Liquid-gas phase combined olefin continuous polymerization method and device
阅读说明：本技术 一种液相-气相组合的烯烃连续聚合方法和装置 (Liquid-gas phase combined olefin continuous polymerization method and device ) 是由 刘立新 李化毅 张毅 于 2019-11-28 设计创作，主要内容包括：本发明提供了一种液相-气相组合的烯烃连续聚合方法和装置,所述装置包括催化剂进料系统、烯烃进料系统、氢气进料系统和聚合反应系统；所述催化剂进料系统、烯烃进料系统、氢气进料系统分别与所述聚合反应系统连接。所述方法特别适合于烯烃均聚物及共聚物的生产,例如烯烃均聚物、烯烃无规共聚物和烯烃抗冲共聚物(例如可以生产丙烯均聚物、丙烯无规共聚物和丙烯抗冲共聚物),其聚合反应釜具有更灵活的组合,可根据不同产品的要求进行组成,以生产不同类型的产品,生产中低端产品具有更短的流程和更低的成本；生产高端产品,具有更高的品质。(The invention provides a liquid phase-gas phase combined olefin continuous polymerization method and a device, wherein the device comprises a catalyst feeding system, an olefin feeding system, a hydrogen feeding system and a polymerization reaction system; the catalyst feeding system, the olefin feeding system and the hydrogen feeding system are respectively connected with the polymerization reaction system. The method is particularly suitable for the production of olefin homopolymers and copolymers, such as olefin homopolymers, olefin random copolymers and olefin impact copolymers (such as propylene homopolymers, propylene random copolymers and propylene impact copolymers can be produced), the polymerization reaction kettle has more flexible combination, can be composed according to the requirements of different products to produce different types of products, and the production of middle-end and low-end products has shorter flow and lower cost; high-end products are produced, and the quality is higher.)
1. A polymerization reaction system for olefin polymerization, characterized in that the polymerization reaction system comprises a prepolymerization reactor (R101), a first liquid phase polymerization reactor (R201), a second liquid phase polymerization reactor (R202), a first gas phase polymerization reactor (R301), a second gas phase polymerization reactor (R302), a gas lock, a first high-pressure flash distillation reactor (R401) and a second high-pressure flash distillation reactor (R402);
the prepolymerization kettle (R101) is respectively connected with a first liquid phase polymerization reaction kettle (R201) and a second liquid phase polymerization reaction kettle (R202); the first liquid phase polymerization reaction kettle (R201) is directly connected with the first gas phase polymerization reaction kettle (R301) or indirectly connected with the first gas phase polymerization reaction kettle (R301) through a first high-pressure flash evaporation kettle (R401); the second liquid phase polymerization reaction kettle (R202) is directly connected with the first gas phase polymerization reaction kettle (R301), or indirectly connected with the first gas phase polymerization reaction kettle (R301) through a second high-pressure flash evaporation kettle (R402), or directly connected with the second gas phase polymerization reaction kettle (R302), or indirectly connected with the second gas phase polymerization reaction kettle (R302) through the second high-pressure flash evaporation kettle (R402); the first liquid phase polymerization reaction kettle (R201) is connected with the second liquid phase polymerization reaction kettle (R202); the first gas phase polymerization reaction kettle (R301) is connected with the second gas phase polymerization reaction kettle (R302) through a gas lock.
2. The polymerization system according to claim 1, wherein the first liquid phase polymerization reactor (R201) and the second liquid phase polymerization reactor (R202) are vertical stirred tank reactors or loop reactors, preferably vertical stirred tank reactors.
Preferably, the first gas phase polymerization reactor (R301) and the second gas phase polymerization reactor (R302) are horizontal plug flow gas phase reactors, vertical stirred gas phase reactors, or fluidized bed gas phase reactors; preferably a horizontal plug flow gas phase reactor.
3. The polymerization system according to claim 1 or 2, wherein the prepolymerization vessel (R101) is connected to a first liquid phase polymerization reactor (R201) and a second liquid phase polymerization reactor (R202), respectively, the first liquid phase polymerization reactor (R201) is connected to a first gas phase polymerization reactor (R301), and the second liquid phase polymerization reactor (R202) is connected to a second gas phase polymerization reactor (R302), i.e. the flow direction is as follows:
or, the prepolymerization reactor (R101) is connected with a first liquid phase polymerization reactor (R201), the first liquid phase polymerization reactor (R201) is connected with a second liquid phase polymerization reactor (R202), the second liquid phase polymerization reactor (R202) is connected with a first gas phase polymerization reactor (R301), the first gas phase polymerization reactor (R301) is connected with a second gas phase polymerization reactor (R302) through gas lock, that is, the material flow direction is:
r101 → R201 → R202 → R301 → airlock → R302 → polymer post-treatment system.
Or, the prepolymerization reactor (R101) is connected with a first liquid phase polymerization reactor (R201), the first liquid phase polymerization reactor (R201) is connected with a second liquid phase polymerization reactor (R202), the second liquid phase polymerization reactor (R202) is connected with a first gas phase polymerization reactor (R301) through a second high pressure flash distillation reactor (R402), the first gas phase polymerization reactor (R301) is connected with a second gas phase polymerization reactor (R302) through an air lock, that is, the material flow direction is:
r101 → R201 → R202 → R402 → R301 → airlock → R302 → polymer post-treatment system.
Or, prepolymerization cauldron (R101) are connected with first liquid phase polymerization reation kettle (R201) and second liquid phase polymerization reation kettle (R202) respectively, first liquid phase polymerization reation kettle (R201) is connected with first high-pressure flash distillation cauldron R401, first high-pressure flash distillation cauldron R401 is connected with first gas phase polymerization reation kettle (R301), second liquid phase polymerization reation kettle (R202) is connected with second high-pressure flash distillation cauldron (R402), second high-pressure flash distillation cauldron (R402) are connected with second gas phase polymerization reation kettle (R302), and the commodity circulation direction is promptly:
4. a combined liquid-gas phase continuous olefin polymerization plant comprising a catalyst feed system, an olefin feed system, a hydrogen feed system, and the polymerization reaction system of any one of claims 1-3;
the catalyst feeding system, the olefin feeding system and the hydrogen feeding system are respectively connected with the polymerization reaction system.
