire comprenant une première résine de polymère et le catalyseur de polymérisation ; le chauffage de la composition intermédiaire à une température suffisante pour modifier la première activité catalytique en une seconde activité catalytique, ce qui forme ainsi une composition intermédiaire chauffée ; et la mise en contact de la composition intermédiaire chauffée avec un second monomère dans des conditions efficaces pour produire un produit résine de polymère.
PCT/US2020/057485 2019-11-07 2020-10-27 Procédé de réglage d'activité de réacteur en phase gazeuse WO2021091725A1 (fr)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994026792A1 (fr) * 1993-05-18 1994-11-24 Exxon Chemical Patents Inc. Procede de desactivation de catalyseurs a base de metaux de transition
WO2000058377A1 (fr) * 1999-03-31 2000-10-05 Chevron Phillips Chemical Company Lp Processus de transition entre des catalyseurs de polymerisation incompatibles
EP1316566A2 (fr) * 2001-12-03 2003-06-04 Fina Technology, Inc. Méthode de transition entre catalyseurs Ziegler-Natta et catalyseurs à base de métallocène dans un réacteur à boucles pour la préparation de polypropylène
EP1415999A1 (fr) * 2002-10-30 2004-05-06 Borealis Technology Oy Procédé et dispositif pour la production de polymères d' oléfines
WO2009037080A1 (fr) * 2007-09-19 2009-03-26 Basell Poliolefine Italia S.R.L. Procédé en plusieurs étapes pour la polymérisation d'oléfines
WO2014202432A1 (fr) * 2013-06-19 2014-12-24 Borealis Ag Procédé pour la production de polypropylène ayant une polydispersité élevée
EP3394110A1 (fr) * 2015-12-21 2018-10-31 Basell Poliolefine Italia S.r.l. Procédé de polymérisation d'oléfines en présence d'une composition antistatique

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994026792A1 (fr) * 1993-05-18 1994-11-24 Exxon Chemical Patents Inc. Procede de desactivation de catalyseurs a base de metaux de transition
WO2000058377A1 (fr) * 1999-03-31 2000-10-05 Chevron Phillips Chemical Company Lp Processus de transition entre des catalyseurs de polymerisation incompatibles
EP1316566A2 (fr) * 2001-12-03 2003-06-04 Fina Technology, Inc. Méthode de transition entre catalyseurs Ziegler-Natta et catalyseurs à base de métallocène dans un réacteur à boucles pour la préparation de polypropylène
EP1415999A1 (fr) * 2002-10-30 2004-05-06 Borealis Technology Oy Procédé et dispositif pour la production de polymères d' oléfines
WO2009037080A1 (fr) * 2007-09-19 2009-03-26 Basell Poliolefine Italia S.R.L. Procédé en plusieurs étapes pour la polymérisation d'oléfines
WO2014202432A1 (fr) * 2013-06-19 2014-12-24 Borealis Ag Procédé pour la production de polypropylène ayant une polydispersité élevée
EP3394110A1 (fr) * 2015-12-21 2018-10-31 Basell Poliolefine Italia S.r.l. Procédé de polymérisation d'oléfines en présence d'une composition antistatique

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