CN119303508A - A gas phase production device and production method of polyolefin elastomer - Google Patents
A gas phase production device and production method of polyolefin elastomer Download PDFInfo
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Abstract
本发明涉及一种聚烯烃弹性体的气相法生产装置和生产方法，属于石油化工技术领域。所述生产装置包括气相流化床反应器、深冷液化器、液化乙烯泵、乙烯喷射器和循环气换热器；其中，深冷液化器与裂解装置的乙烯管路连接，用于将裂解装置制备得到的乙烯液化形成液化乙烯；乙烯喷射器与液化乙烯泵和气相流化床反应器的流化回路分别连接，用于将液化乙烯喷射式输送至所述气相流化床反应器的流化回路，参与聚烯烃弹性体的聚合反应。本发明利用烯烃原料固有的气化潜热特性对聚烯烃弹性体生产过程中的反应体系进行撤热，显著降低聚合反应的温度，从而实现聚烯烃弹性体生产过程的热管理优化，提升生产负荷，制备出更低熔点的聚烯烃弹性体。
The present invention relates to a gas phase production device and production method of polyolefin elastomer, belonging to the field of petrochemical technology. The production device includes a gas phase fluidized bed reactor, a cryogenic liquefier, a liquefied ethylene pump, an ethylene injector and a circulating gas heat exchanger; wherein the cryogenic liquefier is connected to the ethylene pipeline of the cracking device, and is used to liquefy the ethylene prepared by the cracking device to form liquefied ethylene; the ethylene injector is respectively connected to the liquefied ethylene pump and the fluidizing circuit of the gas phase fluidized bed reactor, and is used to inject the liquefied ethylene to the fluidizing circuit of the gas phase fluidized bed reactor to participate in the polymerization reaction of the polyolefin elastomer. The present invention utilizes the inherent latent heat of gasification characteristics of olefin raw materials to remove heat from the reaction system in the production process of polyolefin elastomer, significantly reducing the temperature of the polymerization reaction, thereby realizing the thermal management optimization of the production process of polyolefin elastomer, increasing the production load, and preparing polyolefin elastomers with lower melting points.
Description
Technical Field
The invention belongs to the technical field of petrochemical industry, and relates to a gas-phase method production device and a production method of a polyolefin elastomer.
Background
Polyolefin elastomer (Polyolefin elastomer, POE for short) is a product formed by copolymerizing ethylene and alpha-olefin (usually 1-butene, 1-hexene, 1-octene, etc.), the content of comonomer is generally more than 20%, and the alpha-olefin greatly weakens the crystallization area of the carbon-carbon main chain and forms an amorphous structure similar to rubber elasticity because the content of comonomer is far higher than that of the conventional polyolefin resin, so that the product has excellent optical property, mechanical property and processability, and the transmittance, elongation at break and low-temperature brittleness of the product are all due to general polyethylene and polypropylene.
The solution method is one of the main production methods of polyolefin elastomer (POE), and has the characteristics of excellent product performance, wide product index range, multiple molecular weight adjustment means and the like. The polyolefin elastomer is produced by the process in the abroad Dow chemistry, sanjing, and Exxon Mobil. However, the solution method also has the defects of difficult solvent recovery, higher energy consumption, large equipment investment and the like.
Currently, gas phase processes for producing polyethylene have been developed and used in the production process. The gas-phase fluidized bed is a common polymerization reactor for producing polyethylene, and has the characteristics of short reaction flow, simple reactor structure, good deashing and degassing effects and the like. However, the gas-phase fluidized-bed reactor is difficult to be compatible with the contradiction between the reaction temperature and the melting point of the polymer. The polymerization temperature is too high, the polymer powder is sticky, the fluidization state is influenced by lump generation, and the catalyst yield is influenced by strict control of the heat release amount of the polymerization reaction, so that the production cost is negatively influenced.
Patent CN 107531827B discloses a process and a system for olefin polymerization. The system includes flowing a catalyst through an injection nozzle and into a fluidized bed disposed within a reactor. The method includes flowing a material comprising one or more monomers, one or more inert fluids, or a combination thereof through the injection nozzle and into the fluidized bed, which material may be at a temperature exceeding ambient temperature. The method further comprises contacting one or more olefins with the catalyst within the fluidized bed under conditions sufficient to produce a polyolefin.
Patent CN 105705532B discloses a process for producing a polyolefin comprising contacting a reaction mixture with a reduced chromium oxide catalyst in a gas phase reactor to produce a polyolefin, wherein the reaction mixture comprises a monomer and a comonomer, and varying the reaction temperature in the gas phase reactor by about 1 ℃ or more, thereby varying the gas molar ratio of the comonomer to the monomer by about 2% or more and varying the comonomer content of the polyolefin of a substantially constant density by about 2% or more.
Patent CN 103638877B discloses a gaseous phase fluidized bed reactor, including gas collecting section, straight section of thick bamboo and expansion section, separate through gas distribution board between gas collecting section and the straight section of thick bamboo, be equipped with pivot and stirring paddle in the straight section of thick bamboo, still be equipped with the baffle in the straight section of thick bamboo, the baffle cooperatees with stirring paddle for shearing the material. The patent also discloses a gas-phase fluidized-bed reactor with a stirring system, which can prevent agglomeration among high-viscosity polymer particles and adhesion of the polymer particles to the inner wall of the reactor without adding auxiliary inert particles, can produce an effective stirring and mixing effect and improve fluidization stability of the high-viscosity polymer particles.
