CN114957530B - Solution polymerization method of ethylene and alpha-olefin - Google Patents
Solution polymerization method of ethylene and alpha-olefin Download PDFInfo
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- 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
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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. The ethylene, the alpha-olefin and the solvent are mixed and temperature-regulated by a feed unit to obtain a reaction feed stream, which is fed to a solution polymerization unit, a solution of a polymer comprising ethylene and alpha-olefin is obtained under the action of a catalyst, and subsequently a recycle stream comprising unreacted ethylene, alpha-olefin and solvent is obtained by a separation and recovery unit, as well as a polymer product. The invention controls the temperature of the reaction feed stream at-30-0 ℃, the mass concentration of the solvent in the reaction feed stream is 70-85 wt%, the residence time of the reaction unit is 5-15 min, the ethylene conversion rate can reach over 70%, the mass concentration of the polymer solution at the outlet of the reaction unit is 10-20 wt%, and the space-time yield is 45%0kg ethylene and alpha-olefin copolymer per cubic meter of reaction volume per hour (kg/m 3 And/h) above.
Description
Technical Field
The invention belongs to the field of polyolefin, in particular to the field of ethylene and alpha-olefin solution polymerization, and more particularly relates to a method for improving the space-time yield of solution polymerization reaction.
Background
Ethylene polymerization is a strongly exothermic reaction and in order to increase the reaction efficiency, it is generally required to remove the heat of reaction at a higher rate to ensure the catalyst reactivity. The gas phase polymerization process may be carried out by adjusting the reaction temperature by adding a condensing agent, for example, patent CN 110023346B provides a gas phase olefin polymerization process using propane and isobutane as condensing agents, which comprises contacting one or more monomers, at least one catalyst system and condensing agent under polymerization conditions to obtain a polymer, the condensing agent comprising at least 25mol% propylene and at least 20ml% isobutane. The slurry polymerization process is to control the temperature of the reactor in the modes of solvent gasification, jacket heat removal or external circulation, such as the combined heat removal method of a slurry kettle type polyethylene reactor disclosed in patent CN 110918018A, and the three heat removal methods of slurry external circulation, solvent evaporation and reactor jacket are combined and applied simultaneously to strengthen the heat removal effect.
The solution polymerization process has the advantages of high reaction rate, short residence time, high polymer solution viscosity, small heat transfer coefficient and low heat transfer efficiency of the reactor jacket. In addition, the solution process polyethylene process requires maintenance of higher temperatures to reduce the viscosity of the polymer solution. Thus, solution polyolefin processes typically employ adiabatic reactors. The adiabatic reactor refers to a reactor that does not exchange heat with the outside. Solution polymerization refers to a polymerization process in which a polymer is dissolved in a liquid polymerization system, such as an inert solvent and monomers. 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 process of ethylene and α -olefins in a mixed organic solvent at a polymerization temperature and pressure 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 a temperature rise of the feed and the discharge. The greater the extent of reaction, i.e. the higher the conversion of ethylene monomer, the greater the temperature rise of its polymer solution. For the polymerization of ethylene and alpha-olefins, the reaction temperature is also limited by the range of catalyst activity, and too high a reaction temperature may result in deactivation of the catalyst, so solution polymerization generally requires a low temperature feed to control the reaction temperature. CN 107614541B describes a continuous solution polymerization process where the feed is cooled down to 50 to-15 ℃ with a freezer and the heat of polymerization increases the temperature to about 85 to 150 ℃ with an outlet polymer concentration in the range of 8wt.% to 15wt.%.
The temperature, composition and residence time of the reaction feed 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. Space-time yield, which is the ratio between the amount of polymer producible per unit time and the volume of the reaction apparatus, is an important measure for the production efficiency.
Increasing the space-time yield is critical to increasing the throughput of the olefin polymerization process. The above-mentioned patent CN 110023346B proposes a gas-phase ethylene polymerization process using propane and isobutane as condensing agents, with a productivity at least 5% higher than the same process in which isopentane is the condensing agent, with a space-time yield greater than 224kg/m 3 And/h. Patent CN 109996818B also discloses a gas-phase olefin polymerization process using at least two condensing agents, the optimum vapor pressure of which is determined by the following formula 614-716 x d+2.338 x p+3.603 x ln (MI), wherein D is the polymer density, P is the polymerization pressure, MI is the polymer melt index, the process has a space-time yield of greater than 250kg/m 3 And/h. Patent CN 103328518B proposes a method of having a diameter of at least 250m 3 In a vertical fluidized bed reactor, cooledThe coagulation rate is higher than 15%, the catalyst is present and the coagulation rate is not lower than 120kg/m 3 Operation at a space-time yield of/h.
