WO2020263113A1 - Procédé de réduction de dépôts de polymère sur les surfaces de l'équipement de réacteur dans le processus d'oligomérisation d'oléfines - Google Patents

Procédé de réduction de dépôts de polymère sur les surfaces de l'équipement de réacteur dans le processus d'oligomérisation d'oléfines Download PDF

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WO2020263113A1
WO2020263113A1 PCT/RU2019/000466 RU2019000466W WO2020263113A1 WO 2020263113 A1 WO2020263113 A1 WO 2020263113A1 RU 2019000466 W RU2019000466 W RU 2019000466W WO 2020263113 A1 WO2020263113 A1 WO 2020263113A1
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zinc
reactor equipment
reactor
equipment
containing coating
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PCT/RU2019/000466
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English (en)
Inventor
Maxim Vladimirovich Lipskikh
Yury Vladimirovich PROTSAY
Airat Faritovich KHUSAINOV
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Public Joint Stock Company "Sibur Holding"
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Priority to PCT/RU2019/000466 priority Critical patent/WO2020263113A1/fr
Publication of WO2020263113A1 publication Critical patent/WO2020263113A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
    • C23C10/28—Solid state diffusion of only metal elements or silicon into metallic material surfaces using solids, e.g. powders, pastes
    • C23C10/30—Solid state diffusion of only metal elements or silicon into metallic material surfaces using solids, e.g. powders, pastes using a layer of powder or paste on the surface
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
    • C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
    • C07C2/08—Catalytic processes
    • C07C2/26—Catalytic processes with hydrides or organic compounds
    • C07C2/32—Catalytic processes with hydrides or organic compounds as complexes, e.g. acetyl-acetonates
    • 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
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02—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
    • C08F2/002—Scale prevention in a polymerisation reactor or its auxiliary parts
    • C08F2/004—Scale prevention in a polymerisation reactor or its auxiliary parts by a prior coating on the reactor walls
    • 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
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/02—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using non-aqueous solutions
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • C07C2531/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • C07C2531/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • C07C2531/22—Organic complexes
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/73—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process

Definitions

  • the invention relates to the field of olefin oligomerization in order to obtain linear a-olefins, in particular hexene- 1, as well as to the field of olefin polymerization and copolymerization in order to obtain valuable polymer products such as linear low- density polyethylene, polyhexene, etc.
  • the invention relates to a method for reducing polymer deposits on the internal surfaces of reactor equipment, where the polymer is either a by-product of the olefin oligomerization process or a desired polymer formed during the polymerization or copolymerization of olefins.
  • the process of selective oligomerization of ethylene is known as an effective method of producing a-olefins of higher molecular weight, which are used as intermediates in the chemical industry or used directly as a raw material in the field of polymer chemistry.
  • the process of ethylene trimerization is of great industrial importance, since the trimer obtained in this process, hexene- 1, is especially in demand, for example, for the production of linear polyethylene of low, medium and high density and other equally valuable products.
  • hexene- 1, other hexene isomers for example, 2-hexene and 3- hexene
  • higher ethylene oligomers for example, octene, decene and dodecene
  • the use of the claimed catalytic system allows to achieve selectivity to hexene- 1 of more than 90%, while the purity of hexene- 1 in the hexene fraction is 99.9%.
  • W02003053891A1 discloses a catalytic system based on bis-(2- diethylphosphino-ethyl)-amine and a solution of CrCb in tetrahydrofuran (1 :1), wherein methylalumoxane (850 eq.) is used as an activator.
  • a catalytic system allows to provide selectivity to hexene- 1 around 93.2%, however, about 2% of the by-product polymer is also formed.
  • the formation of polymeric by-products during the olefin oligomerization leads to negative consequences.
  • the polymer can form deposits on the inner surfaces of the oligomerization reactors and/or product lines, as well as on other equipment coming into contact with the reaction mixture and the product mixture. In this regard, it becomes necessary to remove polymer deposits formed on the surfaces of the reactor equipment in order to avoid decrease of technological process parameters.
  • a hot solvent with a temperature of 75°C is introduced into the reactor after the completion of the oligomerization reaction, resulting in the dissolution of the polymer deposits.