5. The apparatus for continuous polymerization of olefins according to claim 4, further comprising a polyolefin post-treatment system, a polymerization killing system, and an olefin monomer recovery system;
the polyolefin post-treatment system and the polymerization reaction killing system are respectively connected with the polymerization reaction system; the olefin monomer recovery system is respectively connected with the polymerization reaction system and the polyolefin post-treatment system.
6. The continuous olefin polymerization apparatus according to claim 4 or 5, further comprising an auxiliary agent feeding system, a pelletizing system and a packaging system; the polyolefin post-treatment system is connected with the granulation system; the packaging system is connected with a pelletizing system and/or a polyolefin post-treatment system.
7. The apparatus for continuous polymerization of olefins according to any of claims 4 to 6, wherein the apparatus comprises a catalyst feeding system, an olefin feeding system, a hydrogen feeding system, a polymerization reaction system according to any of claims 1 to 3, a polyolefin post-treatment system, a polymerization reaction killing system, an olefin monomer recovery system, an auxiliary agent feeding system, a pelletizing system and a packaging system; the catalyst feeding system, the olefin feeding system, the hydrogen feeding system, the polyolefin post-treatment system and the polymerization reaction killing system are respectively connected with the polymerization reaction system; the olefin monomer recovery system is respectively connected with the polymerization reaction system and the polyolefin post-treatment system; the polyolefin post-treatment system is connected with the granulation system; the packaging system is connected with a pelletizing system and/or a polyolefin post-treatment system.
8. A combined liquid-gas phase continuous olefin polymerization process based on a combined liquid-gas phase continuous olefin polymerization unit according to any one of claims 4 to 7, comprising the steps of:
(1) and continuously adding a catalyst, an olefin monomer and hydrogen into the polymerization reaction system, and converting the olefin monomer into polyolefin primary particles under the action of the catalyst to obtain a mixed system containing the polyolefin primary particles.
9. The continuous process for the polymerization of olefins according to claim 8, characterized in that it further comprises the following steps:
(2) and (2) sending the mixed system obtained in the step (1) into a polymerization reaction post-treatment system, realizing the separation of polyolefin primary particles and unreacted olefin monomers, and inactivating the catalyst.
Preferably, the process further comprises the steps of:
(3) and (3) mixing the polyolefin primary particles obtained by the separation in the step (2) with an auxiliary agent, and granulating.
Also preferably, the process further comprises the steps of:
(4) recovering the unreacted olefin monomer separated in the step (2); optionally, the gas escaping from the polymerization system, the gas escaping from the high-pressure flash tank and the gas escaping from the gas lock are recovered.
Further preferably, the process further comprises the steps of:
(5) adding a substance poisoning the catalyst to the polymerization reaction system of the step (1) through the polymerization killing system to terminate the reaction.
10. The continuous olefin polymerization process according to claim 9, wherein in the step (2), the polyolefin post-treatment system comprises a separation tank, a wet nitrogen feeding unit and a solid delivery unit, the separation tank is connected with the polymerization reaction system, and the wet nitrogen feeding unit and the solid delivery unit are respectively connected with the separation tank.
Preferably, in the step (4), the recovered unreacted olefin monomer is purified and then sent to the polymerization reaction system for reuse.
Also preferably, in the step (5), the polymerization killing system comprises a gas storage tank, and the gas storage tank is connected with the polymerization system through a pipeline, in particular, connected with each reaction kettle in the polymerization system.
Still preferably, in the step (5), when the polymerization reaction system is abnormal, for example, the temperature and the pressure exceed set values, a valve of the gas storage tank is opened, and the gas in the gas storage tank enters a liquid phase reaction kettle and a gas phase reaction kettle in the polymerization reaction system to rapidly terminate the polymerization reaction; at the same time, the catalyst feed system, hydrogen feed system, and olefin monomer feed system were stopped.
Technical Field
The invention relates to a liquid phase-gas phase combined continuous olefin polymerization method and a device, in particular to a liquid phase-gas phase combined continuous polymerization method and a device for propylene homopolymerization and propylene copolymerization, belonging to the technical field of olefin polymerization.
Background
Polypropylene is the second largest synthetic resin second to polyethylene, and has the advantages of low price, excellent performance, easy processing and molding, and wide application field. The polypropylene is polymerized by taking propylene as a monomer, or is copolymerized by propylene and a small amount of other olefin monomers.
Typically, polypropylene is polymerized by catalyzing propylene monomer or comonomer with a catalyst. The polymerization reaction can be in a batch mode or a continuous mode, and the continuous mode has lower production cost and better product performance. The continuous propylene polymerization can be classified into different types according to the reactor structure, the combination method, and the presence of propylene monomers. Depending on the monomer form, the polymerization method can be classified into a liquid bulk polymerization method, a gas phase polymerization method, and a liquid bulk-gas phase tandem polymerization method. Depending on the reactor configuration, there are a ring method (e.g., Spheripol), a gas phase fluidized bed method (e.g., Unipol), a gas phase vertical stirred tank method (e.g., Novolen), a liquid phase vertical stirred tank method (e.g., Hypol), a horizontal gas phase stirred tank method (e.g., Innovene), and a combination of different reaction tanks. In the liquid phase polymerization process, the polymerization reaction is carried out in a liquid phase, and in order to control the reaction temperature and the degree of polymerization, prepolymerization is generally provided. In the gas phase polymerization process, the catalyst and the raw material propylene are directly added into the reaction, and prepolymerization is not generally arranged. Some of the currently available polymerization processes are listed below.
The batch-process bulk polymerization process is independently developed by China, and has the advantages of short process, low investment, quick response, and the disadvantages of backward process, low automation degree, unstable product quality, high operation cost and poor product quality.
The Spheripol process is developed by Basell company, and is a propylene liquid-phase bulk polymerization process which adopts a loop reaction kettle and adopts forced circulation of an axial flow pump, wherein heat is removed by a jacket outside the loop. The process has the advantages of easily controlled reaction conditions, large heat transfer coefficient of the reactor, high yield per unit volume, stable product performance and wide range of brands; the disadvantages are large investment, low conversion per pass of reaction, large rotating equipment, high energy consumption, long construction period and complex post-treatment system.
