CN114957530A - Solution polymerization method of ethylene and alpha-olefin - Google Patents
Solution polymerization method of ethylene and alpha-olefin Download PDFInfo
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- CN114957530A CN114957530A CN202210751567.7A CN202210751567A CN114957530A CN 114957530 A CN114957530 A CN 114957530A CN 202210751567 A CN202210751567 A CN 202210751567A CN 114957530 A CN114957530 A CN 114957530A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
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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
- C08F2400/00—Characteristics for processes of polymerization
- C08F2400/02—Control or adjustment of polymerization parameters
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Abstract
The invention discloses a solution polymerization preparation method of an ethylene and alpha-olefin copolymer, wherein an adiabatic reactor is used in the polymerization process. Mixing ethylene, alpha-olefin and solvent by a feeding unit, adjusting the temperature to obtain a reaction feeding stream, feeding the stream into a solution polymerization reaction unit, obtaining a solution of polymer containing ethylene and alpha-olefin under the action of a catalyst, and then obtaining a circulating stream containing unreacted ethylene, alpha-olefin and solvent and a polymer product through a separation and recovery unit. The temperature of a reaction feeding stream is controlled to be-30-0 ℃, the mass concentration of a solvent in the reaction feeding stream is 70-85 wt.%, the residence time of a reaction unit is 5-15 min, and the ethylene conversion rate can reach 70 percentThe mass concentration of the polymer in the polymer solution at the outlet of the reaction unit is 10-20 wt.%, and the space-time yield is 450kg of ethylene and alpha-olefin copolymer per cubic meter of reaction volume per hour (kg/m) 3 H) above.
Description
Technical Field
The invention belongs to the field of polyolefin, particularly relates to the field of solution polymerization of ethylene and alpha-olefin, and more particularly relates to a method for improving space-time yield of solution polymerization.
Background
Ethylene polymerization is a strongly exothermic reaction and, in order to increase the efficiency of the reaction, it is generally required to remove the heat of reaction at a high rate to ensure the catalyst reactivity. Gas phase polymerization processes in which the reaction temperature can be adjusted by adding a condensing agent, for example patent CN 110023346B, provides a method for gas phase olefin polymerization using propane and isobutane as condensing agents, comprising contacting one or more monomers, at least one catalyst system, and a condensing agent under polymerization conditions to obtain a polymer, the condensing agent comprising at least 25 mol% propylene and at least 20 ml% isobutane. The slurry polymerization process controls the temperature of the reactor by means of solvent gasification, jacket heat removal or external circulation, for example, the invention of patent CN 110918018A discloses a slurry tank type polyethylene reactor combined heat removal method, which combines and simultaneously applies three heat removal methods of slurry external circulation, solvent evaporation and reactor jacket to strengthen the heat removal effect.
The solution polymerization process has the advantages of high reaction rate, short retention time, high polymer solution viscosity, small heat transfer coefficient and low heat transfer efficiency of a reactor jacket. In addition, the solution process polyethylene process requires higher temperatures to be maintained to reduce the viscosity of the polymer solution. Therefore, solution-process polyolefin processes typically employ adiabatic reactors. The adiabatic reactor refers to a reactor which does not exchange heat with the outside. Solution process polymerization refers to a polymerization process in which a polymer is dissolved in a liquid polymerization system such as an inert solvent and a monomer. The temperature and pressure of the solution polymerization are selected to ensure a single homogeneous polymerization phase in the reactor. For example, patent CN 103880999B describes a solution polymerization method of ethylene and α -olefin in a mixed organic solvent, the polymerization temperature and pressure are higher than the supercritical temperature and pressure of the supercritical fluid in the mixed solvent, thereby reducing the viscosity of the polymer system.
