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WO2025002964A1 - Procédé de polymérisation d'oléfines - Google Patents

Procédé de polymérisation d'oléfines Download PDF

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Publication number
WO2025002964A1
WO2025002964A1 PCT/EP2024/067214 EP2024067214W WO2025002964A1 WO 2025002964 A1 WO2025002964 A1 WO 2025002964A1 EP 2024067214 W EP2024067214 W EP 2024067214W WO 2025002964 A1 WO2025002964 A1 WO 2025002964A1
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WO
WIPO (PCT)
Prior art keywords
reactor
stream
gas
polymer particles
propylene
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/EP2024/067214
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English (en)
Inventor
Erik René Delsman
Kiran Abraham JACOB
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
SABIC Global Technologies BV
Original Assignee
SABIC Global Technologies BV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by SABIC Global Technologies BV filed Critical SABIC Global Technologies BV
Publication of WO2025002964A1 publication Critical patent/WO2025002964A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • 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
    • C08F6/001—Removal of residual monomers by physical means
    • C08F6/005—Removal of residual monomers by physical means from solid polymers
    • 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
    • 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
    • B01J8/085—Feeding reactive fluids
    • 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
    • B01J2208/00256—Controlling the temperature by indirect heat exchange with heat exchange elements outside the bed of solid particles in a heat exchanger for the heat exchange medium separate from the 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
    • 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
    • B01J2208/00274—Part of all of the reactants being heated or cooled outside the reactor while recycling involving reactant vapours
    • 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
    • B01J2208/00743—Feeding or discharging of solids
    • B01J2208/00761—Discharging
    • 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
    • B01J2208/00743—Feeding or discharging of solids
    • B01J2208/00769—Details of feeding or discharging
    • B01J2208/00787—Bringing the solid in the form of a slurry before feeding it to the 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/24—Stationary reactors without moving elements inside
    • B01J2219/2401—Reactors comprising multiple separate flow channels
    • B01J2219/245—Plate-type reactors
    • B01J2219/2475—Separation means, e.g. membranes inside the reactor

