WO2019162448A1 - Processus - Google Patents

Processus Download PDF

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Publication number
WO2019162448A1
WO2019162448A1 PCT/EP2019/054457 EP2019054457W WO2019162448A1 WO 2019162448 A1 WO2019162448 A1 WO 2019162448A1 EP 2019054457 W EP2019054457 W EP 2019054457W WO 2019162448 A1 WO2019162448 A1 WO 2019162448A1
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WO
WIPO (PCT)
Prior art keywords
hydrogen
solvent
feed stream
unreacted monomer
polymerisation
Prior art date
Application number
PCT/EP2019/054457
Other languages
English (en)
Inventor
Mohammad AL-HAJ ALI
Noureddine AJELLAL
Vasileios KANELLOPOULOS
Henry Sleijster
Samuli Zitting
Irfan Saeed
Original Assignee
Borealis Ag
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 Borealis Ag filed Critical Borealis Ag
Priority to SG11202007620YA priority Critical patent/SG11202007620YA/en
Priority to BR112020016242-6A priority patent/BR112020016242A2/pt
Publication of WO2019162448A1 publication Critical patent/WO2019162448A1/fr

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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
    • 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
    • C08F10/02—Ethene
    • 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
    • C08F2/04—Polymerisation in solution
    • C08F2/06—Organic solvent