  • the solvent used is a hydrocarbon solvent, preferably toluene.
  • reactor washing methods known in the art often permit the removal of polymer deposits without the need for subsequent mechanical cleaning, but the use of washing solutions entails the need for their disposal.
  • the washing of the reactor is accompanied by the downtime of the equipment operation, which is undesirable due to economic aspects.
  • the object of the present invention is to develop a method to reduce the deposition of polymer on the internal surfaces of the reactor equipment, wherein the polymer is a by-product of the process of olefin oligomerization.
  • the technical result resides in the reduction of deposits of a by-product polymer on the surfaces of the reactor equipment and, as a consequence, an increase in the equipment uptime.
  • Another technical result resides in facilitating reactor equipment cleaning operation in case of need, which is achieved by reducing the number of surface sites of polymer growth on the equipment surfaces, due to which the polymer chains are not predisposed to form long fibrous structures; instead, the polymer is formed into fine globules that are easily removed from the reaction zone.
  • the technical result resides in removing residual moisture and oxygen-containing compounds toxic for the catalytic system from the reactor equipment, thereby increasing the efficiency of the used catalytic system and reducing its expenditure.
  • the additional technical result resides in providing a method of applying a zinc-containing coating in a hydrocarbon solvent medium, which then serves as a medium for carrying out the oligomerization process without the need for the solvent replacement.
  • FIG. 1 and FIG. 2 are provided.
  • FIG. 1 shows the tube lattice of the reactor equipment after the oligomerization process, wherein no zinc-containing coating was applied on the surface of the reactor equipment.
  • White coat present is the deposits of the by-product polymer.
  • FIG. 2 shows the tube lattice of the reactor equipment after the oligomerization process, where a zinc-containing coating was preliminarily applied on the surface of the reactor equipment. The figure shows that the tube lattice is clear of the by-product polymer deposits.
  • the method of reducing polymer deposits on the surfaces of the reactor equipment in the process of olefin oligomerization comprises the preliminary deposition of a zinc-containing coating onto the internal surfaces of the reactor equipment exposed to the reaction medium.
  • the application of zinc-containing coatings on the internal surfaces of the reactor equipment is carried out by galvanizing with metallic zinc or by treating the surfaces with the reaction solution comprising zinc compounds.
  • reactor equipment means any container(s) in which the process of olefin oligomerization proceeds.
  • the surfaces of the reactor equipment include equipment surfaces that are in contact with or can be in contact with the reaction medium, as well as other surfaces that come into contact with the reaction medium, on which polymer deposits can be formed.
  • Any highly dispersed zinc metal powder can be used as a source of zinc for applying onto the surface of the reactor equipment.
  • the shape of the particles can be varied: e.g. spherical particles, or particles of a scaly, elongated, oblong shape.
  • the process of coating the reactor equipment surfaces with metallic zinc is carried out by any method known in the art.
  • galvanizing is used, which is known as hot or cold galvanizing, as well as diffusion galvanizing.
  • a zinc-containing coating can be deposited onto the surface of the reactor equipment by saturating the surface of the reactor equipment with zinc in the environment of highly dispersed zinc powder at a temperature of from 290°C to 450°C. (See GOST 9.316-2006: "Unified system of protection against corrosion and aging. Zinc thermal diffusion coatings. General requirements and methods of control”.)
  • Another method of applying a zinc-containing coating is dipping of small-sized equipment into a batch with molten zinc, preferably at a temperature of about 450- 470°C (hot-dip galvanizing). More specifically, the method involves surface preparation (pre-treatment) of the reactor equipment to remove contaminants, preparing a zinc alloy by heating zinc to a temperature of 450-470°C and then immersing the equipment into a molten zinc bath. The final step is the removal of the equipment from the molten zinc bath, the removal of excess zinc by drainage, vibration, and/or centrifuging and subsequent cooling of the equipment to obtain a zinc-containing coating on its surface. (See GOST ISO 10684-2015: Fasteners.
  • hydrocarbon solvent for the alkylzinc aliphatic or cycloaliphatic hydrocarbons containing from 6 to 16 carbon atoms are used.
  • the composition of the hydrocarbon solvent may also comprise unsaturated hydrocarbons, such as olefins or aromatic compounds.