On the basis of producing polyethylene by a gas phase method, the production process of the POE by the gas phase method is gradually developed. Patent CN 108948248B discloses a method for producing polyolefin elastomer by gas phase method, in which the polymerization reaction of POE is carried out in a reactor using polyethylene particles as seed bed, concretely, a raw material mixture comprising ethylene, hydrogen and nitrogen is introduced into the reactor, so that the polyethylene particles in the seed bed flow and reach fluidization state, then a catalyst is added into the reactor, and an atomized droplet-shaped comonomer is introduced into the reactor for reaction, wherein the comonomer is long-chain olefin with 6-18 carbon atoms, the density of the prepared polymerization product is 0.865-0.910 g/cm 3, and the content of long-chain olefin is 6-40 wt%.
However, a key technical problem faced in the production of POE by gas phase processes is that POE materials, because of their unique low melting point characteristics, require that the polymerization reaction be carried out at relatively low reaction temperatures, which place more stringent demands on external heat exchange systems. Conventionally, a gas phase process polyethylene production apparatus generally relies on a circulating water system to achieve effective heat removal, but this process has significant limitations in terms of heat removal capability when dealing with the large amount of polymerization heat generated during POE production. Because the reaction temperature in the POE production process is close to the temperature of the circulating water of the heat exchanger, the polymerization heat is difficult to remove, the production load and the production efficiency are restricted, and the product quality stability is possibly adversely affected.
Therefore, a novel heat removing device and technology which are more efficient and adapt to the low-temperature polymerization environment need to be explored and developed, and more accurate and efficient temperature control is realized, so that the production efficiency and the product quality of POE products are ensured.
Disclosure of Invention
The invention provides a gas phase method production device and a production method of polyolefin elastomer, which are used for solving the problems of low POE heat removal capacity and low production load of the conventional gas phase method device. The device and the method can effectively withdraw the polymerization reaction heat in the POE production process, and reduce the production cost of the POE.
In a first aspect, the present invention provides a device for the production of polyolefin elastomer by gas phase process, comprising the following components:
a gas-phase fluidized bed reactor, which comprises a polymerization reactor and a fluidization loop (also called as a gas-phase fluidization loop, a reaction fluidization loop or a reaction loop), wherein the polymerization reactor comprises a diameter section and an expansion section, the diameter section comprises a gas-phase distribution plate positioned at the bottom of the diameter section;
The cryogenic liquefier is connected with an ethylene pipeline of the cracking device and is used for liquefying ethylene (or refined ethylene) prepared by the cracking device to form liquefied ethylene (or low-temperature ethylene);
A liquefied ethylene tank connected to the cryogenic liquefier for storing liquefied ethylene (also referred to as cryogenic ethylene, or cryogenic liquefied ethylene) cooled by the cryogenic liquefier;
A liquefied ethylene pump connected to the liquefied ethylene tank, a reaction fluidization circuit for transferring the liquefied ethylene stored in the liquefied ethylene tank to the polymerization reactor, and
An ethylene injector which is respectively connected with the liquefied ethylene pump and the fluidization loop of the gas-phase fluidized bed reactor and is used for carrying liquefied ethylene in a spraying manner to the fluidization loop of the gas-phase fluidized bed reactor to participate in the polymerization reaction of the polyolefin elastomer;
and the circulating gas heat exchanger is positioned in the fluidization loop and connected with the top and the bottom of the polymerization reactor through a pipeline (for example, a 24-inch pipeline) and is used for exchanging heat of circulating gas in the fluidization loop in the gas-phase fluidized bed reactor and removing reaction heat in the fluidization loop.
As an alternative embodiment, the cryogenic liquefier comprises a compressor and a liquid nitrogen heat exchanger.
As an alternative implementation mode, the ethylene ejector is arranged in a pipeline of the fluidization loop, the direction of a nozzle of the ethylene ejector is the same as the direction of circulating gas in the fluidization loop, and the nozzle is a horn mouth of 15-45 degrees.
As an alternative embodiment, the ethylene injector is mounted at the outlet of the recycle gas heat exchanger at a distance above line 10m into the polymerization reactor.
As an alternative implementation mode, the ethylene ejector is positioned within 3 meters from the front to the back of the inlet of the fluidization loop, and is positioned at a position, the inner diameter of the fluidization pipeline of the fluidization loop is 1.1-1.5 times that of the fluidization pipeline of other fluidization loops.