Definitions

  • This invention relates to a process for separating hydrogen from a fluid feed stream in a polymerisation process, in particular to a process wherein said fluid feed stream is contacted with a heterogeneous catalyst.
  • the invention further relates to apparatus arranged to perform the process of the invention and to the use of a heterogeneous catalyst for the separation of hydrogen in the process of the invention.
  • Hydrogen is frequently employed as a reactant (chain transfer agent) in polymerisation reactions, particularly those used to prepare polyolefins, to control polymer properties, such as molecular weight. It also affects polymerisation rate, although this is further influenced by other factors such as catalyst type, monomers used and process conditions, i.e. temperature and pressure. Hydrogen is also typically produced as a side-product during olefin polymerisation. This gas will therefore normally be present in the product reaction mixture.
  • EP 1605000 discloses the use of a hydrogenating agent which is contacted with the catalyst prior to polymerisation.
  • EP 0905153 considers the removal of hydrogen wherein a hydrogenation catalyst is added into the process stream in between two loop reactors employing Ziegler-Natta polymerisation catalysts.
  • the hydrogenation catalyst typically a metallocene, acts to consume the hydrogen gas, converting it to ethane, prior to entry into a second reactor.
  • a process with high separation efficiency is desirable.
  • a process which can easily be incorporated into existing technologies and plant set-ups is looked-for. Preferably, more than one of these factors is achieved. Summary
  • the invention provides a process for separating hydrogen from a fluid feed stream in a polymerisation process, comprising the steps:
  • the invention provides a process as hereinbefore defined wherein step i. is a solution polymerisation process.
  • the invention provides the use of a heterogeneous hydrogenation catalyst for the separation of hydrogen in a process as
  • the invention provides apparatus arranged to perform the process as hereinbefore defined comprising:
  • At least one reactor configured to receive an olefin monomer, solvent and optionally at least one olefin comonomer, and optionally hydrogen, via at least one first inlet so as to produce a polymerisation reaction mixture comprising a polyolefin polymer, unreacted monomer(s), solvent and hydrogen;
  • a separator in fluid communication with said reactor configured to receive said polymerisation reaction mixture via at least one second inlet so as to separate said polyolefin polymer from said unreacted monomer(s), solvent and hydrogen and to produce a fluid feed stream comprising said unreacted monomer(s), solvent and hydrogen;
  • a hydrogenation column comprising a heterogeneous hydrogenation catalyst in fluid communication with said separator configured to receive said fluid feed stream via at least one third inlet so as to produce a hydrogen-lean fluid stream.
  • the invention provides a process for controlling the molecular weight of a polyolefin polymer comprising the comprising the steps:
  • step iii contacting said fluid feed stream with a heterogeneous hydrogenation catalyst so as to form a hydrogen-lean fluid stream; and iv. recycling the hydrogen-lean fluid stream from step iii to step i.
  • polypropylene is meant a polymer containing at least 70 wt% of propylene residues, preferably at least 80 wt% of propylene residues. Any comonomer present in a polypropylene of the invention is another alpha olefin.
  • polyethylene is meant a polymer containing at least 50 wt% of ethylene residues, preferably at least 60 wt% of ethylene residues. Any comonomer present in a polyethylene of the invention is another alpha olefin.
  • the processes of the invention comprise a first step in which an olefin monomer and optionally at least one comonomer, in the presence of a solvent (typically a mixture of hydrocarbons), are polymerised (optionally in the presence of hydrogen) so as to form a polymerisation reaction mixture comprising a polyolefin polymer, unreacted monomer(s), solvent and hydrogen.
  • a solvent typically a mixture of hydrocarbons
  • hydrogen hydrogen
  • the polyolefin for the polymer composition is preferably selected from a polypropylene (PP) or polyethylene (PE), preferably from a polyethylene.
  • PP polypropylene
  • PE polyethylene
  • ethylene will form the major monomer content present in any polyethylene polymer.
  • the polyolefin is a polyethylene.
  • the preferred olefin monomer of the invention is ethylene.
  • a polyolefin is a copolymer of ethylene with at least one comonomer
  • such comonomer(s) is selected from non-polar comonomer(s) or polar comonomers, or any mixtures thereof.
  • Preferable optional non-polar comonomers and polar comonomers are described below. These comonomers can be used in any polyolefin of the invention.
  • the polyolefin is typically one prepared in the presence of an“olefin polymerisation catalyst”, which is preferably a conventional coordination catalyst. It is preferably selected from a Ziegler-Natta catalyst, single site catalyst (which term encompasses a metallocene and a non-metallocene catalyst), or a chromium catalyst, or any mixture thereof. The terms have a well-known meaning.
  • an“olefin polymerisation catalyst is preferably a conventional coordination catalyst. It is preferably selected from a Ziegler-Natta catalyst, single site catalyst (which term encompasses a metallocene and a non-metallocene catalyst), or a chromium catalyst, or any mixture thereof.
  • the terms have a well-known meaning.
  • the polyolefin is selected from a homopolymer or a copolymer of ethylene produced in the presence of a coordination catalyst.
  • the polyolefin is a polyethylene (PE)
  • PE polyethylene
  • VLDPE very low density ethylene copolymer
  • LLDPE linear low density ethylene copolymer
  • MDPE medium density ethylene copolymer
  • HD PE high density ethylene homopolymer or copolymer
  • VLDPE includes herein polyethylenes which are also known as plastomers and elastomers and covers the density range of from 850 to 909 kg/m 3 .