The Unipol process adopts a gas-phase fluidized bed reactor, wherein polymerization heat is taken away by sensible heat of gas, the gas circulation amount is large, and the polymerization can be realized only by a high-power booster fan; the reaction kettle is of a fully mixed type, and the product quality is not uniform. The process has the advantages of suitability for copolymerization of ethylene and propylene, simple flow, good physical properties of products and wide brand coverage; the disadvantages are high energy consumption, large equipment size, high processing difficulty, high investment and low equipment efficiency.
The innoven process employs a horizontal gas phase stirred reactor, which is close to a plug flow type reactor, wherein heat is removed by vaporization of liquid phase propylene. The process has the advantages of high heat removal efficiency of the reactor, stable production operation, uniform material retention time in the reaction period, wide melt index range of the produced product and low energy consumption; the disadvantages are that hot spots and plasticizing blocks are easy to generate in the reaction kettle, the processing difficulty of the reactor is high, key equipment needs to be imported, and the investment is high.
The Hypol process for producing polypropylene by adopting a liquid phase body and gas phase combination method in the Japan three-well comprises at least four kettles, wherein the first two kettles are vertical stirring liquid phase reaction kettles, and the second two kettles are vertical gas fluidized bed polymerization kettles. The process has the advantages that random copolymerization products and block copolymerization products can be produced; the disadvantages are long flow, low equipment efficiency, fully mixed gas phase reaction, non-uniform product quality, poor catalyst adaptability and small device scale.
The SPG process adopts a liquid phase body and gas phase combination method to produce polypropylene, and comprises at least two kettles, wherein the first kettle is a vertical stirring liquid phase reaction kettle, and the second kettle is a horizontal gas phase polymerization kettle. The process has the advantage of low investment and the disadvantage of being able to produce only polypropylene homopolymers and random copolymers and not impact copolymers.
It can be seen that each process has its advantages and disadvantages, and there is a great development space in the process.
Disclosure of Invention
In order to remedy the disadvantages of the prior art, it is an object of the present invention to provide a combined liquid-gas phase continuous olefin polymerization process and apparatus, which is particularly suitable for the production of olefin homopolymers and copolymers, such as olefin homopolymers, olefin random copolymers and olefin impact copolymers, with a more flexible combination of polymerization reactors, i.e. combinations according to the requirements of different products to produce different types of products, with shorter flow and lower costs for the production of low-end products; high-end products are produced, and the quality is higher.
In order to achieve the above purpose, the invention provides the following technical scheme:
a polymerization reaction system for olefin polymerization comprises a prepolymerization kettle, a first liquid phase polymerization reaction kettle, a second liquid phase polymerization reaction kettle, a first gas phase polymerization reaction kettle, a second gas phase polymerization reaction kettle, a gas lock, a first high-pressure flash evaporation kettle and a second high-pressure flash evaporation kettle;
the prepolymerization kettle is respectively connected with the first liquid phase polymerization reaction kettle and the second liquid phase polymerization reaction kettle; the first liquid phase polymerization reaction kettle is directly connected with the first gas phase polymerization reaction kettle or indirectly connected with the first gas phase polymerization reaction kettle through a first high-pressure flash evaporation kettle; the second liquid-phase polymerization reaction kettle is directly connected with the first gas-phase polymerization reaction kettle, or indirectly connected with the first gas-phase polymerization reaction kettle through a second high-pressure flash evaporation kettle, or directly connected with the second gas-phase polymerization reaction kettle, or indirectly connected with the second gas-phase polymerization reaction kettle through the second high-pressure flash evaporation kettle; the first liquid-phase polymerization reaction kettle is connected with the second liquid-phase polymerization reaction kettle; the first gas-phase polymerization reaction kettle is connected with the second gas-phase polymerization reaction kettle through a gas lock.
The invention further provides the following technical scheme:
a liquid phase-gas phase combined olefin continuous polymerization device comprises a catalyst feeding system, an olefin feeding system, a hydrogen feeding system and the polymerization reaction system;
the catalyst feeding system, the olefin feeding system and the hydrogen feeding system are respectively connected with the polymerization reaction system.
The invention also provides the following technical scheme:
a liquid-gas phase combined olefin continuous polymerization process is characterized in that the process is based on the liquid-gas phase combined olefin continuous polymerization device, and the process comprises the following steps:
(1) and continuously adding a catalyst, an olefin monomer and hydrogen into the polymerization reaction system, and converting the olefin monomer into polyolefin primary particles under the action of the catalyst to obtain a mixed system containing the polyolefin primary particles.
The invention has the beneficial effects that:
the invention provides a liquid-gas phase combined olefin continuous polymerization method and a device, the method is particularly suitable for the production of olefin homopolymers and copolymers, such as olefin homopolymers, olefin random copolymers and olefin impact copolymers (for example, propylene homopolymers, propylene random copolymers, propylene impact copolymers and the like can be produced), a polymerization reaction kettle has more flexible combination, can be composed according to the requirements of different products to produce different types of products, and the production of middle-end and low-end products has shorter flow and lower cost; high-end products are produced, and the quality is higher.
Drawings
FIG. 1 is a flow chart of a polymerization system according to a preferred embodiment of the present invention.