The adiabatic reactor is characterized in that the heat of polymerization will be converted into an increase in the temperature of the feed and the discharge. The greater the degree of reaction, i.e., the higher the conversion of ethylene monomer, the greater the temperature rise of the polymer solution. For ethylene and alpha-olefin polymerization, the reaction temperature is also limited by the activity range of the catalyst, and too high reaction temperature may cause catalyst deactivation, so the solution method polymerization generally requires low-temperature feeding to control the reaction temperature. CN 107614541B describes a continuous solution polymerization process using a refrigerator to cool the feed down to 50-15 ℃, the heat of polymerization to raise the temperature to about 85-150 ℃, and the exit polymer concentration in the range of 8-15 wt.%.
The temperature, composition of the reaction feed and the residence time of the reactor, together affect the space-time yield of the reactor and also determine the energy consumption of the feed unit and the separation and recovery unit. The space-time yield is the ratio of the amount of polymer producible per unit time to the volume of the reaction apparatus and is an important measure of the efficiency of the process.
Increasing the space-time yield is key to increasing the productivity of olefin polymerization processes. The above-mentioned patent CN 110023346B proposes a process for the polymerization of ethylene in the gas phase using propane and isobutane as condensing agents, with a productivity which is at least 5% higher than that of the same process in which isopentane is used as condensing agent, and with a space-time yield of more than 224kg/m 3 H is used as the reference value. Patent CN 109996818B also invented a gas phase olefin polymerization process using at least two condensing agents, the optimum vapor pressure of which is determined by the following formula 614 + 716D + 2.338P +3.603 ln (MI), where D is the polymer density, P is the polymerization pressure, and MI is the polymer melt index, and the process space time yield is greater than 250kg/m 3 H is used as the reference value. Patent CN 103328518B proposes a method for producing a coating having a thickness of at least 250m 3 Has a condensation rate of more than 15%, in the presence of a catalyst and in a range of not less than 120kg/m 3 Operating at a space-time yield of/h.
For the polyolefin solution polymerization process, there are also related patents which propose methods for increasing the production efficiency, for example, CN1283204A describes a method for producing a polymer solution with a polymer content of 3-24 wt.% in an olefin solution polymerization process by polymerization in a sufficient amount of solvent in at least one reactor at a polymerization temperature of 150-. However, there is no clear description of how to improve the space-time yield of a solution process polyethylene process.
For solution polymerization, the temperature of the feed stream is reduced and the temperature rise of the reaction solution can absorb more heat of reaction, i.e., the reaction conversion can be higher. However, high conversions lead to a lower reaction rate and thus to a lower space-time yield. In addition, in industrial processes, stream cooling temperatures are limited by cooling utilities, and excessively low feed temperatures result in increased production costs. Aiming at the difficult problems of high space-time yield and low process energy consumption of the solution polymerization of ethylene and alpha-olefin which is difficult to realize, a new method needs to be found, and the process energy consumption and the space-time yield can be considered at the same time.
Defining:
"alpha-olefin" means a monoolefin having a double bond at the end of the molecular chain, such as 1-butene, 1-hexene, 1-octene.
A "polymer" is a polymer of ethylene and an alpha-olefin comonomer.
"continuous" refers to a system that operates without interruption. For example, reactants may be introduced into one or more reactors continuously and polymer product withdrawn continuously.
A "heat exchanger" is a device used to transfer heat from a hot fluid to a cold fluid to meet specified process requirements. The heat exchanger plays an important role in chemical industry, petroleum industry, power industry, food industry and other industrial production, particularly can be used as a heater, a cooler, a condenser, an evaporator, a reboiler and the like in chemical industry production, and is widely applied.
A "separation system" is a system comprising multiple separation and recovery operations, the purpose of which is generally to separate the polymer obtained from the polymerization reaction from the polymer solution and obtain monomer, comonomer, solvent components that can be recycled, and/or to remove impurity components. The separation system of an olefin polymerization production process typically comprises multiple stages of flashing, devolatilization, recycle, extrusion, and the like.
"flash separation" means a separation step that results in phase separation by a reduction in pressure.