  • Suitable hydrocarbon solvents or solvent components are represented by heptane, cyclohexane, decane, undecane, iso-decane fraction, hexene- 1, IsoparTM (ExxonMobil), or mixtures thereof.
  • the process of applying a zinc-containing coating onto the internal surfaces of the reactor equipment includes the following steps:
  • the zinc reaction solution is a zinc compound in a hydrocarbon solvent.
  • the concentration of zinc in the hydrocarbon solvent is not limited and is determined based on the required concentration of zinc compounds in the reaction solution.
  • the delivery of the zinc reaction solution into the reactor equipment is carried out by any available procedure.
  • all space of the reactor equipment within which polymer deposition is possible is filled with a solvent before introducing the zinc reaction solution, wherein the solvent used is any hydrocarbon solvent suitable for carrying out the oligomerization process.
  • the zinc reaction solution is injected into the reactor equipment filled with a hydrocarbon solvent, wherein the amount of the zinc reaction solution is defined at a rate of from 0.1 to 5.0 g, preferably 2.0 g of zinc compound calculated as zinc metal per one liter of total solvent being found in the reactor equipment.
  • Stirring of the zinc reaction solution in the reactor equipment is carried out at a temperature corresponding to the decomposition temperature of the selected zinc compound.
  • the stirring of the zinc reaction solution in the reactor equipment is carried out at a temperature in the range of from 25°C to 150°C, most preferably from 90°C to 100°C.
  • an increase of the temperature up to the specified values is carried out gradually, while permanently stirring. It is preferable to carry out the gradual increase of the temperature at the rate of from 20°C to 100°C/hour, preferably at the rate of 50°C/hour.
  • reactor equipment can be used for the oligomerization process without the need to change the solvent.
  • the olefins and the components of the catalytic system are introduced directly into the reactor equipment filled with the hydrocarbon solvent.
  • the olefin oligomerization process according to the present invention includes reacting raw materials containing a-olefin, under oligomerization conditions and in the presence of a catalytic system comprising a chromium source, a nitrogen-containing ligand, and an alkylaluminum in the reactor equipment, the inner surfaces of which have a zinc-containing coating applied.
  • a catalytic system comprising a chromium source, a nitrogen-containing ligand, and an alkylaluminum in the reactor equipment, the inner surfaces of which have a zinc-containing coating applied.
  • the process and conditions for a-olefins oligomerization can be any process and conditions known from the prior art, for example those known from WO 2011/093748.
  • the catalytic system comprises a chromium source, a nitrogen-containing ligand, and an alkylaluminum.
  • the advantage of the method of the present invention is the reduction, up to 100%, of the diethyl zinc amount in the composition of the catalytic system.
  • the inventors have found that carrying out the olefin oligomerization in reactor equipment having the inner surfaces with a zinc-containing coating applied thereto contributes to the efficiency increase of the catalytic system without the need to include a zinc compound thereinto.
  • the activity of the catalytic system was found to be maintained for a long period of time, which is probably due to the neutralization of catalytic poisons, in particular water and/or oxygen, in the reactor equipment and the recycled solvent by treating the reactor equipment with a zinc reaction solution, which provides applying a zinc-containing coating onto the internal surfaces of the equipment.
  • a catalytic system comprising a source of chromium, a nitrogen- containing ligand and an alkylaluminum is sufficient to achieve the desired technical result.
  • the chromium source as a part of the catalytic system may be represented by organic and/or inorganic chromium compounds.
  • the oxidation state of chromium in the compounds can vary and can be +1, +2, +3, +4, +5 and +6.
  • the chromium source is a compound of the general formula CrX n , wherein X may be the same or different organic or inorganic substituents, and n is an integer from 1 to 6.
  • Organic substituents (X) may have from 1 to 20 carbon atoms and represent alkyl group, alkoxy group, carboxy group, acetylacetonate, amino group, amido group, etc.
  • Suitable inorganic substituents represented by X are halides, sulfates, etc.
  • chromium sources include: chromium (III) chloride, chromium (III) acetate, chromium (III) 2-ethylhexanoate, chromium (III) acetylacetonate, chromium (III) pyrrolide, chromium (II) acetate, chromium (IV) dioxide (CrC Cb), etc.