  • the LLDPE has a density of from 909 to 930 kg/m 3 , preferably of from 910 to 929 kg/m 3 , more preferably of from 915 to 929 kg/m 3 .
  • the MDPE has a density of from 930 to 945 kg/m 3 , preferably 931 to 945 kg/m 3 .
  • the HDPE has a density of more than 945 kg/m 3 , preferably of more than 946 kg/m 3 , preferably from 946 to 977 kg/m 3 , more preferably from 946 to 965 kg/m 3 .
  • the polyolefin is an ethylene copolymer it is typically copolymerised with at least one comonomer selected from C3-20 alpha olefin, more preferably from C4-12 alpha-olefin, more preferably from C4-8 alpha-olefin, e.g. with 1- butene, 1 -hexene or l-octene, or a mixture thereof.
  • the amount of comonomer(s) present in a PE copolymer is from 0.1 to 25 mol%, typically 0.25 to 20 mol%.
  • polymerisation methods well known to the skilled person may be used. Typically, however, a solution polymerisation process is employed.
  • “solution polymerisation” is intended to mean a process in which all reactants and products (in particular, the polyolefin product) remain in solution.
  • the polyolefin polymer is soluble in any hydrocarbons present in the mixture (such as solvent, monomer and comonomer), thereby forming a homogenous single phase in the reactor.
  • suitable polymerisation conditions may be selected to ensure this solubility. With specific reference to the processes of the invention, therefore, the polymerisation reaction mixture produced in step i. is a homogenous single phase.
  • The“solution” processes of the invention may thus be contrasted with “slurry” processes which are typically carried out in loop reactors.
  • the reaction temperature will generally be in the range 60 to 1 l0°C, e.g. 85- 110 °C
  • the reactor pressure will generally be in the range 5 to 80 bar, e.g. 50-65 bar
  • the residence time will generally be in the range 0.3 to 5 hours, e.g. 0.5 to 2 hours.
  • the diluent used will generally be an aliphatic hydrocarbon having a boiling point in the range -70 to +100 °C, e.g. propane.
  • the polyolefin product forms a separate phase in the reactor and does not remain in solution.
  • the processes of the invention are used to separate hydrogen from a fluid feed stream in a solution polymerisation process.
  • Polymerisation conditions will be dependent on several factors, such as the olefin monomer(s) used, and the skilled person will appreciate how to select the most appropriate conditions. Temperatures of at least 140 °C are generally used, such as 140 to 300 °C, preferably 150 to 250 °C. Typical pressures are in the range 40 to 150 bar.
  • the polymerisation may be carried out in a single reactor.
  • two or more reactors configured either in parallel or series may be employed.
  • Any suitable conventional reactor may be used, such as a stirred tank reactor.
  • Step i. of the processes of the invention is preferably carried out in the presence of a polymerisation catalyst, such as a Ziegler-Natta or single-site catalyst, such as a metallocene.
  • a polymerisation catalyst such as a Ziegler-Natta or single-site catalyst, such as a metallocene.
  • the catalyst is a metallocene
  • Any ordinary stereospecific Ziegler-Natta catalysts can be used.
  • An essential component in those catalysts are solid catalyst components comprising a titanium compound having at least one titanium-halogen bond, an internal electron donor compound and a magnesium halide in active form as a carrier for both the titanium component and the donor compound.
  • the catalysts may contain - as internal electron donor - compounds selected from ethers, ketones, lactones, compounds containing N, P and/or S atoms and esters of mono and dicarboxylic acids.
  • Any metallocene catalyst capable of catalysing the formation of an olefmic polymer can also be used.
  • a suitable metallocene catalyst comprises a
  • the catalyst complex comprises a ligand which is typically bridged, and a transition metal of group IVa to Via, and an organoaluminium compound.
  • the catalytic metal compound is typically a metal halide.
  • Suitable metallocene compounds are those which have a formula (Cp) m R n MR' o X p , where Cp is an unsubstituted or substituted and/or fused homo or heterocyclopentadienyl, R is a group having 1-4 atoms and bridging two Cp rings,
  • M is a transition metal of group 4, 5 or 6 in the Periodic Table of Elements (IUPAC, 1985), R' is Ci -C 2 hydrocarbyl or hydrocarboxy group and X is a halogen atom, wherein m is 1-3, n is 0 or 1, o is 0-3 and p is 0-3 and sum n+o+p corresponds the oxidation state of the transition metal M.
  • the transition metal M is preferably zirconium, hafnium or titanium, most preferably hafnium. Examples of suitable metallocene compounds are, among others,
  • metallocene catalysts are frequently used with catalyst activators or co- catalysts, e.g. alumoxanes such as methylaluminoxane, which are widely described in the literature.
  • the metallocene catalyst may be supported as is well known in the art.
  • Any suitable support or carrier material can be used, which may be any porous, substantially inert support, such as an inorganic oxide or salt.
  • the support used is preferably a fine-grained inorganic oxide such as an inorganic oxide of an element of Group 2, 13 or 14 in the Periodic Table of Elements (IUPAC, 1985), most preferably silica, alumina or a mixture or derivative of these.
  • Other inorganic oxides which can be used either alone or together with silica, alumina or silica- alumina are magnesium oxide, titanium dioxide, zirconium oxide, aluminum phosphate etc.
  • the catalyst may be used in non-supported form or in solid form.
  • Non-supported catalyst systems suitable for the present invention can be prepared in solution, for example in an aromatic solvent like toluene, by contacting the metallocene (as a solid or as a solution) with the cocatalyst(s), for example methylaluminoxane and/or a borane or a borate salt previously in an aromatic solvent, or can be prepared by sequentially adding the dissolved catalyst components to the polymerisation medium.
  • an aromatic solvent like toluene