"reaction rate" refers to the rate at which reactants are converted to products (also referred to as products) in a chemical reaction, and is generally expressed as the molar amount of reactants converted to products per unit time and per unit reactor volume, e.g., mol/(L · s), mol/(L · min), and the like.
Disclosure of Invention
In order to overcome the problems of the prior art, the present invention provides a solution polymerization process for copolymerizing ethylene and α -olefins, the process comprising: mixing ethylene, alpha-olefin and solvent through a feeding unit (1) and adjusting the temperature to obtain a reaction feeding stream, feeding the stream into a reaction unit (2), obtaining a solution of a polymer containing ethylene and alpha-olefin under the action of a catalyst, and discharging the polymer solution of the reaction unit (2) into a separation and recovery unit (3) to obtain a circulating stream containing unreacted ethylene, alpha-olefin and solvent and a polymer product.
The method is characterized in that the temperature rise of the reactor is controlled to be 130-180 ℃, namely the temperature difference between a discharging stream and a feeding stream is 130-180 ℃, the mass concentration of a solvent in a reaction feeding stream is 70-85 wt.%, and the residence time of a reaction unit is 5-15 min.
According to the process of the invention, the reaction conditions are controlled so that the ethylene conversion is above 70%, and/or the polymer mass concentration of the polymer solution at the outlet of the reaction unit is between 10 and 20 wt.%, and/or the space-time yield is 450kg of ethylene and alpha-olefin copolymer per cubic meter of reaction volume per hour (kg/m) 3 H) above.
According to the method, the temperature of the reaction feed stream is-30-0 ℃, preferably-30-18 ℃.
According to the process of the invention, the temperature of the reaction feed stream is controlled in parallel by a heater and a cooler, so that the temperature control is more precise and the space-time yield is always operated at the highest value.
The method of the invention, wherein the solvent is selected from chain alkane or cycloalkane of C4-C12, aromatic hydrocarbon of C6-C9 or a mixed solvent thereof, preferably C5-C8 chain alkane or cycloalkane.
According to the process of the invention, the reaction unit (2) comprises at least one adiabatic solution polymerization reactor.
The process according to the invention, wherein the alpha-olefin is a C3-C12 olefin, preferably a C4-C8 alpha-olefin.
According to the method, the reactor pressure of the reaction unit is 30-200 bar, preferably 35-50 bar.
According to the method, the temperature of the reactor of the reaction unit is 100-220 ℃, and preferably 120-180 ℃.
The object of the present invention is to overcome the disadvantages of the prior art by providing a process for controlling the ethylene conversion by adjusting the feed temperature and composition, the reaction residence time, so that the space-time yield is in a preferred range of 450kg of ethylene and alpha-olefin copolymer per cubic meter of reaction volume per hour (kg/m) 3 H) above.
Compared with the prior art, the invention has the following advantages: 1) higher polymer content of the polymer solution is achieved by low temperature feeding; 2) the low-temperature feeding requirements of a plurality of brands can be realized by propylene refrigeration, so that the investment of a cold public engineering system is reduced; 3) controlling the reaction residence time, and considering both the monomer conversion rate and the reaction rate; 4) the space-time yield is high.
Drawings
Fig. 1 is a schematic view of the overall structure of the present invention.
In the figure, 1-feed unit; 2-a reaction unit; 3-a separation and recovery unit; 4-ethylene; 5-alpha-olefins; 6-solvent; 7-a catalyst; 8-reacting the feed stream; 9-polymer solution; 10-recycle stream; 11-Polymer product.
Detailed Description
The invention will be further illustrated and described with reference to specific embodiments. The described embodiments are merely exemplary of the disclosure and are not intended to limit the scope thereof. The technical characteristics of the embodiments of the invention can be correspondingly combined without mutual conflict.