  • the nitrogen-containing ligand as a part of the catalytic system is an organic compound that includes the pyrrole ring moiety, i.e. a five-membered aromatic ring with one nitrogen atom.
  • Suitable nitrogen-containing ligands include, but are not limited to pyrrole, 2,5-dimethylpyrrole, lithium pyrrolide C4H4NL1, 2-ethylpyrrole, 2- allylpyrrole, indole, 2-methylindole, 4,5,6,7-tetrahydroindole. Most preferably, pyrrole or 2,5-dimethylpyrrole is used.
  • Alkylaluminum as a part of the catalytic system can be represented by an alkylaluminum compound, as well as a halogenated alkylaluminum compound, an alkoxyalkylaluminum compound, and mixtures thereof.
  • said compounds that were not in contact with water (non-hydrolyzed), the compounds being represented by the general formulas AIR3, AlR2Hal, AIRHab, AIR2OR, AIRHalOR and/or Ab jHab, wherein R is an alkyl group, Hal is a halogen atom.
  • Suitable alkylaluminum compounds include, but are not limited to, triethylaluminum, diethylaluminum chloride, tripropylaluminum, triisobutylaluminum, diethylaluminum ethoxide and/or ethylaluminum sesquichloride, or mixtures thereof. Most preferred is the use of triethyl aluminum or a mixture of triethyl aluminum with diethyl aluminum chloride.
  • the ratios of the components of the catalytic system may vary.
  • the aluminum to chromium molar ratio may vary from 5:1 to 500:1, preferably from 10:1 to 100:1, most preferably from 20:1 to 50:1.
  • the ligand to chromium molar ratio may vary from 2:1 to 50:1, preferably from 2.5:1 to 5:1.
  • the catalytic system for carrying out the oligomerization reaction is obtained using microwave irradiation.
  • the organoaluminum compound (alkylaluminum).
  • the organoaluminum compound possibly in the form of a solution in a hydrocarbon solvent, is subjected to microwave radiation, and then mixed with the chromium source and the nitrogen-containing ligand.
  • the catalytic system components subjected to activation it is necessary for the catalytic system components subjected to activation, to be placed in a vessel that is transparent to microwave radiation, for example, in a vessel made of glass, fluoroplastic, polypropylene.
  • Microwave radiation to be used can have a frequency in the range of from 0.2 to 20 GHz. It is particularly preferable to use microwave radiation having the frequency of 2.45 GHz, which does not cause radio interference and is commonly used in domestic and industrial sources of microwave radiation.
  • the effective microwave power is from 1 W to 5,000 W per 1 g of alkylaluminum to be used calculated as elemental aluminum.
  • the irradiation time ranges from 20 seconds to 20 minutes, preferably 15 minutes. Irradiation duration of more than 20 minutes usually does not provide additional improvements in the properties of the resulting catalytic system. Irradiation with a duration of less than 20 seconds may be insufficient to modify significantly the properties of the components subjected to activation, which in turn will lead to an insufficient increase in the activity and/or selectivity of the resulting catalytic system.
  • Mixing of the alkylaluminum activated by microwave irradiation with the chromium source and the nitrogen-containing ligand is carried out in no more than 3 minutes following the completion of the irradiation, preferably no more than 1 minute following the completion of the irradiation. If the time interval between mixing the irradiated alkylaluminum with the chromium source and the nitrogen-containing ligand is 3 minutes or more, the properties of the resulting catalytic system deteriorate significantly compared to a system for which the specified time interval is less than 1 minute.
  • the mixing of the catalytic system components can be accomplished by any method known in the art.
  • the mixing of the catalytic system components is carried out for the time period of from 1 minute to 30 minutes, preferably not less than 2 minutes, not less than 4 minutes, not less than 8 minutes, not less than 15 minutes, not less than 25 minutes.
  • alkylaluminum subjected to activation by microwave irradiation can be gradually fed into mixing with other components of the catalytic system directly from a tank subjected to microwave irradiation, so that the mixing time can be any suitable time, while preventing the loss of special properties acquired by the component by microwave radiation.
  • the components of the catalytic system can be mixed in any order.