In a second aspect, the present invention provides a gas phase process production method of the above polyolefin elastomer, the production method employing the gas phase process production apparatus of the above polyolefin elastomer, performing a polymerization reaction in the presence of a metallocene catalyst, the production method comprising the steps of:
1) The polymerization reaction is carried out by establishing a gas phase state by virtue of a seed bed, and after the gas phase in a fluidization loop is compressed by a compressor, the gas phase is injected from the bottom of the polymerization reactor, so that powder in the polymerization reactor is in a fluidization state;
2) Injecting low-temperature liquefied ethylene treated by a cryogenic liquefier into a fluidization loop through an ethylene injector, exchanging heat between the low-temperature liquefied ethylene and circulating gas in the fluidization loop, and liquefying gaseous condensing agent and comonomer in the circulating gas to form a mixed liquid-phase raw material (for example, in a mixed liquid drop shape) comprising the liquefied ethylene, the condensing agent and the comonomer;
3) Introducing hydrogen (e.g., in gaseous form) into the fluidization loop, wherein the mixed liquid phase feedstock and hydrogen form a feedstock mixture into the polymerization reactor, providing fluidization power to the powder within the polymerization reactor;
4) The metallocene catalyst is injected into the polymerization reactor to initiate the polymerization reaction.
In the method, the POE is polymerized in the presence of a metallocene catalyst, the polymerization reaction is carried out by establishing a gas phase state by virtue of a seed bed, and circulating gas in a fluidization loop is injected from the bottom of a polymerization reactor after being compressed by a compressor, so that powder in the polymerization reactor is in a fluidization state. The metallocene catalyst is directly injected into the polymerization reactor. The low-temperature liquefied ethylene is injected into the fluidization loop, and after heat exchange is carried out with the circulating gas in the fluidization loop, the temperature of the circulating gas in the fluidization loop is reduced, so that gaseous ethylene, pentane and comonomer in the fluidization loop are liquefied, the liquefied ethylene, pentane and comonomer and hydrogen form low-temperature raw material mixed gas which enters the polymerization reactor, the powder in the polymerization reactor is provided with fluidization power, and heat exchange is carried out with a reaction system in the polymerization reactor, so that the reaction heat generated by the polymerization reaction is removed.
As an alternative embodiment, the comonomer comprises an alpha-olefin having 4 to 18 carbon atoms.
As an alternative embodiment, the comonomer is added in an amount of 20 to 400 kg/t.
As an alternative embodiment, the temperature of the liquefied ethylene (or low temperature ethylene) injected into the reaction loop is-50 to-90 ℃.
As an alternative embodiment, the seed bed accounts for 20% -45% of the mass fraction of the fluidized powder in the polymerization reactor.
As an alternative embodiment, the ethylene content in the liquefied ethylene is 98.3 wt% -99.98 wt%, and the acetylene content is not higher than 1 wt%.
As an alternative implementation mode, the partial pressure of ethylene in the raw material mixture is 550-950 kPa, and the partial pressure ratio of hydrogen to ethylene is 0.0001-0.004:1.
As an alternative embodiment, the metallocene catalyst comprises a single metallocene catalyst.
As an alternative embodiment, the polymerization reaction temperature is 30-90 ℃ and the pressure is 1400-2600 kPa during the polymerization reaction.
As an alternative embodiment, the temperature in the lower part of the distribution plate of the polymerization reactor is 5-25 ℃.
In the invention, the temperature of the upper part of the distribution plate of the polymerization reactor reflects the temperature of the polymerization reaction, and the difference between the temperature of the lower part of the distribution plate and the uppermost end of the polymerization reactor can reflect the exothermic condition of the polymerization reaction. The condensing agent (including pentane) enters from the bottom and has a condensing effect, so that the temperature of the bottom of the distribution plate can monitor the phase state of the condensing agent. The temperature at which the polymerization of the olefin is initiated varies with the catalyst.
In the invention, the technical characteristics can be freely combined to form a new technical scheme under the condition of no conflict.
Compared with the prior art, the technical scheme of the invention has the following beneficial technical effects:
(1) The gas phase method production method of POE provided by the invention utilizes the inherent gasification latent heat characteristic of the polymer raw material, designs a high-efficiency temperature control method, and obviously reduces the temperature in a polymerization reactor, thereby realizing the thermal management optimization of the POE (polyolefin elastomer) production process, greatly improving the production load capacity of POE and creating conditions for preparing POE with lower melting point;
(2) The gas phase method production device of POE provided by the invention has a more efficient and advanced heat removal system, the heat removal technology in the production method is more efficient, the heat generated in the polymerization reaction process can be rapidly and accurately removed, the whole production process is ensured to be in an optimal temperature range, the production efficiency of POE products can be effectively improved, the improvement of productivity is realized, and the product quality can be ensured under the condition of strict temperature control;
(3) The invention utilizes the inherent vaporization heat absorption property of the polymerization raw material, effectively enhances the heat removal efficiency in the polymerization reaction process, does not need to carry out large-scale modification on the existing polymerization reactor, realizes the improvement of the yield of POE products while ensuring the control of the production cost, and can also produce POE products with lower melting points after the effective removal of the polymerization reaction heat in the polymerization reactor.
Drawings
FIG. 1 is a schematic structural view of a vapor phase process production apparatus for polyolefin elastomer according to the present invention.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present application more apparent, the technical solutions of the embodiments of the present application will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present application, and it is apparent that the described embodiments are some embodiments of the present application, but not all embodiments of the present application. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
The application will be further illustrated with reference to specific examples. It is to be understood that these examples are illustrative of the present application and are not intended to limit the scope of the present application. The experimental procedures, which are not specified in the following examples, are generally determined according to national standards. If the corresponding national standard does not exist, the method is carried out according to the general international standard, the conventional condition or the condition recommended by the manufacturer.