As shown in fig. 1, after mixing and temperature adjustment of ethylene 4, α -olefin 5 and solvent 6 in a feeding unit 1, a reaction feeding stream 8 is obtained, the reaction feeding stream 8 is fed into a reaction unit 2, a polymer solution 9 containing ethylene and α -olefin is obtained under the action of a catalyst 7, the polymer solution 9 of the reaction unit 2 is discharged to a separation and recovery unit 3, and a circulating stream 10 containing unreacted ethylene, α -olefin and solvent and a polymer product 11 are obtained. The main feeds of the present invention comprise ethylene monomer, alpha-olefin comonomer and solvent, as is known in the art, and the copolymerization of ethylene and alpha-olefin is a process for producing Linear Low Density Polyethylene (LLDPE) having properties of different density, molecular weight, etc., such as ethylene and 1-octene. The role played by solvents in different polymerization processes is not exactly the same, as is known in the art, solution polymerization requires large amounts of solvent to maintain the ethylene monomer, alpha-olefin comonomer, catalyst, molecular weight regulator, and polymer product in a single phase in the reactor. The solvent needs to be inert to the catalyst system and reactants and stable during the reaction, n-hexane being one of the well known and widely used in the art.
As is known in the art, ethylene and alpha-olefin polymerization are desirably fed over a catalyst, which may be any catalyst known in the art capable of copolymerizing ethylene with alpha-olefin comonomers, including Z-N catalysts and metallocene catalysts, such as the procatalyst being a Constrained Geometry Catalyst (CGC) and the cocatalyst being Methylaluminoxane (MAO).
As is known in the art, the molecular weight of the polymer is often reduced by the addition of small amounts of a substance having a large chain transfer constant, i.e., a molecular weight regulator, and suitable chain transfer agents are various, such as hydrogen, are commonly used. Although a hydrogen feed line is not shown in FIG. 1, the method may include a method of controlling the molecular weight of the copolymer by using hydrogen, which is added in a manner depending on the condition of hydrogen, and may be fed through the feeding unit, mixed and fed, or may be fed separately to the reaction unit.
The polymer solution leaving the reactor is subjected to a termination of the reaction before entering the separation stage, i.e. the catalyst is deactivated, and the reaction is continued in the separation stage with unreacted monomer and comonomer, resulting in an excessive molecular weight or an exotherm which is difficult to control, and the substances which deactivate the catalyst (deactivators) are numerous and can be deactivated by the addition of water, as is known in the art.
Before entering the separation system, the polymer solution usually needs to be heated to obtain a better gas-liquid separation effect and remove volatile components in the polymer solution. As is known in the art, a heat exchanger is a device used to transfer heat from a hot fluid to a cold fluid to meet process requirements. In the present process, a heat exchanger is used to control the temperature of the polymerization solution leaving the reaction unit so as to reach the temperature specified for the separation system.
As is known in the art, a polymer separation system is a system comprising multiple separation, recovery operations, typically involving multiple flash, rectification, recycle, extrusion, etc., when only two flashes are considered, the heated polymer solution from the outlet of the heat exchanger is fed to a flash drum for separation, the overhead vapor stream is sent to a heat recovery unit, a portion is sent to a feed unit for recycle to the reaction unit, the remainder is sent to a downstream rectification operation, the bottom liquid stream is sent to a second stage flash drum for continued separation, and the temperature is adjusted as required before being sent to the second stage flash unit.
The process of the present invention is further described below by reference to examples and comparative examples (detailed results are shown in Table 1), which should be construed as merely illustrative and not limitative of the present invention.