Definitions

  • the present invention relates to an olefin polymerization process comprising polymerization of olefin monomer(s) in one or more polymerization reactors.
  • Polyolefins such as polyethylene and polypropylene, may be prepared by particle form polymerization, also referred to as slurry polymerization.
  • a monomer feed may be polymerized in a reaction zone in the presence of a catalyst and optionally, a solvent (also known as a diluent) to produce a polymerization effluent containing a slurry of polymer solids in a liquid medium comprising unreacted hydrocarbon monomer and optionally, solvent.
  • the polymerization effluent may be withdrawn from the reactor and the polymer solids may be separated from the liquid medium.
  • Typical polymer recovery and separation systems include subjecting the polymerization effluent to a reduction in pressure so that the liquid medium may vaporize leaving concentrated polymer solids.
  • the vaporized liquid medium may exit at an upper portion of a flash tank, while the polymer solids may be recovered through a lower portion of the flash tank. The vaporized liquid medium can then be recycled back to the reaction zone.
  • WO 2017/102303 in the name of the present applicant relates to an olefin polymerization process comprising polymerization of at least one olefin monomer in one or more polymerization reactors wherein the polymerization process is carried out in an apparatus comprising one or more reactor vessels to which olefin monomer and catalyst components can be added and which contain an agitated bed of forming polymer particles, means for removing a stream comprising polymer particles from the reactor, means for removing a gas-liquid stream comprising unreacted olefin monomers from the reactor, means for withdrawing a liquid recycle stream from the gas-liquid stream, means for recycle a gas-liquid stream to the reactor, wherein the process further comprises the steps of withdrawing a gaseous stream from the stream comprising polymer particles, contacting a liquid recycle stream with the gaseous stream thereby forming a mixture, withdrawing a liquid stream from the mixture and recycling a vapor stream from the mixture to the polymerization reactor.
  • EP 1 853 635 relates to a process for the polymerization of ethylene in which the ethylene is polymerized in the presence of a catalyst in a gas-phase reactor to form polymer particles and reaction gas comprising propane and unpolymerized ethylene is circulated to remove the heat of polymerization, wherein the polymer particles are discharged continuously or discontinuously from the reactor, the polymer particles are separated from the major part of the concomitantly discharged gas and the polymer particles are degassed, the gas is freed of entrained fine particles, the gas is separated from a low-boiling fraction comprising in a first separation stage, a propane fraction is separated off in a second separation stage and this propane fraction is used for degassing the polymer particles discharged from the reactor.
  • EP 2 083 020 relates to a process for the recovery of unreacted monomers from a polyolefin polymerization process, comprising the steps of recovering a fluid stream generated by the separation of the polyolefin product from the polymerization fluid comprising unreacted monomers and optionally comonomers, contacting said fluid stream in an absorption zone with a scrub liquid, thereby absorbing at least a portion of the unreacted monomers in said scrub liquid; and withdrawing from said absorption zone a vapor overhead comprising light gas and an absorber bottoms scrub liquid comprising said unreacted monomer and thereby recovering said unreacted monomer in said absorber bottoms scrub liquid.
  • WO 2019/027565 relates to a method for separating gaseous unreacted hydrocarbon monomer and/or solvent from polyolefin solids, wherein the method consists essentially of contacting a first stream comprising the polyolefin solids and the gaseous unreacted hydrocarbon monomer and/or solvent with a first purge gas in a gas-solid separation vessel to separate the gaseous unreacted hydrocarbon monomer and/or solvent from the polyolefin solids to produce a second stream comprising polyolefin solids substantially free of gaseous unreacted hydrocarbon monomer and/or solvent and a third stream comprising the gaseous unreacted hydrocarbon monomer and/or solvent, wherein the first purge gas comprises hydrocarbon monomer and/or solvent and has a temperature of at least about 70°C when entering the gas-solid separation vessel.
  • WO 2019/027566 relates to a method for separating gaseous unreacted hydrocarbon monomer and/or solvent from polyolefin solids, wherein the method consists essentially of flowing a first stream comprising polyolefin solids and gaseous unreacted hydrocarbon monomer and/or solvent through a portion of a gas-solid separation vessel having a volume sufficient so that polyolefin solids present in the first stream have a residence time within the gas-solid separation vessel > about 5.0 minutes to separate gaseous unreacted hydrocarbon monomer and/or solvent from the polyolefin solids to produce a second stream comprising polyolefin solids substantially free of gaseous unreacted hydrocarbon monomer and/or solvent and a third stream comprising the gaseous unreacted hydrocarbon monomer and/or solvent.
  • the present inventors found that when producing polypropylene or polyethylene copolymers with 1-hexene (C6) or 1-butene (C4), a large amount will remain dissolved in the polymer powder leaving the reactor. For safety and product quality reasons, these components need to be removed from the polymer powder, typically using purging with nitrogen. In addition, for example hexene is a valuable component and that component need to be recovered from this stream as well. The recovery of these valuable components is most effectively done before the purge column, because at that stage the monomers need to be separated from a large amount of nitrogen, which involves additional costs.