Detailed Description
[ polymerization reaction System ]
As described above, the present invention provides a polymerization reaction system suitable for olefin polymerization, which is used for realizing olefin polymerization, and can realize the preparation of olefin homopolymer, olefin random copolymer and olefin impact copolymer by adjusting the connection relationship of each reaction kettle in the polymerization reaction system, i.e. the material orientation. Specifically, the polymerization reaction system comprises a prepolymerization reactor R101, a first liquid phase polymerization reactor R201, a second liquid phase polymerization reactor R202, a first gas phase polymerization reactor R301, a second gas phase polymerization reactor R302, an air lock, a first high-pressure flash evaporation reactor R401 and a second high-pressure flash evaporation reactor R402;
the prepolymerization reactor R101 is respectively connected with a first liquid phase polymerization reactor R201 and a second liquid phase polymerization reactor R202; the first liquid phase polymerization reaction kettle R201 is directly connected with the first gas phase polymerization reaction kettle R301 or indirectly connected with the first gas phase polymerization reaction kettle R301 through a first high-pressure flash evaporation kettle R401; the second liquid-phase polymerization reaction kettle R202 is directly connected with the first gas-phase polymerization reaction kettle R301, or indirectly connected with the first gas-phase polymerization reaction kettle R301 through a second high-pressure flash evaporation kettle R402, or directly connected with the second gas-phase polymerization reaction kettle R302, or indirectly connected with the second gas-phase polymerization reaction kettle R302 through the second high-pressure flash evaporation kettle R402; the first liquid-phase polymerization reaction kettle R201 is connected with the second liquid-phase polymerization reaction kettle R202; the first gas phase polymerization reaction kettle R301 is connected with the second gas phase polymerization reaction kettle R302 through a gas lock.
In a preferred embodiment of the present invention, the flow direction of the materials in the polymerization reaction system can be adjusted according to the target product, for example, the flow direction of the materials can be realized through the control of a valve, and the valve can be arranged on a pipeline connecting each polymerization reaction kettle, for example.
Wherein, the first liquid phase polymerization reaction kettle R201 and the second liquid phase polymerization reaction kettle R202 can be vertical stirring reaction kettles, can also be loop reactors, and are preferably vertical stirring reaction kettles; wherein the olefin monomer exists in the reaction kettle mainly in a liquid state, and polymer particles generated by the reaction are dispersed in the liquid olefin monomer;
wherein, the first gas phase polymerization reaction kettle R301 and the second gas phase polymerization reaction kettle R302 can be a horizontal plug flow gas phase reactor, a vertical stirring gas phase reactor, or a fluidized bed gas phase reactor; preferably a horizontal plug flow gas phase reactor.
In a preferred embodiment of the present invention, the prepolymerization reactor R101 is connected to a first liquid phase polymerization reactor R201 and a second liquid phase polymerization reactor R202, respectively, the first liquid phase polymerization reactor R201 is connected to a first gas phase polymerization reactor R301, and the second liquid phase polymerization reactor R202 is connected to a second gas phase polymerization reactor R302, that is, the flow direction is as shown in the following flow pattern a.
In a preferred embodiment of the present invention, the prepolymerization reactor R101 is connected to a first liquid phase polymerization reactor R201, the first liquid phase polymerization reactor R201 is connected to a second liquid phase polymerization reactor R202, the second liquid phase polymerization reactor R202 is connected to a first gas phase polymerization reactor R301, and the first gas phase polymerization reactor R301 is connected to a second gas phase polymerization reactor R302 through a gas lock, that is, the flow direction is as shown in the following flow pattern B.
R101 → R201 → R202 → R301 → airlock → R302 → polymer post-treatment system (stream mode B)
In a preferred embodiment of the present invention, the prepolymerization reactor R101 is connected to a first liquid phase polymerization reactor R201, the first liquid phase polymerization reactor R201 is connected to a second liquid phase polymerization reactor R202, the second liquid phase polymerization reactor R202 is connected to a first gas phase polymerization reactor R301 through a second high pressure flash reactor R402, and the first gas phase polymerization reactor R301 is connected to a second gas phase polymerization reactor R302 through a gas lock, that is, the material flow direction is as shown in the following material flow manner C.
R101 → R201 → R202 → R402 → R301 → airlock → R302 → polymer post-treatment system
(physical distribution mode C)
In a preferred embodiment of the present invention, the prepolymerization reactor R101 is connected to a first liquid phase polymerization reactor R201 and a second liquid phase polymerization reactor R202, the first liquid phase polymerization reactor R201 is connected to a first high pressure flash evaporation reactor R401, the first high pressure flash evaporation reactor R401 is connected to a first gas phase polymerization reactor R301, the second liquid phase polymerization reactor R202 is connected to a second high pressure flash evaporation reactor R402, and the second high pressure flash evaporation reactor R402 is connected to a second gas phase polymerization reactor R302, i.e., the material flow direction is as shown in the following material flow mode D.
Wherein, the catalyst and part of olefin monomer are added into the prepolymerization reactor R101 for realizing the premixing of materials and a small amount of polymerization reaction, and the catalyst can be prevented from cracking in the subsequent polymerization.
Wherein, the rest olefin monomer and hydrogen are added into at least one of the first liquid phase polymerization reaction kettle R201, the second liquid phase polymerization reaction kettle R202, the first gas phase polymerization reaction kettle R301 and the second gas phase polymerization reaction kettle R302 for realizing polymerization reaction and converting the polymerization monomer into polymer.
Wherein, the first gas phase polymerization reaction kettle R301 and the second gas phase polymerization reaction kettle R302 are respectively connected with a polyolefin post-treatment system.
[ liquid-gas phase Combined olefin continuous polymerization apparatus ]
As described above, the present invention provides a combined liquid-gas phase continuous olefin polymerization apparatus comprising a catalyst feeding system, an olefin feeding system, a hydrogen feeding system and the above polymerization reaction system;
the catalyst feeding system, the olefin feeding system and the hydrogen feeding system are respectively connected with the polymerization reaction system.
In a preferred embodiment of the present invention, the apparatus further comprises a polyolefin post-treatment system, a polymerization killing system, and an olefin monomer recovery system;
the polyolefin post-treatment system and the polymerization reaction killing system are respectively connected with the polymerization reaction system; the olefin monomer recovery system is respectively connected with the polymerization reaction system and the polyolefin post-treatment system.
In a preferred scheme of the invention, the device further comprises an auxiliary agent adding system, a granulating system and a packaging system; the polyolefin post-treatment system is connected with the granulation system; the packaging system is connected with a pelletizing system and/or a polyolefin post-treatment system.