  • alkylaluminum is added to the mixture of the chromium source and the nitrogen- containing ligand.
  • the mixing of the components is carried out in a reactor equipment which could be any suitable device for carrying out oligomerization, for example, a bubble-agitated apparatus, an apparatus with a stirrer, a static mixer.
  • hydrocarbon solvent examples include, but are not limited to hexene- 1, benzene, toluene, ethylbenzene, xylene, or mixtures thereof.
  • aromatic hydrocarbons are used as the solvents to increase the stability of the catalytic system and to obtain a highly active and selective catalytic system.
  • the aromatic hydrocarbon solvent is selected from the group comprising toluene, ethylbenzene or mixtures thereof.
  • Ethylbenzene is the most preferred aromatic hydrocarbon. It is preferable to carry out the process of mixing the components and the subsequent oligomerization using that one solvent in which the pretreatment of the reactor equipment with zinc was carried out. However, other solvents may be used too.
  • oligomerization catalysts comprising a chromium source, a nitrogen-containing ligand, and an alkylaluminum
  • oligomerization catalysts known from the prior art can be used to implement the present invention.
  • the olefin oligomerization process is carried out by bringing a catalytic system diluted with a hydrocarbon solvent into a contact with raw materials, such as olefins, represented by ethylene (ethene), propylene (propene) and butylene (butene).
  • the pressure of the raw materials including olefin(s) is in the range of from 1 to 200 atm.
  • the ethylene pressure can vary in the range of from 1 to 200 atm, preferably from 10 to 60 atm, most preferably from 15 to 40 atm. It is preferable to increase ethylene pressure in order to increase the rate of oligomerization.
  • the temperature of the oligomerization process can vary in the range of from 0°C to 160°C inclusive, preferably from 40°C to 130°C. It is most preferable to maintain the temperature in the reactor in the range of from 80°C to 120°C. At this temperature, the polymer by-product, in particular polyethylene, does not precipitate from the solution and is removed from the reactor in a form of the solution, and the catalytic system remains the most active and selective. Carrying out the oligomerization process at higher temperature (above 120°C inclusive) can lead to deactivation of the catalytic system.
  • the reaction time may vary.
  • the reaction time can be defined as the residence time for the raw material and solvent in the oligomerization reaction zone.
  • the reaction time can be defined as the average residence time of the raw materials and solvent in the oligomerization reaction zone.
  • the reaction time may vary depending on the olefin used as the raw material, the reaction temperature, the pressure, and other process parameters. In the process embodiments, the reaction time usually does not exceed 24 hours.
  • the reaction time may be less than 12 hours, less than 6 hours, less than 3 hours, less than 2 hours, less than 1 hour, less than 30 minutes, less than 15 minutes, less than 10 minutes.
  • the most preferred reaction time period is ranging from 30 minutes to 90 minutes.
  • the olefin and the catalytic system can be contacted with hydrogen, which is fed to the oligomerization reactor and used as a diluent.
  • Hydrogen can accelerate the oligomerization reaction and/or increase the activity of the organometallic catalyst.
  • hydrogen can reduce the amount of the produced by-product polymer and limit the deposition of the polymer on the surface of the equipment.
  • the olefin oligomerization process must be carried out in the absence of water and oxygen.
  • the effluent from the oligomerization reactor may contain organometallic compounds, the desired product (oligomer), by-products, a solvent, as well as polymers that may be formed during the oligomerization process.
  • the effluent from the reactor can be treated with an agent deactivating the catalytic system.
  • Suitable deactivating agents known in the art are water, alcohols, amines, amino alcohols, or mixtures thereof, as well as various sorbents, such as silica gel, alumina, aluminosilicates, or mixtures thereof with water, alcohols, amines, amino alcohols.
  • sorbents such as silica gel, alumina, aluminosilicates, or mixtures thereof with water, alcohols, amines, amino alcohols.
  • alcohols or amino alcohols supported on silica gel are used as the deactivating agents.
  • the effluent from the reactor can be cooled off by passing, for example, through a heat exchanger.
  • the cooling process of the effluent coming from the reactor may comprise mixing hot effluent with cool effluent. Cooling the reactor effluent is carried out until the temperature reaches the range from 20°C to 100°C, preferably to a temperature less than 95 °C. Cooling the reactor effluent can be carried out to ambient temperature, for example, in the range of from 20°C to 25 °C.