For polyolefin solution polymerization processes, there are also related patents which propose a method for increasing the production efficiency, for example CN1283204a describes a method for the polymer content at the outlet of a reactor in an olefin solution polymerization process, which comprises polymerizing a polymer solution having a polymer content of 3 to 24wt.% in a sufficient amount of a solvent in at least one reactor at a polymerization temperature of 150 to 260 ℃, wherein the reactor used is a "boiling reactor", which is a reactor capable of flashing the polymer reaction solution in the reactor, i.e. a reactor in which a liquid phase and a gas phase are present at the same time, and a part of the monomers and the solvent leave the reactor by vaporization, whereby a part of the reaction heat can be removed. However, there is no clear description of how to increase the space-time yield of a solution polyethylene process.
For solution polymerization, lowering the temperature of the feed stream, the reaction solution temperature rise may absorb more of the heat of reaction, i.e., the reaction conversion may be higher. However, high conversions result in lower reaction rates and, in turn, lower space-time yields. In addition, during industrial processes, stream cooling temperatures are limited by cold 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, a new method capable of combining the process energy consumption and the space-time yield needs to be found.
Definition:
"alpha-olefin" refers to a mono-olefin having a double bond at the end of the molecular chain, such as 1-butene, 1-hexene, 1-octene.
"Polymer" is a polymer of ethylene and an alpha-olefin comonomer.
"continuous" refers to a system that operates without interruption. For example, reactants are continuously introduced into one or more reactors and polymer product is continuously withdrawn.
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 has important roles in chemical industry, petroleum, power, food and other industrial production, and especially has wide application as heater, cooler, condenser, evaporator, reboiler, etc.
A "separation system" is a system that includes multiple separation and recovery operations, the purpose of which is typically to separate the polymer resulting from the polymerization reaction from the polymer solution and to obtain recyclable monomers, comonomers, solvent components, and/or to remove impurity components. The separation system of an olefin polymerization production process typically comprises multiple flash, devolatilization, recycle, extrusion, and the like processes.
"flash separation" means a separation step that results in phase separation by pressure drop.
"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 in terms of the molar amount of reactants converted to products per unit time and per unit reactor volume, such as mol/(L.s), mol/(L.min), and the like.
Disclosure of Invention
In order to overcome the problems in the prior art, the present invention provides a solution polymerization process for copolymerizing ethylene with an α -olefin, the process comprising: ethylene, alpha-olefin and solvent are mixed and temperature-regulated by a feeding unit (1) to obtain a reaction feeding stream, the stream is sent to a reaction unit (2) to obtain a polymer solution containing ethylene and alpha-olefin under the action of a catalyst, and the polymer solution of the reaction unit (2) is discharged to a separation and recovery unit (3) to obtain a recycle 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 flow and a feeding flow is 130-180 ℃, the mass concentration of a solvent in the feeding flow is 70-85 wt.%, and the residence time of the reaction unit is 5-15 min.
According to the process of the invention, the ethylene conversion is brought to above 70% and/or the polymer mass concentration of the polymer solution at the outlet of the reaction unit is brought to 10 to 20% by weight and/or the space-time yield is brought to 450kg of ethylene and alpha-olefin copolymer per cubic meter by controlling the reaction operating conditionsShould be of volume per hour (kg/m) 3 And/h) above.
The process according to the invention, wherein the reaction feed stream temperature is from-30 to 0 ℃, preferably from-30 to-18 ℃.
According to the inventive method, the temperature of the reaction feed stream is controlled by a heater and a cooler in parallel, so that the temperature control is more precise and the space-time yield is always operated at the highest value.
The process according to the invention wherein the solvent is selected from the group consisting of C4 to C12 chain alkanes or cycloalkanes, C6 to C9 aromatic hydrocarbons or mixtures thereof, preferably C5 to C8 chain alkanes or cycloalkanes.
According to the inventive method, 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 to C12 olefin, preferably a C4 to C8 alpha-olefin.
According to the process of the invention, the reactor pressure of the reaction unit is between 30 and 200bar, preferably between 35 and 50bar.
According to the process of the invention, the reactor temperature of the reaction unit is between 100 and 220 ℃, preferably between 120 and 180 ℃.
The invention aims to overcome the defects in the prior art and provide a method for controlling the ethylene conversion rate by adjusting the feeding temperature, the composition and the reaction residence time to ensure that the space-time yield is in a better range and the reaction volume per cubic meter per hour (kg/m) of 450kg of ethylene and alpha-olefin copolymer 3 And/h) above.
Compared with the prior art, the invention has the following advantages: 1) Achieving a higher polymer content of the polymer solution by low temperature feeding; 2) The low-temperature feeding requirements of a plurality of brands can be realized through propylene refrigeration, so that the investment of a cold public engineering system is reduced; 3) Controlling the reaction residence time, and considering the monomer conversion rate and the reaction rate; 4) The space-time yield is high.
Drawings
Fig. 1 is a schematic diagram of the overall structure of the present invention.