Illustratively, the apparatus includes a catalyst feed system, an olefin feed system, a hydrogen feed system, a polymerization reaction system, a polyolefin post-treatment system, a polymerization reaction kill system, an olefin monomer recovery system, an auxiliary addition system, a pelletizing system, and a packaging system; the catalyst feeding system, the olefin feeding system, the hydrogen feeding system, the polyolefin post-treatment system and the polymerization reaction killing system are respectively connected with the polymerization reaction system; the olefin monomer recovery system is respectively connected with the polymerization reaction system and the polyolefin post-treatment system; the polyolefin post-treatment system is connected with the granulation system; the packaging system is connected with a pelletizing system and/or a polyolefin post-treatment system.
< catalyst feeding System >
In a preferred embodiment of the present invention, the catalyst feed system comprises a catalyst storage tank and a feeding device; the catalyst feed system is used to provide catalyst to a polymerization reaction system.
Wherein the feeding device may be a metering pump, for example.
The catalyst storage tank stores a main catalyst, an activator and an optional regulator, wherein the main catalyst is a solid particle, and the activator and the regulator are liquid;
the main catalyst can be directly added in a solid mode or added in a metering pump after being prepared into slurry; the activating agent and the regulator are added through a metering pump;
the procatalyst is, for example, a Ziegler-Natta catalyst (e.g., MgCl)2Supported TiCl4Catalyst) or a silica gel supported metallocene catalyst.
The activator is, for example, one or more of an aluminum alkyl, an aluminum alkyl chloride, a methylaluminoxane.
The modifier is, for example, an alkylalkoxysilane, such as one or more of cyclohexyldimethoxysilane, dicyclopentyldimethoxysilane, diisobutyldimethoxysilane or diisopropyldimethoxysilane.
When the procatalyst is a Ziegler-Natta catalyst, the activator is an aluminum alkyl or an aluminum alkyl chloride, such as triethylaluminum, triisobutylaluminum or diethylaluminum chloride; the regulator is an alkylalkoxysilane such as cyclohexyldimethoxysilane, dicyclopentyldimethoxysilane, diisobutyldimethoxysilane or diisopropyldimethoxysilane.
When the main catalyst is a metallocene catalyst loaded on silica gel, the activator is methylaluminoxane and no regulator is used.
< olefin feed System >
In a preferred embodiment of the present invention, the olefin feed system comprises a plurality of olefin monomer storage tanks, a plurality of olefin monomer purification units, and a feeding unit; the olefin feed system is used to provide olefin monomer to a polymerization reaction system.
Wherein, the olefin monomer can be liquid, gas or compressed gas-liquid mixed state; the olefin monomer comprises one or more of ethylene, propylene, butene, hexene, octene, preferably propylene, ethylene and butene.
The feeding device can be, for example, a metering pump, such as a liquid or gas metering pump.
Wherein, the olefin monomer purification device comprises but is not limited to a dehydration unit (for example, dehydration by using a molecular sieve), a deoxidation unit (for example, deoxidation by using a deoxidizer), a desulfurization unit (for example, desulfurization by using a desulfurizing agent), a carbon monoxide removal unit, a carbon dioxide removal unit and the like, and is used for providing qualified olefin monomers with qualified impurity content for a polymerization reaction system. After passing through the olefin monomer purifying device, the olefin monomer with purity of more than 98 wt% and qualified impurity content can be obtained, for example, the water content is not more than 10ppm, the sulfur content is not more than 5ppm, the carbon dioxide content is not more than 10ppm, and the carbon monoxide content is not more than 10ppb, and the impurities have great influence on the activity of the catalyst and even cause the complete deactivation of the catalyst.
< Hydrogen feeding System >
In a preferred embodiment of the present invention, the hydrogen feeding system comprises a hydrogen storage tank and a feeding device; the hydrogen feeding system is used for providing hydrogen for the polymerization reaction system. The addition of hydrogen can regulate the molecular weight of the polyolefin.
Wherein the feeding device may be a metering pump, for example.
< polyolefin post-treatment System >
In a preferred embodiment of the present invention, the polyolefin post-treatment system comprises a separation tank, a wet nitrogen feeding unit and a solid delivery unit, the separation tank is connected to the polymerization reaction system and the olefin monomer recovery system, and the wet nitrogen feeding unit and the solid delivery unit are respectively connected to the separation tank.
Wherein the separation tank is used for realizing the separation of the polyolefin primary particles and the unreacted olefin monomers; when the mixed system obtained by the reaction of the polymerization reaction system enters a separation storage tank, unreacted olefin monomers are gasified and separated from polyolefin primary particles under the action of pressure drop, and the gasified olefin monomers enter an olefin monomer recovery system.
The wet nitrogen feeding unit is used for providing water vapor and nitrogen for the separation storage tank, and is used for further realizing volatilization of olefin monomers and better realizing separation of unreacted olefin monomers and polyolefin primary particles; in addition, because the water vapor can react with the catalyst, the method can also be used for realizing the inactivation treatment of the catalyst.
Wherein nitrogen from the wet nitrogen feed unit is also passed to the olefin monomer recovery system, said nitrogen being present in the system as an inert component.
Wherein, wet nitrogen gas feed unit is connected with the bottom of separation storage tank.
< polymerization reaction killing System >
In a preferred embodiment of the present invention, the polymerization killing system comprises a gas storage tank, which is connected to the polymerization system, in particular, to each reaction vessel in the polymerization system, via a pipeline.
Wherein at least one of wet nitrogen, oxygen and carbon monoxide is stored in the gas storage tank.
When the polymerization reaction system is abnormal, such as the temperature and the pressure exceed set values, a valve of a gas storage tank is opened, and gas in the gas storage tank enters a liquid phase reaction kettle and a gas phase reaction kettle in the polymerization reaction system to rapidly terminate the polymerization reaction; at the same time, the catalyst feed system, hydrogen feed system, and olefin monomer feed system were stopped.
< olefin monomer recovery System >
In a preferred embodiment of the present invention, the olefin monomer recovery system is used for recovering gas overflowed from the polymerization reaction system and the polyolefin post-treatment system, and nitrogen, hydrogen and olefin monomers are obtained after separation.
The olefin monomer recovery system is used for recovering gas overflowing from each reaction kettle in the polymerization reaction system, gas overflowing from the high-pressure flash evaporation kettle, gas overflowing from the airlock, olefin monomers, hydrogen, nitrogen, water vapor and the like volatilized from the polyolefin aftertreatment system.