  • the choice of the temperature to which the effluent is cooled is determined taking into account the goal of increasing the precipitation of the polymer from the solvent.
  • the effluent from the oligomerization reactor is separated from the solid phase prior to the separation of the liquid oligomerization product.
  • the separation of the stream from the oligomerization reactor from the by-product polymer can be carried out before the step of separation of gaseous olefins (degassing stage), if such a step is present, or after the degassing step.
  • the separation of the by-product polymer can be carried out by any known separation method, for example, by centrifugation or filtration.
  • the oligomerization reactor effluent is subjected to the product separation step, during which at least one olefin product is isolated.
  • the product separation step during which at least one olefin product is isolated.
  • the main products of oligomerization such as hexene and octene, are usually separated at the distillation stage.
  • Such separation can be done in any way, for example, by distillation.
  • the problem of deposition of polymers on the surfaces of the reactor equipment is associated not only with the oligomerization processes, but also with the polymerization processes.
  • the present inventors have also conducted experiments, which include running polymerization processes in reactor equipment, on the surface of which a zinc-containing coating has been applied. It was found that the application of a zinc-containing coating onto the surface of the reactor equipment eliminates the problem of polymer deposits for the olefin polymerization processes as well.
  • the process and conditions for carrying out the olefin polymerization reaction may include any process(es) and conditions known in the art, for example, a process/conditions disclosed in WO 2011/093748, RU2471813, RU2434888 documents.
  • a monomer having from 2 to 6 carbon atoms for example, ethylene, propylene or hexene- 1 is used as an olefin.
  • the polymerization reaction can be carried out after completion of the oligomerization process, with the preliminary separation of the olefin oligomer produced.
  • the oligomerization and polymerization reactions can proceed simultaneously; in this case, the copolymerization of the resulting olefin oligomer and the initial olefin monomer usually occurs.
  • Example 1 (comparative). The process of ethylene oligomerization in the reactor equipment without zinc-containing coating
  • chromium ethylhexanoate (Cr(CH3C(C2H5)C3H6COO)3) (63.5% solution in CIO and C12 alkanes) and 17.39 mg of 2,5-dimethylpyrrole (DMP) were placed in a 50 ml round-bottom flask. 1 ml of ethylbenzene was then added, and the flask was filled with dry nitrogen. 0.5 g of the triethylaluminum (TEA) solution in heptane at the concentration of 25 wt.% was mixed with 0.44 g of the dialuminium chloride (DEAH) solution in heptane at a concentration of 15 wt%.
  • TEA triethylaluminum
  • DEAH dialuminium chloride
  • the resulting solution was subjected to microwave irradiation for 6 minutes with a power rating of 400 watts. Then, no later than 30 seconds after the irradiation, the resulted mixture was added to said Cr(CH3C(C 2 H 5 )C 3 H 6 COO) 3 and DMP in ethylbenzene. After 15 minutes the residue in the flask was diluted with 20 ml of cyclohexane to prepare the catalyst solution.
  • Catalyst activity g / (g Cr * h): 5800.
  • Stable operation of the reactor equipment lasted for 10-15 days. Starting of the oligomerization reaction was observed within 5-10 hours after the introduction of ethylene and the catalyst. A ramp-up to a stable operation mode was observed within the period of 8 hours to 3 days following the start of the reaction.
  • Example 2 The process of ethylene oligomerization in the reactor equipment, on the surface of which a zinc-containing coating has been applied Treating the reactor equipment with zinc reaction solution
  • the reactor equipment was cleaned, purged with inert gas, filled with moisture- free hydrocarbon solvent; wherein, in this particular embodiment cyclohexane was used.
  • a sealed container with a solution of diethyl zinc (DEZ) at the 15 wt.% concentration in the amount of 20 kg was connected to dried nitrogen tank and the prepared reactor, and then the solution was pressurized by nitrogen to enter a reaction zone filled with the solvent.
  • the concentration of zinc was about 2.25 g per 1 liter for the total amount of solvent in the reactor equipment.