Unless otherwise specifically indicated, the various raw materials, reagents, instruments, equipment and the like used in the present application are commercially available or may be prepared by existing methods.
Some embodiments of the present invention provide a vapor phase process apparatus for producing polyolefin elastomer, as shown in FIG. 1, comprising the following components:
the gas-phase fluidized bed reactor comprises a polymerization reactor and a fluidization loop, wherein the polymerization reactor comprises a diameter section and an expansion section, and the diameter section comprises a gas-phase distribution plate positioned at the bottom of the diameter section;
The cryogenic liquefier is connected with an ethylene pipeline of the cracking device and is used for liquefying ethylene (or refined ethylene) prepared by the cracking device to form liquefied ethylene (or low-temperature ethylene);
A liquefied ethylene tank connected to the cryogenic liquefier for storing liquefied ethylene (i.e., low temperature ethylene or low temperature cold ethylene) cooled by the cryogenic liquefier;
A liquefied ethylene pump connected to the liquefied ethylene tank, a reaction fluidization circuit for transferring the liquefied ethylene stored in the liquefied ethylene tank to the polymerization reactor, and
An ethylene injector which is respectively connected with the liquefied ethylene pump and the fluidization loop of the gas-phase fluidized bed reactor and is used for carrying liquefied ethylene in a spraying manner to the fluidization loop of the gas-phase fluidized bed reactor to participate in the polymerization reaction of the polyolefin elastomer;
and the circulating gas heat exchanger is positioned in the fluidization loop and connected with the top and the bottom of the polymerization reactor through a pipeline (for example, a 24-inch pipeline) and is used for exchanging heat of circulating gas in the fluidization loop in the gas-phase fluidized bed reactor and removing reaction heat in the fluidization loop.
In the invention, the ethylene injector can fully disperse the liquefied ethylene, and avoid the erosion of a large amount of concentrated liquefied ethylene on the pipeline of the fluidization loop. The fluidization loop is a loop of fluidization gas formed by the steps of heat exchange, compression, separation and the like of the fluidization gas coming out of the top of the polymerization reactor and returning the fluidization gas to the bottom of the reactor.
The invention adopts a cryogenic liquefier (or a refrigerating station) to cryogenic ethylene (or refined ethylene) in a boundary region, the ethylene is added into a gas-phase fluidized bed reactor in a liquid phase form, a great amount of reaction heat is absorbed by utilizing vaporization latent heat, and the reaction heat generated by polymerization reaction in the gas-phase fluidized bed reactor is quickly removed, so that the production efficiency of POE is improved. Here, the boundary ethylene means ethylene obtained by a device other than the polyethylene production device, for example, by a cracking device.
As an alternative embodiment, the cryogenic liquefier comprises a compressor and a liquid nitrogen heat exchanger.
As an alternative embodiment, the ethylene injector is installed in a pipeline of the fluidization loop, the direction of the nozzle of the ethylene injector is the same as the direction of circulating gas in the fluidization loop, and the nozzle is a horn mouth of 15-45 degrees (for example, 20-25-30-35-40 degrees).
As an alternative embodiment, the ethylene injector is mounted at the outlet of the recycle gas heat exchanger at a distance above line 10 m into the polymerization reactor.
As an alternative embodiment, the ethylene ejector is located within 3 meters before and after the inlet of the fluidization circuit, and is located at a position where the inner diameter of the fluidization line of the fluidization circuit is 1.1-1.5 times that of the fluidization lines of other fluidization circuits.
In a second aspect, the present invention provides a gas phase process production method of the above polyolefin elastomer, the production method employing the gas phase process production apparatus of the above polyolefin elastomer, performing a polymerization reaction in the presence of a metallocene catalyst, the production method comprising the steps of:
1) The polymerization reaction is carried out by establishing a gas phase state by virtue of a seed bed, and after the gas phase in a fluidization loop is compressed by a compressor, the gas phase is injected from the bottom of the polymerization reactor, so that powder in the polymerization reactor is in a fluidization state;
2) Injecting low-temperature liquefied ethylene treated by a cryogenic liquefier into a fluidization loop through an ethylene injector, exchanging heat between the low-temperature liquefied ethylene and circulating gas in the fluidization loop, and liquefying gaseous condensing agent and comonomer in the circulating gas to form a mixed liquid-phase raw material (for example, in a mixed liquid drop shape) comprising the liquefied ethylene, the condensing agent and the comonomer;
3) Introducing hydrogen (e.g., in gaseous form) into the fluidization loop, wherein the mixed liquid phase feedstock and hydrogen form a feedstock mixture into the polymerization reactor, providing fluidization power to the powder within the polymerization reactor;
4) The metallocene catalyst is injected into the polymerization reactor to initiate the polymerization reaction.