Wherein the separation may be, for example, a method using compression, distillation, and/or membrane separation.
The separated nitrogen enters the polymerization reaction post-treatment system again after being purified, the separated hydrogen enters the hydrogen feeding system again after being purified, and the separated olefin monomer enters the polymerization reaction system again after being purified.
< adjuvant addition System >
In a preferred embodiment of the present invention, the additive adding system comprises a plurality of additive storage tanks and a feeding device; the additive adding system is used for improving the performance of polyolefin.
The auxiliary agents include, but are not limited to, those known in the art that can be added to polyolefins, particularly polypropylene, such as antioxidants, acid scavengers, nucleating agents, and antistatic agents.
Wherein the feeding device may be a metering pump, for example. The proportion of different added additives can be controlled by a metering pump, wherein a plurality of additives can be pre-mixed according to the proportion and added at one time, or can be added respectively; preferably, the premixed adjuvant is added at one time.
< granulation System >
In a preferred embodiment of the invention, the pelletizing system comprises a pelletizer, which may be a pelletizer as known in the art.
< packaging System >
In a preferred embodiment of the invention, the packaging system may be a packaging system known in the art.
Wherein the packaging system is used for packaging the granulated polyolefin large particles or packaging the polyolefin primary particles in the polymerization post-treatment system.
[ liquid-gas phase Combined olefin continuous polymerization Process ]
As described above, the present invention provides a liquid-gas phase combined olefin continuous polymerization process, which is based on the above-mentioned liquid-gas phase combined olefin continuous polymerization apparatus, and comprises the following steps:
(1) and continuously adding a catalyst, an olefin monomer and hydrogen into the polymerization reaction system, and converting the olefin monomer into polyolefin primary particles under the action of the catalyst to obtain a mixed system containing the polyolefin primary particles.
In a preferred embodiment of the present invention, the process further comprises the steps of:
(2) and (2) sending the mixed system obtained in the step (1) into a polymerization reaction post-treatment system, realizing the separation of polyolefin primary particles and unreacted olefin monomers, and inactivating the catalyst.
In a preferred embodiment of the present invention, the process further comprises the steps of:
(3) and (3) mixing the polyolefin primary particles obtained by the separation in the step (2) with an auxiliary agent, and granulating.
In a preferred embodiment of the present invention, the process further comprises the steps of:
(4) recovering the unreacted olefin monomer separated in the step (2); optionally, the gas escaping from the polymerization system, the gas escaping from the high-pressure flash tank and the gas escaping from the gas lock are recovered.
In a preferred embodiment of the present invention, the process further comprises the steps of:
(5) adding a substance poisoning the catalyst to the polymerization reaction system of the step (1) through the polymerization killing system to terminate the reaction.
In a preferred embodiment of the present invention, step (1) specifically includes the following steps:
(1-1) continuously adding a catalyst and a part of olefin monomers into a prepolymerization reactor R101 in a polymerization reaction system, mixing, and then sending into a first liquid phase polymerization reactor R201 and/or a second liquid phase polymerization reactor R202 polymerization reactor in the polymerization reaction system;
(1-2) continuously adding the rest olefin monomer and hydrogen into a first liquid phase polymerization reaction kettle R201 and/or a second liquid phase polymerization reaction kettle R202 polymerization kettle and/or a first gas phase polymerization reaction kettle R301 and/or a second gas phase polymerization reaction kettle R302 in a polymerization reaction system, and converting the olefin monomer into polyolefin primary particles under the action of a catalyst to obtain a mixed system.
In a preferred embodiment of the present invention, in step (1), the preparation of olefin homopolymer, olefin random copolymer and olefin impact copolymer can be realized by adjusting the connection relationship among the first liquid phase polymerization reactor R201, the second liquid phase polymerization reactor R202, the first gas phase polymerization reactor R301, the second gas phase polymerization reactor R302, the first high-pressure flash distillation reactor R401, the second high-pressure distillation reactor R402 and the gas lock in the polymerization reaction system, the reaction temperature, the reaction pressure and the hydrogenation amount of each reactor.
In a preferred embodiment of the present invention, step (1) specifically includes the following steps:
(1-0-a) the polymerization reaction system comprises a prepolymerization reactor R101, a first liquid phase polymerization reactor R201, a second liquid phase polymerization reactor R202, a first gas phase polymerization reactor R301 and a second gas phase polymerization reactor R302;
prepolymerization cauldron R101 is connected with first liquid phase polymerization reation kettle R201 and second liquid phase polymerization reation kettle R202 respectively, first liquid phase polymerization reation kettle R201 is connected with first gaseous phase polymerization reation kettle R301, second liquid phase polymerization reation kettle R202 is connected with second gaseous phase polymerization reation kettle R302, and the commodity circulation direction is promptly:
(1-1-a) continuously adding a catalyst and a part of olefin monomers into a prepolymerization reactor R101 in a polymerization reaction system, mixing, and then sending into a first liquid phase polymerization reactor R201 and a second liquid phase polymerization reactor R202 in the polymerization reaction system;
(1-2-a) continuously adding the rest olefin monomer and hydrogen into a first liquid phase polymerization reaction kettle R201, a second liquid phase polymerization reaction kettle R202, a first gas phase polymerization reaction kettle R301 and a second gas phase polymerization reaction kettle R302 in a polymerization reaction system, and converting the olefin monomer into polyolefin primary particles under the action of a catalyst to obtain a mixed system.