Example, carried out according to the process of the invention, the feed comprises ethylene monomer at a flow rate of 400kg/h, comonomer 1-octene at a flow rate of 225kg/h and solvent n-hexane at a flow rate of 2200 kg/h. After mixing the monomer, the comonomer and the solvent, adjusting the temperature to-25 ℃ and entering a reaction kettle. The feed stream was split into two streams, one (2726.125kg/h) was adjusted to-28 ℃ by a cooler, the other (98.875kg/h) was adjusted to 50 ℃ by a heater, and the mixed feed stream reached the established-25 ℃. The main catalyst is CGC, the auxiliary catalyst is MAO, 0.02kg/h of the main catalyst and 0.2kg/h of the auxiliary catalyst are dissolved in 2kg/h of n-hexane solvent, and the mixture is injected into a reactor. Hydrogen is selected as the molecular weight regulator, and 0.2kg/h is introduced. The reactor is an adiabatic kettle type reactor, a stirring part is arranged in the reactor, the reaction pressure is 40bar, and the retention time is 10 min. The separation system adopts a three-stage flash evaporation mode, wherein the first stage is medium-pressure flash evaporation, the pressure is 15bar, and the temperature is 200 ℃; the second stage was a low pressure flash I at 3bar and 190 ℃. The third stage is low pressure flash evaporation II at 1bar and 190 deg.C. After the third flash, the polymer solution enters an extruder to obtain a polymer.
Under the reaction conditions of the examples, the reactor temperature was 140 ℃, the outlet polymer solution contained 403.3kg/h of polymer and the space-time yield was 488.8kg/m 3 /h。
Comparative example 1, which was carried out in a similar manner to the examples for the polymerization of olefins, with the difference that the feed temperature was lower and-40 ℃ i.e.the polymer solution absorbed more heat of reaction, increasing the residence time to 13.2min, the ethylene conversion was higher, the reactor temperature was also 140 ℃ and the outlet polymer solution contained 434.5kg/h of polymer, giving a space-time yield of 402.8kg/m 3 H is used as the reference value. The feed temperature in comparative example 1 was achieved by only one cooler.
The space-time yields are higher for the examples than for comparative example 1. Comparative example 1 the conversion of ethylene was higher by lowering the reaction feed temperature, but the space-time yield was lower due to the increased residence time, i.e. the return from the reactor equipment investment of comparative example 1 was small; and comparative example 1 feed cooling temperature was as low as-40 ℃, with higher utility costs.
Comparative example 2, which was used for olefin polymerization in a similar manner to example and comparative example 1, except that the residence time was increased to 16min while maintaining the reaction feed temperature of-25 ℃, the conversion of ethylene was higher than in the examples, the reactor temperature reached 150.9 ℃, the outlet polymer solution contained 433.3kg/h of polymer, and the space-time yield was 326.1kg/m 3 /h。
The space-time yields are higher for the examples than for comparative example 2. Comparative example 2 increased the conversion of ethylene, i.e. greater polymer production, but lower its space-time yield by increasing the reaction residence time.
Comparative example 3, which was olefin polymerization conducted using a similar method to the example except that the solvent flow of the reaction feed stream was increased to 4200kg/h, the reaction feed temperature was 20 ℃, and the residence time was 20 min. The reactor temperature was 140.1 ℃ and the ethylene conversion reached 90%, the outlet polymer solution contained 462.2kg/h of polymer, but the space-time yield was only 165.6kg/m 3 H is used as the reference value. The feed temperature in comparative example 3 was achieved by only one cooler.
The space-time yields are higher for the examples than for comparative example 3. Comparative example 3 increased the cooling temperature of the reaction feed stream by increasing the solvent content of the reaction feed stream and increased the reaction residence time to increase the ethylene conversion, but the air-time yield was lower.
TABLE 1
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
Claims (10)
1. A solution polymerization method for copolymerizing ethylene and alpha-olefin is characterized in that ethylene, alpha-olefin and solvent are mixed by a feeding unit (1) and the temperature is adjusted to obtain a reaction feeding stream, the reaction feeding stream is sent into a reaction unit (2) to obtain a solution of polymer containing ethylene and alpha-olefin under the action of catalyst, the polymer solution of the reaction unit (2) is discharged into a separation and recovery unit (3) to obtain a circulating material flow containing unreacted ethylene, alpha-olefin and solvent and a polymer product;
the temperature rise of the reactor is controlled to be 130-180 ℃, namely the temperature difference between the discharging stream and the feeding stream is 130-180 ℃, the mass concentration of the solvent in the reaction feeding stream is 70-85 wt.%, and the residence time of the reaction unit is 5-15 min.