In the figure, 1-feeding unit; a 2-reaction unit; 3-a separation and recovery unit; 4-ethylene; 5-alpha-olefins; 6-solvent; 7-a catalyst; 8-reaction feed stream; 9-polymer solution; 10-recycle stream; 11-polymer product.
Detailed Description
The invention is further illustrated and described below in connection with specific embodiments. The described embodiments are merely exemplary of the present disclosure and do not limit the scope. The technical features of the embodiments of the invention can be combined correspondingly on the premise of no mutual conflict.
As shown in fig. 1, ethylene 4, alpha-olefin 5 and solvent 6 are mixed and temperature-regulated by a feed unit 1 to obtain a reaction feed stream 8, the reaction feed stream 8 is fed into a reaction unit 2, a polymer solution 9 comprising ethylene and alpha-olefin is obtained under the influence of a catalyst 7, the polymer solution 9 of the reaction unit 2 is discharged to a separation and recovery unit 3 to obtain a recycle stream 10 comprising unreacted ethylene, alpha-olefin and solvent, and a polymer product 11. The primary feeds of the present invention include ethylene monomer, alpha-olefin comonomer and solvent, as is known in the art, ethylene and alpha-olefin copolymerization are processes for producing Linear Low Density Polyethylene (LLDPE) having different density, molecular weight, etc. properties, such as ethylene and 1-octene. The solvent does not perform exactly the same in different polymerization processes, as is known in the art, solution polymerization requires a large amount of solvent to maintain the ethylene monomer, the alpha-olefin comonomer, the catalyst, the molecular weight regulator, and the polymer product in a single phase in the reactor. The solvent needs to be inert to the catalyst system and reactants and remain stable during the reaction, n-hexane being a known and widely used one in the art.
As is known in the art, the ethylene and α -olefin polymerization is fed by a catalyst which may be any catalyst known in the art to be capable of copolymerizing ethylene with α -olefin comonomer, including Z-N catalysts and metallocene catalysts, such as a procatalyst which is a Constrained Geometry Catalyst (CGC), and a cocatalyst which is Methylaluminoxane (MAO).
As known in the art, there are a variety of suitable chain transfer agents, commonly used such as hydrogen, often used to reduce the molecular weight of the polymer by adding small amounts of a material having a large chain transfer constant, i.e., a molecular weight regulator. Although the feed line for hydrogen is not shown in fig. 1, the present process may include a method of controlling the molecular weight of the copolymer using hydrogen, which is added depending on the conditions of hydrogen, either by the feed unit, after mixing, or separately to the reaction unit.
The polymer solution leaves the reactor and is terminated prior to entering the separation stage, even if the catalyst is deactivated, and the unreacted monomer and comonomer continue to react during the separation stage, resulting in excessive molecular weight or difficult control of the exotherm, and many materials (deactivators) that deactivate the catalyst, as known in the art, may be added to deactivate the catalyst by the addition of water.
The temperature of the polymer solution is usually raised before the polymer solution enters the separation system, so that a better gas-liquid separation effect is obtained, and volatile components in the polymer solution are removed. 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 exiting the reaction unit to a specified temperature of 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, circulation, extrusion, etc. processes, when only two flashes are considered, the heated polymer solution from the heat exchanger outlet is fed to a flash tank for separation, the overhead vapor phase stream is sent to a heat recovery unit, part is sent to a feed unit for recycle to a reaction unit, the remainder is sent to a downstream rectification operation, the bottom vapor phase stream is sent to a second stage flash tank for continued separation, and the temperature is adjusted as required before being sent to the second stage flash unit.
The process according to the invention is further described below with reference to examples and comparative examples (see Table 1 for detailed results), it being stated that the examples are given here only for the purpose of illustrating the invention and are not intended to limit the invention.
Examples, carried out according to the process of the invention, the feed comprises ethylene monomer at a flow rate of 400kg/h, 1-octene as comonomer, 225kg/h as solvent, n-hexane as feed 2200kg/h. And mixing the monomer, the comonomer and the solvent, regulating the temperature to-25 ℃, and entering a reaction kettle. The feed stream was split into two streams, one stream (2726.125 kg/h) was temperature-regulated to-28℃by the cooler and the other stream (98.875 kg/h) was temperature-regulated to 50℃by the heater, and after mixing the feed streams reached the established-25 ℃. The main catalyst is CGC, the cocatalyst is MAO, and 0.02kg/h of the main catalyst and 0.2kg/h of the cocatalyst are dissolved in 2kg/h of n-hexane solvent and injected into the reactor. The molecular weight regulator is hydrogen, and 0.2kg/h of the hydrogen is introduced. The reactor adopts an adiabatic kettle reactor, a stirring part is arranged in the reactor, the reaction pressure is 40bar, and the residence time is 10min. The separation system adopts a three-stage flash evaporation mode, 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 a pressure of 3bar and a temperature of 190 ℃. The third stage is a low pressure flash II, the pressure is 1bar and the temperature is 190 ℃. After the third stage flash evaporation, the polymer solution enters an extruder to obtain a polymer.