In the method, the POE is polymerized in the presence of a metallocene catalyst, the polymerization reaction is carried out by establishing a gas phase state by virtue of a seed bed, and circulating gas in a fluidization loop is injected from the bottom of a polymerization reactor after being compressed by a compressor, so that powder in the polymerization reactor is in a fluidization state. The metallocene catalyst is directly injected into the polymerization reactor. The low-temperature liquefied ethylene is injected into the fluidization loop, and after heat exchange is carried out with the circulating gas in the fluidization loop, the temperature of the circulating gas in the fluidization loop is reduced, so that gaseous ethylene, pentane and comonomer in the fluidization loop are liquefied, the liquefied ethylene, pentane and comonomer and hydrogen form low-temperature raw material mixed gas which enters the polymerization reactor, the powder in the polymerization reactor is provided with fluidization power, and heat exchange is carried out with a reaction system in the polymerization reactor, so that the reaction heat generated by the polymerization reaction is removed.
In some embodiments, the condensing agent comprises pentane.
In some embodiments, the comonomer comprises an alpha-olefin having 4 to 18 carbon atoms (e.g., 5, 6, 8, 10, 12, 15, or 17).
In some embodiments, the comonomer is added in an amount of 20 to 400 kg/t (e.g., 50 kg/t, 100 kg/t, 150 kg/t, 200 kg/t, 250 kg/t, 300 kg/t, or 350 kg/t).
In some embodiments, the temperature at which the liquefied ethylene (or cryogenic ethylene) is injected into the reaction loop is-50 to-90 ℃ (e.g., -60 ℃, -70 ℃, -80 ℃, or-85 ℃).
In some embodiments, the seedbed comprises 20% -45% (e.g., 25%, 30%, 35%, 40%, or 42%) by mass of fluidized powder in the polymerization reactor.
In some embodiments, the ethylene content in the liquefied ethylene is 98.3 wt% -99.98 wt% and the acetylene content is not higher than 1wt%.
In some embodiments, the partial pressure of ethylene in the feed mixture is 550 to 950 kPa (e.g., 600 kPa, 650 kPa, 700 kPa, 750 kPa, 800 kPa, 850 kPa, or 900 kPa) and the partial pressure ratio of hydrogen to ethylene is 0.0001 to 0.004:1.
In some embodiments, the metallocene catalyst comprises a single metallocene catalyst.
In some embodiments, during the polymerization reaction, the temperature of the polymerization reaction is 30-90 ℃ (e.g., 40 ℃, 50 ℃, 60 ℃, 70 ℃, or 80 ℃) and the pressure is 1400-2600 kPa (e.g., 1500 kPa, 1800 kPa, 2000 kPa, 2200kPa, or 2400 kPa).
In some embodiments, the temperature of the lower portion of the distribution plate of the polymerization reactor (i.e., gas phase fluidized bed reactor) is 5-25 ℃ (e.g., 10 ℃, 15 ℃, or 20 ℃).
In the present invention, the polymerization reactor adopts a gas-phase fluidized-bed reactor which is conventional in the art, and the internal structure of the gas-phase fluidized-bed reactor is not modified, so that the structure of the gas-phase fluidized-bed reactor is not specifically described herein, and only the relevant components involved in the present invention are described.
Example 1
A gas phase method production device of polyolefin elastomer, as shown in figure 1, comprises a gas phase fluidized bed reactor, a cryogenic liquefier, a liquefied ethylene tank, a liquefied ethylene pump, an ethylene ejector and a circulating gas heat exchanger, and is specifically described as follows.
The gas-phase fluidized bed reactor comprises a polymerization reactor and a fluidization loop, wherein the polymerization reactor comprises a diameter section and an expansion section, the bottom of the diameter section is provided with a gas-phase distribution plate which is 0.6-1 m (for example, 0.8 m) away from the bottom end of the polymerization reactor, powder is in a fluidization state on the gas-phase distribution plate, the expansion section is returned, the top of the polymerization reactor is provided with a circulating gas outlet, and the bottom of the polymerization reactor is provided with a raw material gas inlet and a circulating gas inlet.
The cryogenic liquefier is connected with an ethylene pipeline of the cracking device and comprises a compressor and a liquid nitrogen heat exchanger, and is used for carrying out cryogenic liquefaction on refined ethylene prepared by the cracking device to form liquefied ethylene.
The liquefied ethylene tank is connected with the cryogenic liquefier for storing liquefied ethylene (i.e., low temperature ethylene or low temperature cold ethylene) cooled by the cryogenic liquefier.
A liquefied ethylene pump is connected to the liquefied ethylene tank for delivering liquefied ethylene stored in the liquefied ethylene tank to the reaction fluidization loop of the polymerization reactor.
The ethylene ejector is respectively connected with the liquefied ethylene pump and the polymerization reactor, is arranged in a pipeline of the fluidization loop, is positioned at the outlet of the circulating gas heat exchanger and at a position more than 10m m away from a pipeline entering the polymerization reactor, is positioned in front of and behind 3 m at the inlet of the fluidization loop, and the inner diameter of the fluidization pipeline of the fluidization loop is 1.1-1.5 times that of other fluidization loops. The direction of the nozzle of the ethylene injector is the same as the flowing direction of the circulating gas in the fluidization loop, the nozzle is a horn mouth of 15-45 degrees, and the ethylene injector is used for injecting liquefied ethylene to the gas-phase fluidization loop of the polymerization reactor to participate in the polymerization reaction of the polyolefin elastomer.