  • cocatalyst(s) for example methylaluminoxane and/or a borane or a borate salt previously in an aromatic solvent
  • the catalyst system of the invention in solid form preferably in solid particulate form is free from an external carrier, however still being in solid form.
  • the catalyst does not contain an external support, such as an inorganic support, for example, silica or alumina, or an organic polymeric support material.
  • the process involves forming dispersing catalyst components (i) (the complex) and (ii) + optionally (iii) the cocatalysts) in a solvent, and solidifying said dispersed droplets to form solid particles.
  • the method involves preparing a solution of the catalyst components; dispersing said solution in an solvent to form an emulsion in which said one or more catalyst components are present in the droplets of the dispersed phase; immobilising the catalyst components in the dispersed droplets, in the absence of an external particulate porous support, to form solid particles comprising the said catalyst, and optionally recovering said particles.
  • This process enables the manufacture of active catalyst particles with improved morphology, e.g. with a predetermined particle size, spherical shape, compact structure, excellent surface properties and without using any added external porous support material, such as an inorganic oxide, e.g. silica.
  • the catalyst particles can have a smooth surface, they may be compact in nature and catalyst active components can be distributed uniformly thorough the catalyst particles. Full disclosure of the necessary process steps can be found in, for example,
  • All or part of the preparation steps can be done in a continuous manner.
  • the formed catalyst preferably has good stability/kinetics in terms of longevity of reaction, high activity and the catalysts enable low ash contents.
  • heterogeneous, non-supported catalysts i.e. "self-supported” catalysts
  • the heterogeneous, non-supported catalysts might have, as a drawback, a tendency to dissolve to some extent in the polymerisation media, i.e. some active catalyst components might leach out of the catalyst particles during slurry polymerisation, whereby the original good
  • the self-supported catalysts generate, due to the high amount of catalytically active species in the catalyst system, high temperatures at the beginning of the polymerisation which may cause melting of the product material. Both effects, i.e. the partial dissolving of the catalyst system and the heat generation, might cause fouling, sheeting and deterioration of the polymer material morphology.
  • prepolymerisation in this regard is part of the catalyst preparation process, being a step carried out after a solid catalyst is formed. This catalyst prepolymerisation step is not part of the actual
  • polymerisation configuration which might comprise a conventional process prepolymerisation step as well.
  • catalyst prepolymerisation step After the catalyst prepolymerisation step, a solid catalyst is obtained and used in polymerisation.
  • Catalyst "prepolymerisation” takes place following the solidification step of the liquid-liquid emulsion process hereinbefore described. Prepolymerisation may take place by known methods described in the art, such as that described in WO 2010/052263 , WO 2010/052260 or WO 2010/052264 . Use of the catalyst prepolymerisation step offers the advantage of minimising leaching of catalyst components and thus local overheating.
  • the solvent employed in the processes of the invention may be any solvent suitable for use in olefin polymerisation and is typically a mixture of hydrocarbons. Such solvents are well known in the art. Examples of solvents include hexane, cyclohexane, isohexane, n-heptane, C8, C9 isoparaffins and mixtures thereof.
  • the polymerisation is carried out in the presence of hydrogen.
  • Hydrogen is typically employed to help control polymer properties, such as polymer molecular weight.
  • hydrogen is not added in step i.
  • the skilled worker will appreciate, however, that hydrogen may be generated during the polymerisation process.
  • the hydrogen present in the polymerisation reaction mixture formed in step i. of the process may originate from hydrogen which has been added as a reactant and/or hydrogen produced as a side product during polymerisation.
  • the polyolefin polymers may contain standard polymer additives. These typically form less than 5 wt%, such as less than 2 wt% of the polymer material. Additives, such as antioxidants, phosphites, cling additives, pigments, colorants, fillers, anti-static agent, processing aids, clarifiers and the like may thus be added during the polymerisation process. These additives are well known in the industry and their use will be familiar to the artisan.
  • step ii. of the process the polyolefin is separated from any unreacted monomer(s), solvent and hydrogen so as to produce a fluid feed stream comprising unreacted monomer(s), solvent and hydrogen.
  • This separation may be carried out by any suitable method known in the art, however typically it will be performed by flash evaporation in a flash separator or by gravimetric separation.
  • flash separation processes the polyolefin remains as a liquid stream and a vapour stream is produced comprising the more volatile components including unreacted monomer(s), solvent and hydrogen. That vapour stream may also comprise additional materials, such as inert gases.
  • the present invention relates to the separation of hydrogen from a“fluid” feed stream.
  • the term“fluid” covers both vapour and liquids, thus the fluid feed stream of the invention is intended to cover a gaseous feed stream or a liquid feed stream, or a mixture thereof.
  • the vapour stream produced in step ii of the process, as described above may be considered the“fluid feed stream”.
  • an additional step may be employed in which said vapour stream is fed to a heat exchanger or other cooling device (e.g. a condenser) so as to convert said vapour stream to a liquid feed stream from which hydrogen can subsequently be separated.
  • a heat exchanger or other cooling device e.g. a condenser