2. The method according to claim 1, characterized in that the reaction feed stream temperature is-30-0 ℃, preferably-30-18 ℃.
3. A method according to claims 1 and 2, characterized in that the feed temperature is controlled by a heater and a cooler in parallel.
4. The method according to claim 1, wherein the solvent is selected from the group consisting of C4-C12 linear or cyclic alkanes, C6-C9 aromatic hydrocarbons and their mixed solvents, preferably C5-C8 linear or cyclic alkanes.
5. The process according to claim 1, wherein the reaction unit (2) comprises at least one adiabatic solution polymerization reactor.
6. The method of claim 1, wherein the alpha-olefin is a C3-C12 olefin; preferred are C4-C8 alpha-olefins.
7. The method according to claim 1, wherein the method controls the polymer mass concentration of the polymer solution at the outlet of the reaction unit to 10-20 wt.% through controlling the reaction operating conditions; and/or the space-time yield is controlled to 450kg of ethylene and alpha-olefin copolymer per cubic meter of reaction volume per hour (kg/m) 3 H) above; and/or an ethylene conversion of above 70%.
8. The process according to claim 1, wherein the reactor pressure of the reaction unit is between 30 and 200bar, preferably between 35 and 50 bar.
9. The method according to claim 1, wherein the reactor temperature of the reaction unit is 100-220 ℃.
10. The process according to claim 1 or 9, wherein the reactor temperature of the reaction unit is 120 to 180 ℃.
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| CN115677885A (en) * | 2022-11-11 | 2023-02-03 | 山东京博石油化工有限公司 | Method for cooling raw materials in polymerization reaction process |
Citations (27)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1070919A (en) * | 1991-10-03 | 1993-04-14 | 杜邦公司加拿大分公司 | The activation of catalyst for ethylene polymerization at high temperatures |
| CN1182439A (en) * | 1995-04-21 | 1998-05-20 | 埃克森化学专利公司 | Ethylene -'alpha' -olefin/diolefin polymer solution polymerization process |
| US20060106179A1 (en) * | 2004-11-18 | 2006-05-18 | Kim Sang B | Methods of preparing EP(D)M elastomer, of controlling yield thereof, and of recovering the same |
| CN101490096A (en) * | 2006-05-17 | 2009-07-22 | 陶氏环球技术公司 | Polypropylene solution polymerization process |
| CN103003318A (en) * | 2010-07-15 | 2013-03-27 | Sk新技术株式会社 | Ethylene copolymer with improved elasticity and processibility |
| CN103804556A (en) * | 2012-11-07 | 2014-05-21 | 中国石油化工股份有限公司 | Olefin polymerization method, an ethylene polymer, and preparation method of ethylene polymer |
| CN104177526A (en) * | 2014-08-13 | 2014-12-03 | 浙江大学 | Solution polymerization preparation method of propylene-alpha-olefin copolymer |
| CN104704012A (en) * | 2012-10-12 | 2015-06-10 | 埃克森美孚化学专利公司 | Polymerization process |
| CN105017456A (en) * | 2014-04-15 | 2015-11-04 | 中国石化扬子石油化工有限公司 | Ethylene-alpha-olefin copolymer, manufacturing method and applications thereof |
| CN105199031A (en) * | 2015-10-16 | 2015-12-30 | 浙江大学 | Olefin polymerization method and device |
| CN105802033A (en) * | 2016-03-14 | 2016-07-27 | 浙江大学 | Preparation method and application of polyethylene film |