The circulating gas heat exchanger is positioned in the fluidization loop and connected with the top end and the bottom end of the polymerization reactor through pipelines, and is used for exchanging heat of circulating gas in the fluidization loop in the polymerization reactor and removing reaction heat in the fluidization loop.
In the invention, the ethylene injector can fully disperse the liquefied ethylene, and avoid the erosion of a large amount of concentrated liquefied ethylene on the pipeline of the fluidization loop. The fluidization loop is a loop of the fluidization gas formed by returning the fluidization gas coming out of the top of the reactor to the bottom of the reactor after heat exchange, compression, separation and other steps.
The invention adopts a cryogenic liquefier (or a refrigerating station) to cryogenic the refined ethylene, the ethylene is added into a gas-phase fluidized bed reactor in a liquid phase form, and a great amount of reaction heat is absorbed by utilizing vaporization latent heat, so that the POE production efficiency is improved.
Example 2
This example provides a vapor phase process production apparatus for polyolefin elastomer, which is different from example 1 in that,
The ethylene ejector is installed in the fluidization loop pipeline and is positioned at a position which is 3m away from the inlet of the fluidization loop and is 1.4 times of the inner diameter of the other fluidization loop pipeline at the position which is positioned at a distance from the outlet of the circulating gas heat exchanger to the reactor pipeline 12 and m, the nozzle direction of the ethylene ejector is in the same direction as the air flow direction of circulating gas in the fluidization loop, and the nozzle is provided with a horn mouth of 40 degrees.
Example 3
This example provides a vapor phase process production apparatus for polyolefin elastomer, which is different from example 1 in that,
The ethylene ejector is installed in the fluidization loop pipeline and is positioned at a position which is away from the inlet of the fluidization loop by a distance of m from the outlet of the circulating gas heat exchanger and is positioned at a position which is 3m away from the inlet of the fluidization loop and is positioned at a position which is 1.2 times the inner diameter of the other fluidization loop pipeline, and the nozzle direction of the ethylene ejector is in the same direction as the air flow direction of circulating gas in the fluidization loop, wherein the nozzle is provided with a 40-degree horn mouth.
Example 4
This example provides a vapor phase process production apparatus for polyolefin elastomer, which is different from example 1 in that,
The ethylene ejector is installed in the fluidization loop pipe at a position distant from the inlet of the fluidization loop by a distance of 3m from the inlet of the fluidization loop at the outlet of the recycle gas heat exchanger at a position distant from the inlet of the reactor line 12 m, and at a position where the inner diameter of the fluidization line is 1.1 times that of the other fluidization loop lines. The direction of the nozzle of the ethylene ejector is the same as the direction of the circulating gas flow in the fluidization loop, and the nozzle is a 20-degree bell mouth.
Example 5
A process for producing a polyolefin elastomer by a gas phase method, comprising the steps of performing a polymerization reaction in the presence of a metallocene catalyst using the apparatus for producing a polyolefin elastomer by a gas phase method of example 2.
Step S1, establishing a gas phase state by means of a seed bed, compressing the gas phase in a fluidization loop by a compressor, and injecting the gas phase from the bottom of the polymerization reactor to enable powder in the polymerization reactor to be in a fluidization state, wherein the seed bed accounts for 45% of the mass of fluidized powder in the polymerization reactor.
And S2, continuously injecting liquefied ethylene treated by a cryogenic liquefier into a fluidization loop by adopting an ethylene injector, exchanging heat between the low-temperature liquefied ethylene and circulating gas in the fluidization loop, liquefying a gaseous condensing agent (such as pentane) and a comonomer in the circulating gas to form a mixed liquid phase raw material comprising the liquefied ethylene, the condensing agent and the comonomer, wherein the temperature of the liquefied ethylene when the liquefied ethylene is injected into the fluidization loop is 77 ℃ below zero, the comonomer is alpha-olefin with 8 carbon atoms, namely 1-octene, the ethylene content in the liquefied ethylene is 99.98%, and the acetylene content in the liquefied ethylene is 0.01%.
And S3, introducing hydrogen (for example, in a gaseous form) into a fluidization loop, mixing liquid-phase raw materials and hydrogen in the fluidization loop to form raw material mixed gas, and enabling the raw material mixed gas to enter a polymerization reactor, so as to provide fluidization power for powder in the polymerization reactor, and simultaneously exchanging heat with a polymerization reaction system. Wherein the partial pressure of ethylene in the raw material mixture is 940 kPa, the partial pressure ratio of hydrogen to ethylene is 0.003:1, and the addition amount of the comonomer is 45 kg/t.