  • the liquid feed stream formed in the condenser may be considered the“fluid feed stream” of the invention.
  • step ii. of the invention further comprises feeding the unreacted monomer(s), solvent and hydrogen which have been separated from the polyolefin polymer to a heat exchanger.
  • the fluid feed stream comprises unreacted monomer(s), solvent and hydrogen. It will be understood that additional components may also be present, which could include side-products produced during the polymerisation reaction. For example, when 1 -butene is used as a comonomer, components such as iso-butene, 2- butene and butane may also be present in the fluid feed stream. Hydrogen is typically present in the fluid fed stream in amounts of 0.1 to 70 ppm, such as ⁇ 1.0 to 50 ppm.
  • the fluid feed stream further comprises at least one hydrogenating agent, which is usually unreacted monomer(s), such as ethylene, octene or butene .
  • Typical unreacted monomer(s) contents in the fluid feed stream are in the range 0.05 to 25 wt%, preferably 0.1 to 20 wt%, such as 0.15 to 15 wt% relative to the total weight of the fluid stream leaving the separator vessel.
  • the unreacted monomer(s) functions as a key component of the
  • the hydrogen is consumed by reaction with unreacted monomer(s), in conjunction with the hydrogenation catalyst to produce an alkane.
  • Step iii. of the process of the invention involves contacting the fluid feed stream produced in step ii. with a heterogeneous hydrogenation catalyst, so as to form a hydrogen-lean fluid stream.
  • a heterogeneous hydrogenation catalyst we mean a catalyst which is in a different phase to the fluid feed stream and which serves to catalyse the hydrogenation reaction.
  • the catalyst is a solid phase catalyst.
  • Suitable solid phase catalysts are well known in the art but may preferably be selected from the group of nickel, palladium and platinum catalysts.
  • the fluid feed stream may be brought into contact with the hydrogenation catalyst by any suitable means, however it this usually takes place in a hydrogenation column.
  • the separation efficiency (i.e. the efficiency of hydrogen removal) of step iii. of the processes of the invention is preferably at least 75%, preferably at least 80%, such as at least 90%.
  • the hydrogen-lean fluid stream produced in step iii. Typically comprises hydrogen in amounts of less than 5 ppm, preferably less than 2 ppm, more preferably less than 0.5 ppm.
  • the hydrogen-lean fluid stream is recycled back to the polymerisation reactor.
  • the processes of the invention can be incorporated into continuous polymerisation processes where it is desired that the vapour stream produced after separation from the polyolefin product is recycled to be used as further reactant. Incorporating into existing industrial polymerisation plant set-ups is therefore possible and relatively facile.
  • Apparatus in a further aspect, provides apparatus arranged to perform the process as hereinbefore defined comprising:
  • At least one reactor configured to receive an olefin monomer and optionally at least one olefin comonomer, solvent and optionally hydrogen, via at least one first inlet so as to produce a polymerisation reaction mixture comprising a polyolefin polymer, unreacted monomer(s), solvent and hydrogen;
  • a separator in fluid communication with said reactor configured to receive said polymerisation reaction mixture via at least one second inlet so as to separate said polyolefin polymer from said unreacted monomer(s), solvent and hydrogen and to produce a fluid feed stream comprising said unreacted monomer(s), solvent and hydrogen;
  • a hydrogenation column comprising a heterogeneous hydrogenation catalyst in fluid communication with said separator configured to receive said fluid feed stream via at least one third inlet so as to produce a hydrogen-lean fluid stream.
  • step a) a single reactor may be used. Alternatively two or more reactors connected in parallel or series may be employed. Any conventional polymerisation reactor may be employed, however this is preferably a reactor suitable for solution polymerisation, such as a stirred tank reactor.
  • the separator used in step b) may be any suitable separator, but is preferably a flash separator.
  • the hydrogenation column in step c) may be any suitable column, such as a packed bed column.
  • the apparatus further comprises a heat exchanger positioned between the separator and the hydrogenation column, which is in fluid communication with both the separator and hydrogenation column.
  • the processes of the invention may be employed in any polymerisation process to separate hydrogen from a fluid feed stream produced therein. Moreover, as discussed above, because the presence of hydrogen in the polymerisation reactor can influence the molecular weight of the resultant polymer, the processes of the invention may also be considered as processes for controlling the molecular weight of a polyolefin polymer.
  • a “hydrogen-lean liquid stream” is generated which contains very low levels of hydrogen. When this is recycled to the polymerisation reactor, problems such as the generation of off- spec grades are significantly reduced because the possibility of potentially large and unknown levels of hydrogen entering the reactor is minimised.
  • the molecular weight of the polymer can be more precisely controlled.
  • the invention relates to a process for controlling the molecular weight of a polyolefin polymer comprising the comprising the steps:
  • a conventional process configuration is considered (see Figure 2), where a reactor is connected to a flash separator (1). Reactor effluent with temperature around 160 °C (depending on PE grade), is heated up to around 230 °C. The outlet stream from the flash separator is 100% vapor at a temperature close to 180 °C, the temperature of this stream is reduced finally to around 60 °C using a series of heat exchangers.
  • the components of the configuration shown in Figure 2 are as follows:
  • outlet condensate from heat exchanger Example 2 The configuration of the polymerisation process is modified so as to include a hydrogenation column downstream of the flash tank (1).