  • H2 poor quench liquid comprising propylene
  • H2 rich quench liquid comprising H2, ethylene and propylene and 1 -hexene
  • the step of collecting the polymer particles formed in the agitated bed from the reactor comprises a step of contacting the stream of polymer particles with a stripping gas thereby forming a stream of polymer particles having a C4-C8 olefins content that is lower than the C4-C8 olefins content of the stream of polymer particles formed in the agitated bed from the reactor,
  • the stripping gas is chosen from the group of vaporized propylene and ethylene.
  • the step of collecting the polymer particles will result in the formation of a stream of polymer particles having a C4-C8 olefins content that is lower than the C4-C8 olefins content of the stream of polymer particles formed in the agitated bed from the reactor
  • the C4-C8 olefins content of the stream of polymer particles thus obtained is reduced with at least 20 wt.%, preferably at least 40 wt.%, more preferably 50 wt.%, compared to the C4-C8 olefins content of the stream of polymer particles formed in the agitated bed, .
  • the stripping gas is contacted in a countercurrent flow with the polymer particles formed in the agitated bed from the reactor.
  • the stripping gas is chosen from the group of vaporized propylene and ethylene.
  • the temperature during the step of contacting with the stripping gas is in a range of 50 - 70 °C.
  • its temperature might be as low as -30 °C.
  • Figure 1 shows a process flow diagram of an olefin polymerization process according to the present invention.
  • Figure 2 shows a diagram of the temperature of the discharge vessel vs the amount of iso-hexane obtained via a computer simulation program.
  • the olefin polymerization process 100 comprises a reactor 6 with an inlet 1 (liquid) and an inlet 4 (vapor).
  • reactor 6 the reactants form the polymer particles and a mixed stream 10 of polymer particles and vapor is withdrawn from reactor 6.
  • Mixed stream 10 is sent to a product discharge vessel 11 wherein a separation takes place between a stream 12 of polymer particles and a gas stream 13.
  • Stream 20 is a stripping gas.
  • Stream 13 is sent to a multi-stage compressor 14.
  • the resulting compressed stream 17 is contacted with stream 18, i.e. the vapor outlet of reactor 6.
  • the combined stream 19 is sent to a condenser 7 resulting is a cooled stream 8.
  • Part of stream 8 is a purge 3 (liquid) of the recycle loop.
  • the remainder part 9 is recycled to reactor 6.
  • the combination of vapor stream 17 and vapor outlet 18 from reactor 6 is sent to unit 7 resulting in a stream 8 and a stream 4.
  • vapor stream 17 can bypass unit 7 and is thus directly combined with vapor stream 4.
  • the remainder stream 9 is combined with fresh monomer feed as stream 2 and the resulting stream 1 , combined with stream 4, is used as the inlet stream 5 for reactor 6.
  • stream 2 is fed to stream 8 before liquid purge 3, since typical fresh feeds are added to the separator drum .
  • purge 3 is sent to other process units, i.e. there is not direct recycle or return of that purge 3 to the reactor 6.
  • Figure 1 shows a single reactor 6, the reactor may comprise several reactors placed in series.
  • the present inventors found that dissolved monomers require some time to diffuse from the polymer particles to the gas phase, such that the efficiency of the degassing can be improved by increasing the residence time in discharge vessel 11. Adding a stripping gas 20 will further improve the efficiency of the degassing. However, an inert gas cannot be used since it will be directly recycled to reactor 6 and build-up in the process to unacceptable levels. In order to remove the higher molecular weight monomers the present inventors found that vaporized main monomer, e.g. ethylene or propylene, are used as stripping gas to lower specifically the amount of heavier monomer going to the next step of the process.
  • vaporized main monomer e.g. ethylene or propylene
  • the process comprises a sequential polymerization process comprising at least two reactors connected in series, wherein said process comprises the steps of preparing the first terpolymer in a first reactor from propylene, ethylene and 1- hexene, and possibly C4 or C8 as additional monomer, using a first set of conditions, - transferring the first terpolymer and unreacted comonomers of the first reactor to a second reactor, - feeding propylene, ethylene and 1 -hexene to the second reactor, preparing the second terpolymer in the second reactor in the presence of the first terpolymer fraction using a second set of conditions to obtain the terpolymer composition, wherein the first and second set of conditions differ in one or more conditions chosen from the group of pressure, temperature, propylene concentration, ethylene concentration, 1 -hexene concentration and hydrogen concentration.
  • each of the reactors is a gas- phase reactor
  • Figure 2 shows a diagram of the temperature of the discharge vessel vs the amount of iso-hexane obtained via a computer simulation program.
  • the modelling results have been produced for three different temperatures, i.e. 60, 65 and 75°C in combination with four different process conditions, i.e. a situation with no stripping gas, and situations with a varying gas flow rate at a fixed temperature (500, 900 and 1500 kg/h). In all situations the residence time is 8 mins.
  • an amount of 6.5 wt.% dissolved propylene was used, which would be equivalent to 3000 kg/h.
  • the pressure is in a range of 0-1 barg.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