  • the solvent was mixed with the DEZ in the reactor while gradually heating the solvent to 90-100°C at the heating rate of 20°C/h, with the stirring carried out for 4 hours.
  • the reactor equipment coated with a zinc-containing coating was in operation for 60 days. Starting of the oligomerization reaction was observed within 3 hours after the delivery of ethylene and the catalyst. The ramp-up to a stable operation mode was observed within 2 to 4 hours following the start of the reaction.
  • Example 3 The process of ethylene oligomerization in the reactor equipment, on the surface of which a zinc-containing coating has been applied Treating the reactor equipment with zinc reaction solution
  • the reactor equipment was cleaned, purged with inert gas, filled with moisture- free hydrocarbon solvent; wherein, in this particular embodiment cyclohexane was used.
  • a sealed container with a solution of diethyl zinc (DEZ) at the 15 wt.% concentration based on zinc metal, in the amount of 20 kg was connected to dried nitrogen tank and the prepared reactor, and then the solution was pressurized by nitrogen to enter the reaction zone filled with the solvent.
  • the concentration of zinc was about 2.25 g, calculated per 1 liter for the total amount of the solvent in the reactor equipment.
  • the solvent was mixed with the DEZ in the reactor while gradually heating the solvent to 40°C at the heating rate of 20°C/h, with the stirring carried out for 11 hours.
  • Example 4 Polymerization process in the reactor equipment, on the surface of which a zinc-containing coating has been applied
  • a 2-liter reactor equipped with a mixer was filled with cyclohexane (1.8 liter). Diethylzinc was introduced in the amount necessary to obtain a concentration of 0.5 g of zinc metal per liter.
  • the solution was heated to 100°C at the rate of 25°C/h while permanently stirring for 3 hours. Then, it was cooled down to 25°C, the contents were drained from the reactor and the reactor was filled with nitrogen.
  • the preparation of the catalytic system was carried out according to the method described in Example 1.
  • Example 5 The process of ethylene oligomerization in the reactor equipment, on the surface of which a zinc-containing coating has been applied
  • the reactor equipment was cleaned, purged with an inert gas, filled with the moisture-free Cs-io fraction comprising octene-1, decane and decene, as well as ethylbenzene.
  • a sealed container with a solution of diethyl zinc (DEZ) with a concentration of 15 wt.% based on zinc metal, in the amount of 20 kg was connected to dried nitrogen tank and the prepared reactor, then the solution was pressurized by nitrogen to enter the reaction zone filled with the solvent.
  • DEZ diethyl zinc
  • the concentration of zinc was about 2.25 g, calculated per 1 liter for the total amount of the solvent in the reactor equipment.
  • the solvent was mixed with the DEZ in the reactor while gradually heating the solvent to 100°C with a heating rate of 25°C/h, with stirring carried out for 4 hours, then the contents were drained, and the reactor was filled with moisture-free cyclohexane to be used in the synthesis.
  • Example 6 The process of ethylene oligomerization in the reactor equipment, on the surface of which a zinc-containing coating has been applied
  • the reactor equipment was cleaned, purged with an inert gas, filled with the moisture-free IsoparTM (ExxonMobil) (Cl 0-15 paraffins).
  • a sealed container with a solution of diethyl zinc (DEZ) at the 15 wt.% concentration based on zinc metal, in the amount of 20 kg was connected to dried nitrogen tank and the prepared reactor, and then the solution was pressurized by nitrogen to enter a reaction zone filled with the solvent.
  • DEZ diethyl zinc
  • the concentration of zinc was about 2.25 g, calculated per 1 liter for the total amount of the solvent in the reactor equipment.
  • the solvent was mixed with the D Z in the reactor while gradually heating the solvent to 130°C at the heating rate of 40°C/h, with the stirring carried out for 4 hours, then the contents were drained, and the reactor was filled with moisture-free cyclohexane to be used in synthesis.
  • Example 1 The preparation of the catalytic system was carried out according to the method described in Example 1
  • the process of ethylene oligomerization was carried out according to the method described in Example 1.
  • Example 7 The process of ethylene oligomerization in the reactor equipment, on the surface of which a zinc-containing coating has been applied
  • the reactor equipment was cleaned, purged with inert gas, filled with moisture- free hydrocarbon solvent; wherein, in this particular embodiment cyclohexane was used.