Abstract

L'invention concerne un processus de séparation d'hydrogène d'un flux d'alimentation en fluide dans un processus de polymérisation, comprenant les étapes consistant à : i) polymériser un monomère d'oléfine et éventuellement au moins un comonomère d'oléfine en présence d'un solvant, éventuellement en présence d'hydrogène, de manière à former un mélange réactionnel de polymérisation comprenant un polymère de polyoléfine, monomère (s) n'ayant pas réagi, un solvant et de l'hydrogène; ii) séparer ledit polymère de polyoléfine dudit monomère (s) n'ayant pas réagi, un solvant et de l'hydrogène, et éventuellement introduire ledit monomère (s) n'ayant pas réagi, un solvant et de l'hydrogène dans un échangeur de chaleur, de façon à produire ledit flux d'alimentation en fluide comprenant le monomère (s) n'ayant pas réagi, un solvant et de l'hydrogène; et iii) mettre en contact ledit flux d'alimentation en fluide avec un catalyseur d'hydrogénation hétérogène de manière à former un flux de fluide pauvre en hydrogène.
PCT/EP2019/054457 2018-02-22 2019-02-22 Processus WO2019162448A1 (fr)

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SG11202007620YA SG11202007620YA (en) 2018-02-22 2019-02-22 Process
BR112020016242-6A BR112020016242A2 (pt) 2018-02-22 2019-02-22 Processo

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Application Number Priority Date Filing Date Title
EP18158073 2018-02-22
EP18158073.9 2018-02-22

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WO2019162448A1 true WO2019162448A1 (fr) 2019-08-29

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0905153A1 (fr) 1997-09-27 1999-03-31 Fina Research S.A. Production de polyéthylène ayant une large distribution de poids moléculaire
WO2003051934A2 (fr) 2001-12-19 2003-06-26 Borealis Technology Oy Production de catalyseurs de polymerisation d'olefines
EP1605000A1 (fr) 2003-03-10 2005-12-14 Asahi Kasei Chemicals Corporation Polymere d' ethylene de poids moleculaire tres eleve
WO2006069733A1 (fr) 2004-12-31 2006-07-06 Borealis Technology Oy Procede
WO2010052264A1 (fr) 2008-11-07 2010-05-14 Borealis Ag Composition de catalyseur solide
WO2010052263A1 (fr) 2008-11-07 2010-05-14 Borealis Ag Composition de catalyseur solide
WO2010052260A1 (fr) 2008-11-07 2010-05-14 Borealis Ag Composition de catalyseur solide
WO2013154907A2 (fr) * 2012-04-13 2013-10-17 Chevron Phillips Chemical Company Lp Séparations de composants lors d'une polymérisation

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0905153A1 (fr) 1997-09-27 1999-03-31 Fina Research S.A. Production de polyéthylène ayant une large distribution de poids moléculaire
WO2003051934A2 (fr) 2001-12-19 2003-06-26 Borealis Technology Oy Production de catalyseurs de polymerisation d'olefines
EP1605000A1 (fr) 2003-03-10 2005-12-14 Asahi Kasei Chemicals Corporation Polymere d' ethylene de poids moleculaire tres eleve
WO2006069733A1 (fr) 2004-12-31 2006-07-06 Borealis Technology Oy Procede
WO2010052264A1 (fr) 2008-11-07 2010-05-14 Borealis Ag Composition de catalyseur solide
WO2010052263A1 (fr) 2008-11-07 2010-05-14 Borealis Ag Composition de catalyseur solide
WO2010052260A1 (fr) 2008-11-07 2010-05-14 Borealis Ag Composition de catalyseur solide
WO2013154907A2 (fr) * 2012-04-13 2013-10-17 Chevron Phillips Chemical Company Lp Séparations de composants lors d'une polymérisation

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BR112020016242A2 (pt) 2020-12-15

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