| CN106132533A (en) * | 2014-01-06 | 2016-11-16 | 大林产业株式会社 | ethylene and alpha-olefin polymerization device and preparation method |
| CN106471011A (en) * | 2014-06-25 | 2017-03-01 | 巴塞尔聚烯烃股份有限公司 | There is the ethene polymerization method of improved heat exchanger performance |
| CN107075026A (en) * | 2014-10-21 | 2017-08-18 | 诺瓦化学品(国际)股份有限公司 | Solution polymerization process |
| US20190040162A1 (en) * | 2017-08-02 | 2019-02-07 | Equistar Chemicals, Lp | Tri-n-octyl aluminum co-catalyst for higher density homopolymers for the solution process |
| CN110272515A (en) * | 2018-03-15 | 2019-09-24 | 中国石油化工股份有限公司 | The preparation method of ethylene copolymer |
| CN110343206A (en) * | 2018-04-03 | 2019-10-18 | 中国石油化工股份有限公司 | A kind of concatenated ethene polymerization process method of double-reactor |
| CA3007381A1 (en) * | 2018-06-06 | 2019-12-06 | Nova Chemicals Corporation | Off-line filter free ziegler-natta catalyst preparation |
| CN110573538A (en) * | 2017-04-19 | 2019-12-13 | 诺瓦化学品(国际)股份有限公司 | Multi-reactor solution polymerization |
| WO2020178010A1 (en) * | 2019-03-04 | 2020-09-10 | Borealis Ag | Polymerization process |
| CN111788233A (en) * | 2017-11-07 | 2020-10-16 | 诺瓦化学品(国际)股份有限公司 | Production of ethylene interpolymer products at higher productivity |
| WO2021136804A1 (en) * | 2020-01-02 | 2021-07-08 | Borealis Ag | Process for the polymerization of olefins in solution with controlled activity of catalyst in reactor outlet stream |
| CN113248642A (en) * | 2021-05-13 | 2021-08-13 | 浙江大学 | Method for preparing polyolefin elastomer based on microchannel reactor technology and product |
| CN114075309A (en) * | 2020-08-11 | 2022-02-22 | 中国石油化工股份有限公司 | Method and system for regulating and controlling polyolefin performance |
| CN114195925A (en) * | 2022-01-12 | 2022-03-18 | 万华化学集团股份有限公司 | Olefin polymer and solution polymerization method |
| CN114426616A (en) * | 2020-09-30 | 2022-05-03 | 中国石油化工股份有限公司 | Method for synthesizing polyolefin and application thereof |
| CN114507311A (en) * | 2021-02-01 | 2022-05-17 | 中国石油化工股份有限公司 | Ethylene polymer and process for producing the same |
-
2022
- 2022-06-28 CN CN202210751567.7A patent/CN114957530B/en active Active
Patent Citations (27)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1070919A (en) * | 1991-10-03 | 1993-04-14 | 杜邦公司加拿大分公司 | The activation of catalyst for ethylene polymerization at high temperatures |
| CN1182439A (en) * | 1995-04-21 | 1998-05-20 | 埃克森化学专利公司 | Ethylene -'alpha' -olefin/diolefin polymer solution polymerization process |
| US20060106179A1 (en) * | 2004-11-18 | 2006-05-18 | Kim Sang B | Methods of preparing EP(D)M elastomer, of controlling yield thereof, and of recovering the same |
| CN101490096A (en) * | 2006-05-17 | 2009-07-22 | 陶氏环球技术公司 | Polypropylene solution polymerization process |
| CN103003318A (en) * | 2010-07-15 | 2013-03-27 | Sk新技术株式会社 | Ethylene copolymer with improved elasticity and processibility |
| CN104704012A (en) * | 2012-10-12 | 2015-06-10 | 埃克森美孚化学专利公司 | Polymerization process |
| CN103804556A (en) * | 2012-11-07 | 2014-05-21 | 中国石油化工股份有限公司 | Olefin polymerization method, an ethylene polymer, and preparation method of ethylene polymer |