And S4, injecting a metallocene catalyst into the polymerization reactor to initiate polymerization reaction, wherein unreacted ethylene, comonomer and gaseous condensing agent and circulating gas flow out from the top of the polymerization reactor and enter a fluidization loop during the polymerization reaction, and after the liquefied ethylene is continuously injected into the fluidization loop and exchanges heat with the circulating gas in the fluidization loop and the ethylene, the comonomer and the condensing agent, the liquefied ethylene and the circulating gas are injected into the polymerization reactor from the bottom of the polymerization reactor together, so that powder in the polymerization reactor is provided with fluidization power to participate in the polymerization reaction and exchange heat for a polymerization reaction system, and the heat of the polymerization reaction is removed, so that the temperature of the polymerization reaction is reduced, and the normal operation of the polymerization reaction is ensured. Wherein the polymerization temperature is 36 ℃, the pressure is 2400 kPa, the temperature at the lower part of the distribution plate of the fluidized bed reactor is 18 ℃, and after the reaction stays 7: 7h, the prepared polyolefin elastomer powder is pumped out of the gas-phase fluidization reactor.
Example 6
A process for producing a polyolefin elastomer by a gas phase method, comprising the steps of performing a polymerization reaction in the presence of a metallocene catalyst using the apparatus for producing a polyolefin elastomer by a gas phase method of example 3.
Step S1, establishing a gas phase state by means of a seed bed, compressing the gas phase in a fluidization loop by a compressor, and injecting the gas phase from the bottom of the polymerization reactor to enable powder in the polymerization reactor to be in a fluidization state, wherein the seed bed accounts for 35% of the mass of fluidized powder in the polymerization reactor.
And S2, continuously injecting liquefied ethylene treated by a cryogenic liquefier into a fluidization loop by adopting an ethylene injector, exchanging heat between the low-temperature liquefied ethylene and circulating gas in the fluidization loop, liquefying a gaseous condensing agent (such as pentane) and a comonomer in the circulating gas to form a mixed liquid phase raw material comprising the liquefied ethylene, the condensing agent and the comonomer, wherein the temperature of the liquefied ethylene when the liquefied ethylene is injected into the fluidization loop is minus 60 ℃, the comonomer is alpha-olefin with 6 carbon atoms, the ethylene content in the liquefied ethylene is 99.91%, and the acetylene content in the liquefied ethylene is 0.03%.
And S3, introducing hydrogen (for example, in a gaseous form) into a fluidization loop, mixing liquid-phase raw materials and hydrogen in the fluidization loop to form raw material mixed gas, and enabling the raw material mixed gas to enter a polymerization reactor, so as to provide fluidization power for powder in the polymerization reactor, and simultaneously exchanging heat with a polymerization reaction system. Wherein the partial pressure of ethylene in the raw material mixed gas is 790 kPa, the partial pressure ratio of hydrogen to ethylene is 0.0025:1, and the addition amount of the comonomer is 110 kg/t.
And S4, injecting a metallocene catalyst into the polymerization reactor to initiate polymerization reaction, wherein unreacted ethylene, comonomer and gaseous condensing agent and circulating gas flow out from the top of the polymerization reactor and enter a fluidization loop during the polymerization reaction, and after the liquefied ethylene is continuously injected into the fluidization loop and exchanges heat with the circulating gas in the fluidization loop and the ethylene, the comonomer and the condensing agent, the liquefied ethylene and the circulating gas are injected into the polymerization reactor from the bottom of the polymerization reactor together, so that powder in the polymerization reactor is provided with fluidization power to participate in the polymerization reaction and exchange heat for a polymerization reaction system, and the heat of the polymerization reaction is removed, so that the temperature of the polymerization reaction is reduced, and the normal operation of the polymerization reaction is ensured. Wherein the temperature of the polymerization reaction is 42 ℃, the pressure is 2050 kPa, the temperature under the distribution plate of the fluidized bed reactor is 20 ℃, and the prepared polyolefin elastomer powder is pumped out of the gas-phase fluidization reactor after the reaction stays at 7: 7 h.
Example 7
A process for producing a polyolefin elastomer by a gas phase method, which comprises carrying out a polymerization reaction in the presence of a metallocene catalyst using the apparatus for producing a polyolefin elastomer by a gas phase method of example 4, the process comprising the steps of.
Step S1, establishing a gas phase state by means of a seed bed, compressing the gas phase in a fluidization loop by a compressor, and injecting the gas phase from the bottom of the polymerization reactor to enable powder in the polymerization reactor to be in a fluidization state, wherein the seed bed accounts for 27% of the fluidized powder in the polymerization reactor by mass.
And S2, continuously injecting liquefied ethylene treated by a cryogenic liquefier into a fluidization loop by adopting an ethylene injector, exchanging heat between the low-temperature liquefied ethylene and circulating gas in the fluidization loop, liquefying a gaseous condensing agent (such as pentane) and a comonomer in the circulating gas to form a mixed liquid phase raw material comprising the liquefied ethylene, the condensing agent and the comonomer, wherein the temperature of the liquefied ethylene when the liquefied ethylene is injected into the fluidization loop is-57 ℃, the comonomer is alpha-olefin with 4 carbon atoms, the ethylene content in the liquefied ethylene is 98.9%, and the acetylene content in the liquefied ethylene is 0.05%.
And S3, introducing hydrogen (for example, in a gaseous form) into a fluidization loop, mixing liquid-phase raw materials and hydrogen in the fluidization loop to form raw material mixed gas, and enabling the raw material mixed gas to enter a polymerization reactor, so as to provide fluidization power for powder in the polymerization reactor, and simultaneously exchanging heat with a polymerization reaction system. Wherein the partial pressure of ethylene in the raw material mixed gas is 660 kPa, the partial pressure ratio of hydrogen to ethylene is 0.0015:1, and the addition amount of the comonomer is 180 kg/t.