In a preferred embodiment of the present invention, step (1) specifically includes the following steps:
(1-0-b) the polymerization reaction system comprises a prepolymerization reactor R101, a first liquid phase polymerization reactor R201, a second liquid phase polymerization reactor R202, a first gas phase polymerization reactor R301, a second gas phase polymerization reactor R302 and a gas lock;
prepolymerization cauldron R101 is connected with first liquid phase polymerization reation kettle R201, first liquid phase polymerization reation kettle R201 is connected with second liquid phase polymerization reation kettle R202, second liquid phase polymerization reation kettle R202 is connected with first gaseous phase polymerization reation kettle R301, first gaseous phase polymerization reation kettle R301 is connected with second gaseous phase polymerization reation kettle R302 through the gas lock, and the commodity circulation direction is promptly:
r101 → R201 → R202 → R301 → airlock → R302 → polymer post-treatment system;
(1-1-b) continuously adding a catalyst and a part of olefin monomers into a prepolymerization reactor R101 in a polymerization reaction system, mixing, and then sending into a first liquid phase polymerization reactor R201 in the polymerization reaction system;
(1-2-b) continuously adding the rest olefin monomer and hydrogen into a first liquid phase polymerization reaction kettle R201, a second liquid phase polymerization reaction kettle R202, a first gas phase polymerization reaction kettle R301 and a second gas phase polymerization reaction kettle R302 in a polymerization reaction system, and converting the olefin monomer into polyolefin primary particles under the action of a catalyst to obtain a mixed system.
In a preferred embodiment of the present invention, step (1) specifically includes the following steps:
(1-0-c) the polymerization reaction system comprises a prepolymerization reactor R101, a first liquid phase polymerization reactor R201, a second liquid phase polymerization reactor R202, a first gas phase polymerization reactor R301, a second gas phase polymerization reactor R302, a second high-pressure flash evaporation reactor R402 and a gas lock;
prepolymerization cauldron R101 is connected with first liquid phase polymerization reation kettle R201, first liquid phase polymerization reation kettle R201 is connected with second liquid phase polymerization reation kettle R202, second liquid phase polymerization reation kettle R202 is connected with first gas phase polymerization reation kettle R301 through second high-pressure flash distillation cauldron R402, first gas phase polymerization reation kettle R301 is connected with second gas phase polymerization reation kettle R302 through the air-lock, and the commodity circulation direction is promptly:
r101 → R201 → R202 → R402 → R301 → airlock → R302 → polymer post-treatment system;
(1-1-c) continuously adding a catalyst and a part of olefin monomers into a prepolymerization reactor R101 in a polymerization reaction system, mixing, and then feeding into a first liquid phase polymerization reactor R201 in the polymerization reaction system;
(1-2-c) continuously adding the rest olefin monomer and hydrogen into a first liquid phase polymerization reaction kettle R201, a second liquid phase polymerization reaction kettle R202, a first gas phase polymerization reaction kettle R301 and a second gas phase polymerization reaction kettle R302 in a polymerization reaction system, and converting the olefin monomer into polyolefin primary particles under the action of a catalyst to obtain a mixed system.
In a preferred embodiment of the present invention, step (1) specifically includes the following steps:
(1-0-d) the polymerization reaction system comprises a prepolymerization reactor R101, a first liquid phase polymerization reactor R201, a second liquid phase polymerization reactor R202, a first gas phase polymerization reactor R301, a second gas phase polymerization reactor R302, a first high-pressure flash evaporation reactor R401 and a second high-pressure flash evaporation reactor R402;
prepolymerization cauldron R101 is connected with first liquid phase polymerization cauldron R201 and second liquid phase polymerization cauldron R202 respectively, first liquid phase polymerization cauldron R201 links to each other with first high-pressure flash cauldron R401, first high-pressure flash cauldron R401 is connected with first gas phase polymerization cauldron R301, second liquid phase polymerization cauldron R202 links to each other with second high-pressure flash cauldron R402, second high-pressure flash cauldron R402 is connected with second gas phase polymerization cauldron R302, and the commodity circulation direction is promptly:
(1-1-d) continuously adding a catalyst and a part of olefin monomers into a prepolymerization reactor R101 in a polymerization reaction system, mixing, and then sending into a first liquid phase polymerization reactor R201 and a second liquid phase polymerization reactor R202 in the polymerization reaction system;
(1-2-d) continuously adding the rest olefin monomer and hydrogen into a first liquid phase polymerization reaction kettle R201, a second liquid phase polymerization reaction kettle R202, a first gas phase polymerization reaction kettle R301 and a second gas phase polymerization reaction kettle R302 in a polymerization reaction system, and converting the olefin monomer into polyolefin primary particles under the action of a catalyst to obtain a mixed system.
In a preferred embodiment of the present invention, when producing a propylene homopolymer, the polymerization reaction system may be:
the polymerization reaction system has short flow, narrow molecular weight distribution of the polymer, controllable polymerization residence time of 1-2h and high reaction efficiency.
In a preferred embodiment of the present invention, when producing a propylene homopolymer, the polymerization reaction system may be:
r101 → R201 → R202 → R301 → airlock → R302 → polymer post-treatment system;
the polymerization reaction system has long flow, each reaction kettle can be set with different reaction temperature, reaction pressure and hydrogenation amount, and the molecular weight of the generated polymer in each reaction kettle is adjusted to obtain the propylene homopolymer with particularly wide molecular weight distribution.
In a preferred embodiment of the present invention, when producing a propylene homopolymer, the polymerization reaction system may be:
r101 → R201 → R202 → R301 → airlock → R302 → polymer post-treatment system;
the polymerization reaction system has long flow, each reaction kettle can be set with different reaction temperature, reaction pressure and hydrogenation amount, the pressure of R301 and R302 is adjusted, the partial pressure of polypropylene is reduced, the partial pressure of hydrogen is increased, and the propylene homopolymer with particularly high melt index can be produced.
In a preferred embodiment of the present invention, when producing a propylene homopolymer, the polymerization reaction system may be:
r101 → R201 → R202 → R301 → airlock → R302 → polymer post-treatment system;
the polymerization reaction system has long flow, can prolong the residence time of the whole reaction flow, and ensures that the residence time is 3-4 hours, so that the catalyst activity can be exerted more fully, and when the catalyst activity is higher, the ash content of the propylene homopolymer is lower, so that the low-ash propylene homopolymer can be prepared.
In a preferred embodiment of the present invention, when producing a propylene random copolymer, such as a propylene and ethylene copolymer, a propylene and butene copolymer, a propylene and ethylene-butene terpolymer, the polymerization system may be:
the polymerization reaction system has short flow, narrow molecular weight distribution of the polymer, controllable polymerization residence time of 1-2h and high reaction efficiency.