| CN106132533A (en) * | 2014-01-06 | 2016-11-16 | 大林产业株式会社 | ethylene and alpha-olefin polymerization device and preparation method |
| CN105017456A (en) * | 2014-04-15 | 2015-11-04 | 中国石化扬子石油化工有限公司 | Ethylene-alpha-olefin copolymer, manufacturing method and applications thereof |
| CN106471011A (en) * | 2014-06-25 | 2017-03-01 | 巴塞尔聚烯烃股份有限公司 | There is the ethene polymerization method of improved heat exchanger performance |
| CN104177526A (en) * | 2014-08-13 | 2014-12-03 | 浙江大学 | Solution polymerization preparation method of propylene-alpha-olefin copolymer |
| CN107075026A (en) * | 2014-10-21 | 2017-08-18 | 诺瓦化学品(国际)股份有限公司 | Solution polymerization process |
| CN105199031A (en) * | 2015-10-16 | 2015-12-30 | 浙江大学 | Olefin polymerization method and device |
| CN105802033A (en) * | 2016-03-14 | 2016-07-27 | 浙江大学 | Preparation method and application of polyethylene film |
| CN110573538A (en) * | 2017-04-19 | 2019-12-13 | 诺瓦化学品(国际)股份有限公司 | Multi-reactor solution polymerization |
| US20190040162A1 (en) * | 2017-08-02 | 2019-02-07 | Equistar Chemicals, Lp | Tri-n-octyl aluminum co-catalyst for higher density homopolymers for the solution process |
| CN111788233A (en) * | 2017-11-07 | 2020-10-16 | 诺瓦化学品(国际)股份有限公司 | Production of ethylene interpolymer products at higher productivity |
| CN110272515A (en) * | 2018-03-15 | 2019-09-24 | 中国石油化工股份有限公司 | The preparation method of ethylene copolymer |
| CN110343206A (en) * | 2018-04-03 | 2019-10-18 | 中国石油化工股份有限公司 | A kind of concatenated ethene polymerization process method of double-reactor |
| CA3007381A1 (en) * | 2018-06-06 | 2019-12-06 | Nova Chemicals Corporation | Off-line filter free ziegler-natta catalyst preparation |
| WO2020178010A1 (en) * | 2019-03-04 | 2020-09-10 | Borealis Ag | Polymerization process |
| WO2021136804A1 (en) * | 2020-01-02 | 2021-07-08 | Borealis Ag | Process for the polymerization of olefins in solution with controlled activity of catalyst in reactor outlet stream |
| CN114075309A (en) * | 2020-08-11 | 2022-02-22 | 中国石油化工股份有限公司 | Method and system for regulating and controlling polyolefin performance |
| CN114426616A (en) * | 2020-09-30 | 2022-05-03 | 中国石油化工股份有限公司 | Method for synthesizing polyolefin and application thereof |
| CN114507311A (en) * | 2021-02-01 | 2022-05-17 | 中国石油化工股份有限公司 | Ethylene polymer and process for producing the same |
| CN113248642A (en) * | 2021-05-13 | 2021-08-13 | 浙江大学 | Method for preparing polyolefin elastomer based on microchannel reactor technology and product |
| CN114195925A (en) * | 2022-01-12 | 2022-03-18 | 万华化学集团股份有限公司 | Olefin polymer and solution polymerization method |
Non-Patent Citations (4)
| Title |
|---|
| ROGELIO CHARLES ET AL.: "Heterogeneous Copolymerization of Ethylene and a-olefins Using Aluminohydride-Zirconocene/SiO2/ MAO by High-Throughput Screening", MACROMOL. SYMP., pages 90 - 100 * |
| 吴浩等: "α-烯烃合成PAO中本体聚合与溶液聚合的对比研究", 山东化工, pages 10 - 12 * |
| 米普科等: "碳桥限制构型催化剂催化乙烯1-己烯共聚和共聚物结构表征", 分子催化, pages 501 - 512 * |
| 郭峰等: "乙烯基共聚物的溶液聚合生产技术", 合成树脂及塑料, pages 64 - 68 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115677885A (en) * | 2022-11-11 | 2023-02-03 | 山东京博石油化工有限公司 | Method for cooling raw materials in polymerization reaction process |
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