La présente invention concerne un procédé de polymérisation d'oléfines comprenant la polymérisation d'au moins un monomère oléfinique dans un ou plusieurs réacteurs de polymérisation. Un objet de la présente invention est de récupérer des composants n'ayant pas réagi à partir de la poudre de polymère quittant le réacteur d'un procédé de polymérisation d'oléfines. Un autre objet de la présente invention est de réduire la quantité de monomères dissous ayant un poids moléculaire plus élevé pour empêcher des problèmes d'encrassement et de formation de morceaux lors d'opérations de purge ultérieures.
PCT/EP2024/067214 2023-06-27 2024-06-20 Procédé de polymérisation d'oléfines Pending WO2025002964A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP23181860 2023-06-27
EP23181860.0 2023-06-27

Publications (1)

Publication Number Publication Date
WO2025002964A1 true WO2025002964A1 (fr) 2025-01-02

Family

ID=87060073

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2024/067214 Pending WO2025002964A1 (fr) 2023-06-27 2024-06-20 Procédé de polymérisation d'oléfines

Country Status (1)

Country Link
WO (1) WO2025002964A1 (fr)

Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4921919A (en) 1985-12-10 1990-05-01 Amoco Corporation Method and apparatus for minimizing polymer agglomerate or lump formation in a gas-phase polypropylene polymerization reactor
US5376742A (en) * 1993-09-23 1994-12-27 Quantum Chemical Corporation Monomer recovery in gas phase fluid bed olefin polymerization
EP1853635A1 (fr) 2005-02-04 2007-11-14 Basell Polyolefine GmbH Procede et dispositif de polymerisation d'ethylene
WO2008015228A2 (fr) * 2006-08-03 2008-02-07 Basell Polyolefine Gmbh Procédé pour la finition de polyoléfines
EP2083020A1 (fr) 2008-01-18 2009-07-29 Total Petrochemicals Research Feluy Procédé pour la récupération de monomères d'un procédé de polymérisation
WO2013056979A1 (fr) * 2011-10-17 2013-04-25 Ineos Europe Ag Commande de procédé de dégazage de polymère
WO2017023433A1 (fr) * 2015-07-31 2017-02-09 Exxonmobil Chemical Patents Inc. Récupération de monomères n'ayant pas réagi à partir de procédés de polymérisation d'oléfines
WO2017102303A1 (fr) 2015-12-15 2017-06-22 Sabic Global Technologies B.V. Procédé de polymérisation d'oléfines
WO2019022799A1 (fr) * 2017-07-26 2019-01-31 Exxonmobil Chemical Patents Inc. Élimination de monomères n'ayant pas réagi et d'autres matériaux à partir de particules de produit de polyoléfine
EP3438133A1 (fr) * 2017-08-04 2019-02-06 Basell Polyolefine GmbH Processus de polymérisation comprenant des particules de polyoléfine de décharge provenant d'un réacteur de polymérisation en phase gazeuse
WO2019027565A1 (fr) 2017-08-01 2019-02-07 Exxonmobil Chemical Patents Inc. Procédés de récupération de solides de polyoléfine
WO2019027566A1 (fr) 2017-08-01 2019-02-07 Exxonmobil Chemical Patents Inc. Procédés de récupération de solides de polyoléfine
WO2023225453A1 (fr) * 2022-05-20 2023-11-23 Chevron Phillips Chemical Company Lp Systèmes et techniques de dégazage de polymère

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4921919A (en) 1985-12-10 1990-05-01 Amoco Corporation Method and apparatus for minimizing polymer agglomerate or lump formation in a gas-phase polypropylene polymerization reactor
US5376742A (en) * 1993-09-23 1994-12-27 Quantum Chemical Corporation Monomer recovery in gas phase fluid bed olefin polymerization
EP1853635A1 (fr) 2005-02-04 2007-11-14 Basell Polyolefine GmbH Procede et dispositif de polymerisation d'ethylene
WO2008015228A2 (fr) * 2006-08-03 2008-02-07 Basell Polyolefine Gmbh Procédé pour la finition de polyoléfines
EP2083020A1 (fr) 2008-01-18 2009-07-29 Total Petrochemicals Research Feluy Procédé pour la récupération de monomères d'un procédé de polymérisation
WO2013056979A1 (fr) * 2011-10-17 2013-04-25 Ineos Europe Ag Commande de procédé de dégazage de polymère
WO2017023433A1 (fr) * 2015-07-31 2017-02-09 Exxonmobil Chemical Patents Inc. Récupération de monomères n'ayant pas réagi à partir de procédés de polymérisation d'oléfines
WO2017102303A1 (fr) 2015-12-15 2017-06-22 Sabic Global Technologies B.V. Procédé de polymérisation d'oléfines
WO2019022799A1 (fr) * 2017-07-26 2019-01-31 Exxonmobil Chemical Patents Inc. Élimination de monomères n'ayant pas réagi et d'autres matériaux à partir de particules de produit de polyoléfine
WO2019027565A1 (fr) 2017-08-01 2019-02-07 Exxonmobil Chemical Patents Inc. Procédés de récupération de solides de polyoléfine
WO2019027566A1 (fr) 2017-08-01 2019-02-07 Exxonmobil Chemical Patents Inc. Procédés de récupération de solides de polyoléfine
EP3438133A1 (fr) * 2017-08-04 2019-02-06 Basell Polyolefine GmbH Processus de polymérisation comprenant des particules de polyoléfine de décharge provenant d'un réacteur de polymérisation en phase gazeuse
WO2023225453A1 (fr) * 2022-05-20 2023-11-23 Chevron Phillips Chemical Company Lp Systèmes et techniques de dégazage de polymère

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