Under the reaction conditions of the examples, the reactor temperature was 140℃and 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 similar to the example for olefin polymerization, except that the feed temperature was lower, at-40℃i.e.the polymer solution could absorb more heat of reaction, the residence time was increased to 13.2min, the conversion of ethylene was higher, the reactor temperature was 140℃as well, the outlet polymer solution contained 434.5kg/h of polymer and the space time yield was 402.8kg/m 3 And/h. The feed temperature in comparative example 1 was achieved by only one cooler.
The space-time yield is higher for the examples compared to comparative example 1. Comparative example 1 the conversion of ethylene was higher by lowering the reaction feed temperature, but the residence time increased, so the space time yield was lower, i.e. the investment in reactor equipment for comparative example 1 was less profitable; and comparative example 1 had a feed cooling temperature as low as-40 c, with higher utility costs.
Comparative example 2, which was conducted for olefin polymerization using a similar method to the examples and comparative example 1, except that the residence time was increased to that while maintaining the reaction feed temperature of-25 deg.c16min, higher ethylene conversion than in the examples, reactor temperature up to 150.9℃and outlet polymer solution containing 433.3kg/h of polymer with a space-time yield of 326.1kg/m 3 /h。
The space-time yield is higher for the examples compared to comparative example 2. Comparative example 2 increased the reaction residence time, resulted in higher ethylene conversion, i.e., greater polymer production, but lower space-time yields.
Comparative example 3, which was conducted for olefin polymerization using a similar method to the example, except that the solvent flow rate of the reaction feed stream was increased to 4200kg/h, the reaction feed temperature was 20℃and the residence time was 20min. The reactor temperature was 140.1℃and the ethylene conversion was 90%, the outlet polymer solution contained 462.2kg/h of polymer, but the space-time yield was only 165.6kg/m 3 And/h. The feed temperature in comparative example 3 was achieved by only one cooler.
The space-time yield is higher for the examples compared to comparative example 3. Comparative example 3 increases the reaction feed stream cooling temperature by increasing the solvent content of the reaction feed stream and increases the reaction residence time to increase ethylene conversion, but with lower space-time yields.
TABLE 1
The foregoing examples illustrate only a few embodiments of the invention and are described in detail herein without thereby limiting the scope of the invention. It will be apparent to those skilled in the art that various modifications and improvements can be made without departing from the spirit of the invention.
Claims (7)
1. A solution polymerization process for the copolymerization of ethylene with an alpha-olefin, characterized in that after mixing and temperature adjustment of ethylene, an alpha-olefin and a solvent by a feed unit (1) a reaction feed stream is obtained, which reaction feed stream is fed into a reaction unit (2) to obtain a solution of a polymer comprising ethylene and an alpha-olefin under the action of a catalyst, the polymer solution of said reaction unit (2) is discharged to a separation and recovery unit (3) to obtain a recycle stream comprising unreacted ethylene, alpha-olefin and solvent and a polymer product; the alpha-olefin is C3-C12 olefin;
controlling the temperature rise of the reactor to be 130-180 ℃, namely controlling the temperature difference between the discharging flow and the feeding flow to be 130-180 ℃, controlling the mass concentration of the solvent in the feeding flow to be 70-85 wt.% and controlling the residence time of the reaction unit to be 5-15 min; the temperature of the reaction feed stream is-30-0 ℃; the feeding temperature is controlled by a heater and a cooler in parallel; the reactor pressure of the reaction unit is 30-200 bar; the temperature of the reactor of the reaction unit is 100-220 ℃;
the process is controlled by the reaction operating conditions such that the polymer mass concentration of the polymer solution at the outlet of the reaction unit is controlled to be 10 to 20wt.% and the space-time yield of the ethylene and alpha-olefin copolymer is 450 kg/(m) 3 * h) The above and ethylene conversion rates were above 70%.
2. The process of claim 1 wherein the reaction feed stream temperature is from-30 ℃ to-18 ℃.
3. The method according to claim 1, wherein the solvent is selected from the group consisting of C4-C12 chain alkanes or cycloalkanes, C6-C9 aromatic hydrocarbons, and mixtures thereof.
4. The method according to claim 1, characterized in that the reaction unit (2) comprises at least one adiabatic solution polymerization reactor.
5. The process of claim 1, wherein the α -olefin is a C4 to C8 α -olefin.
6. The process according to claim 1, wherein the reactor pressure of the reaction unit is between 35 and 50bar.
7. The process according to claim 1, wherein the reactor temperature of the reaction unit is 120-180 ℃.
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