  • a sealed container with a solution of diethyl zinc (DEZ) (90 g/1), zinc oxide (30 g/1) and zinc hydroxide (40 g/1) in an amount of 20 kg was connected to dried nitrogen tank and the prepared reactor, and then the solution was pressurized by nitrogen to enter a reaction zone filled with the solvent.
  • DEZ diethyl zinc
  • the concentration of zinc was about 2.95 g per 1 liter calculated for the total amount of the solvent present in the reactor equipment.
  • the solvent was mixed with the DEZ, ZnO and Zn(OH)2 in the reactor while gradually heating the solvent to 145°C at the heating rate of 50°C/h, with the stirring carried out for 4 hours.
  • Example 8 The process of ethylene oligomerization in the reactor equipment, on the surface of which a zinc-containing coating has been applied
  • the reactor equipment was cleaned, purged with an inert gas, filled with moisture-free cyclohexane.
  • a galvanized pipe was used to remove the reaction mixture from the reactor.
  • the pipeline was galvanized by hot dip galvanizing.
  • the pipe was submerged into a zinc melt bath at a temperature of about 460°C.
  • purified zinc (Zn) reacts with oxygen (O2) to form zinc oxide (ZnO), followed by the reaction with carbon dioxide (CO2) to form zinc carbonate (ZnCCb), which is gray opaque sufficiently hard substance that prevents further corrosion of the material
  • O2 oxygen
  • CO2 carbon dioxide
  • ZnCCb zinc carbonate
  • the reactor equipment used for oligomerization process is a complex apparatus with a tube bundle.
  • the oligomerization reaction takes place inside the tubes. It is important to eliminate the deposition of polymer formed as a by-product inside the tube space of the reactor equipment. In the case of the formation of such by-product polymer deposits on the surfaces of the reactor equipment, the deposits can lead to a decrease in the efficiency of reaction heat transfer, a decrease in the tube flow capacity and a decrease in the useful volume of the reactor. As a result, an increase in the amount of polymer deposits can lead to blockage of a significant number of tubes and the need for equipment repair.
  • Example 3 shows that the preliminary application of the zinc-containing coating onto the surfaces of the reactor equipment makes it possible to reduce the deposition of polymers during the processes of olefins polymerization as well.
  • High molecular weight polymers in this case, Mw more than 9xl0 6 Da
  • Mw more than 9xl0 6 Da have low solubility, and cleaning the reactor after the polymerization process takes a lot of time.
  • an alkylzinc reagent after treating the reactor with an alkylzinc reagent, a polymer does not stick to the surface, and, as a result, the process of getting the reactor ready for a new synthesis process takes less than an hour.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne un procédé de réduction de dépôts de polymère sur les surfaces internes d'un équipement de réacteur, le polymère étant un sous-produit du processus d'oligomérisation d'oléfines ou étant formé pendant le processus de polymérisation ou de copolymérisation d'oléfines. Le procédé de réduction de dépôts de polymère sur les surfaces d'un équipement de réacteur pendant le processus d'oligomérisation ou de copolymérisation d'oléfines implique l'application préliminaire d'un revêtement contenant du zinc sur les surfaces internes de l'équipement de réacteur qui sont en contact avec le milieu réactionnel. Du zinc métallique et/ou des composés de zinc tels que l'oxyde de zinc, l'hydroxyde de zinc et des composés organiques de zinc, en particulier des alkylzinc, sont utilisés en tant que revêtement contenant du zinc. L'invention concerne en outre un processus d'oligomérisation ou de copolymérisation d'oléfines, qui comprend la réaction de matières premières comprenant des oléfines, dans des conditions de réaction, en présence d'un système catalytique, dans l'équipement de réacteur dont les surfaces internes sont revêtues d'un revêtement contenant du zinc. De plus, l'invention concerne un procédé d'application d'un revêtement contenant du zinc et un revêtement obtenu par ce procédé.
PCT/RU2019/000466 2019-06-26 2019-06-26 Procédé de réduction de dépôts de polymère sur les surfaces de l'équipement de réacteur dans le processus d'oligomérisation d'oléfines WO2020263113A1 (fr)

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