In a preferred embodiment of the present invention, when producing a propylene random copolymer, such as a propylene and ethylene copolymer, a propylene and butene copolymer, a propylene and ethylene-butene terpolymer, the polymerization system may be:
r101 → R201 → R202 → R301 → airlock → R302 → polymer post-treatment system;
the polymerization reaction system has long process flow, each reaction kettle can be set with different reaction temperature, reaction pressure, hydrogenation amount and comonomer concentration, the molecular weight and the molecular structure of the generated polymer in each reaction kettle are adjusted, the propylene random copolymer with particularly wide molecular weight distribution and particularly wide chemical composition is obtained, and the copolymer has better mechanical property, heat sealing property and processing property, such as production of ethylene propylene random copolymer (PPR) base pipes, polypropylene heat sealing film materials and the like.
In a preferred embodiment of the present invention, when producing propylene impact copolymers, the polymerization system is:
propylene homopolymerization is carried out in a first liquid phase polymerization reaction kettle R201 and a second liquid phase polymerization reaction kettle R202; the material from the first liquid phase polymerization reaction kettle R201 enters a first high-pressure flash evaporation kettle R401, liquid phase propylene is evaporated, and the residual polypropylene solid particles are conveyed to a first gas phase polymerization reaction kettle R301; adding a mixture of ethylene and propylene, or a mixture of propylene and butylene, or a ternary mixture of propylene, butylene and ethylene into a first gas phase polymerization reaction kettle R301, simultaneously adding hydrogen, continuing polymerization, and after polymerization, feeding the materials into a polymer post-treatment system. The material from the second liquid phase polymerization reaction kettle R202 enters a second high-pressure flash evaporation kettle R402 to evaporate liquid phase propylene, and the residual polypropylene solid particles are conveyed to a second gas phase polymerization reaction kettle R302; and adding a mixture of ethylene and propylene, or a mixture of propylene and butylene, or a ternary mixture of propylene, butylene and ethylene into the second gas-phase polymerization reactor R302, simultaneously adding hydrogen, continuing polymerization, and after the polymerization is finished, feeding the material into a polymer post-treatment system. The material proportion, the reaction temperature and the reaction pressure in the first liquid phase polymerization reaction kettle R201 and the second liquid phase polymerization reaction kettle R202 are the same, the material proportion, the reaction temperature and the reaction pressure in the first gas phase polymerization reaction kettle R301 and the second gas phase polymerization reaction kettle R302 are the same, and finally the propylene impact copolymer is obtained.
In a preferred embodiment of the present invention, when producing propylene impact copolymers, the polymerization system is:
r101 → R201 → R202 → R402 → R301 → airlock → R302 → polymer post-treatment system;
propylene homopolymerization is carried out in the first liquid phase polymerization reaction kettle R201 and the second liquid phase polymerization reaction kettle R202, and different hydrogenation amounts can be adopted in the two reactors so as to widen the molecular weight of the polypropylene homopolymer and enable the polypropylene homopolymer to have higher rigidity. The material from the second liquid phase polymerization reactor R202 enters a second high pressure flash evaporation reactor R402 to evaporate liquid phase propylene, the residual polypropylene solid particles are conveyed to a first gas phase polymerization reactor R301, a mixture of ethylene and propylene, or a mixture of propylene and butylene, or a ternary mixture of propylene, butylene and ethylene is added into the first gas phase polymerization reactor R301, hydrogen is added at the same time to continue polymerization, the polymer enters an air lock to degas, gaseous monomers in the polymer are conveyed to recycled olefin, the solid particles enter a second gas phase polymerization reactor R302, a mixture of ethylene and propylene, or a mixture of propylene and butylene, or a ternary mixture of propylene, butylene and ethylene is added simultaneously to continue polymerization, and after the polymerization is finished, the material enters a polymer post-treatment system. The material ratio, reaction temperature and reaction pressure in the first gas phase polymerization reaction kettle R301 and the second gas phase polymerization reaction kettle R302 can be the same or different. Finally, the propylene impact copolymer with excellent performance is obtained.
In a preferred embodiment of the present invention, in the step (2), the polyolefin post-treatment system comprises a separation tank, a wet nitrogen feeding unit and a solid delivery unit, the separation tank is connected to the polymerization reaction system, and the wet nitrogen feeding unit and the solid delivery unit are respectively connected to the separation tank.
In a preferred embodiment of the present invention, the step (2) specifically includes the following steps:
(2-1) sending the mixed system in the step (1) into a separation storage tank in a polymerization reaction post-treatment system, and separating unreacted olefin monomers from polyolefin primary particles through gasification;
and (2-2) introducing wet nitrogen into the separation storage tank, further realizing the gasification of the unreacted olefin monomer, and inactivating the catalyst.
In a preferred embodiment of the present invention, in step (3), the granulation temperature is the operating temperature conventional in the art.
In a preferred embodiment of the present invention, in the step (4), the recovered unreacted olefin monomer is purified and then sent to the polymerization reaction system for reuse.
In a preferred embodiment of the present invention, in the step (5), the polymerization killing system comprises a gas storage tank, and the gas storage tank is connected with the polymerization system through a pipeline, in particular, connected with each reaction kettle in the polymerization system.
Wherein at least one of wet nitrogen, oxygen and carbon monoxide is stored in the gas storage tank.
In a preferred embodiment of the present invention, in the step (5), when the polymerization reaction system is abnormal, such as temperature and pressure exceed set values, a valve of a gas storage tank is opened, and gas in the gas storage tank enters a liquid phase reaction kettle and a gas phase reaction kettle in the polymerization reaction system to rapidly terminate the polymerization reaction; at the same time, the catalyst feed system, hydrogen feed system, and olefin monomer feed system were stopped.
The preparation method of the present invention will be described in further detail with reference to specific examples. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; reagents, materials and the like used in the following examples are commercially available unless otherwise specified.
In the description of the present invention, it should be noted that the terms "first", "second", etc. are used for descriptive purposes only and do not indicate or imply relative importance.
Optionally indicating the presence or absence of said feature, or the definite presence of said feature, but the particular choice may be at will