And S4, injecting a metallocene catalyst into the polymerization reactor to initiate polymerization reaction, wherein unreacted ethylene, comonomer and gaseous condensing agent and circulating gas flow out from the top of the polymerization reactor and enter a fluidization loop during the polymerization reaction, and after the liquefied ethylene is continuously injected into the fluidization loop and exchanges heat with the circulating gas in the fluidization loop and the ethylene, the comonomer and the condensing agent, the liquefied ethylene and the circulating gas are injected into the polymerization reactor from the bottom of the polymerization reactor together, so that powder in the polymerization reactor is provided with fluidization power to participate in the polymerization reaction and exchange heat for a polymerization reaction system, and the heat of the polymerization reaction is removed, so that the temperature of the polymerization reaction is reduced, and the normal operation of the polymerization reaction is ensured. Wherein the temperature of the polymerization reaction is 50 ℃, the pressure is 1880 kPa, the temperature under the distribution plate of the fluidized bed reactor is 24 ℃, and after the reaction stays 7: 7h, the prepared polyolefin elastomer powder is pumped out of the gas-phase fluidization reactor.
Comparative example 1
A process for the vapor phase production of polyolefin elastomers which differs from example 5 in that:
Ethylene was fed in gaseous form through an ethylene injector, injected into the fluidization circuit at an inlet temperature of 75 ℃, and the ethylene injector was mounted in the fluidization circuit conduit in the same direction as the fluidization gas flow, with the nozzle being set at a 40 ° bell mouth. The polymerization reactor had a temperature of 50℃and a pressure of 2400 kPa ℃and a temperature under the distributor plate of 42 ℃.
Comparative example 2
A process for the vapor phase production of polyolefin elastomers which differs from example 6 in that:
Ethylene is fed through an ethylene injector in a gas state without cryogenic liquefaction and is injected into a fluidization loop, the inlet temperature is 78 ℃, the ethylene injector is arranged in a fluidization loop pipeline and is in the same direction as the fluidization airflow direction, a nozzle is a horn mouth of 40 ℃, the temperature of a polymerization reactor is about 59 ℃, the pressure is 2400 kPa, and the temperature under a distribution plate is about 47 ℃.
Comparative example 3
A process for the vapor phase production of polyolefin elastomers which differs from example 7 in that:
Ethylene was fed in a gaseous state through an ethylene injector, injected into the fluidization circuit at an inlet temperature of 80 ℃, and the ethylene injector was installed in the center of the fluidization circuit pipe in the same direction as the fluidization air flow direction, with a nozzle set at a bell mouth of 20 ℃. The temperature of the polymerization reactor is about 62.5 ℃ and the pressure is 2400 kPa, and the temperature under a distribution plate of the gas-phase fluidized bed reactor is maintained at about 51 ℃;
the production load of the gas phase process production method using the polyolefin elastomers provided in examples 5 to 7 and comparative examples 1 to 3 and the lowest melting point of the produced POE are shown in table 1.
Table 1:
as is clear from Table 1, the gas phase process production apparatus for polyolefin elastomer provided in examples 2 to 4 of the present invention, the gas phase process production method for polyolefin elastomer provided in examples 5 to 7, can increase the production load of POE, and the melting point of POE produced is significantly reduced.
Table 2 shows a comparison of the properties of polyolefin elastomers POE and conventional PE (LLDPE) prepared using the preparation process of the present invention.
Table 2:
As can be seen from Table 2, the apparatus and method for producing polyolefin elastomer by the gas phase method of the present invention can produce POE having higher melt index, lower density, excellent tensile properties and strong toughness, compared with conventional PE.
Various embodiments of the invention may exist in a range format, it being understood that the description in a range format is merely for convenience and brevity and should not be construed as a rigid limitation on the scope of the invention, as the range format described above specifically disclosing all possible sub-ranges and individual values within the range. For example, a description of a range from 1 to 6 should be considered to have specifically disclosed sub-ranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as single numbers within the range, such as 1,2, 3,4, 5, and 6, as applicable regardless of the range. In addition, whenever a numerical range is referred to herein, it is meant to include any reference number (fractional or integer) within the indicated range.
In the present invention, unless otherwise specified, terms such as "upper" and "lower" are used specifically to refer to the orientation of the drawing in the figures. In addition, in the description of the present specification, the terms "include", "comprising" and the like mean "including but not limited to". Relational terms such as "first" and "second", and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Herein, "and/or" describes an association relationship of an association object, which means that there may be three relationships, for example, A and/or B, and may mean that A exists alone, while A and B exist together, and B exists alone. Wherein A, B may be singular or plural. Herein, "at least one" means one or more, and "a plurality" means two or more. "at least one", "at least one" or the like refer to any combination of these items, including any combination of single item(s) or plural items(s).
The foregoing is only a specific embodiment of the invention to enable those skilled in the art to understand or practice the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (15)
1. A device for the production of polyolefin elastomers by the gas phase process, characterized in that it comprises the following components:
The gas-phase fluidized bed reactor comprises a polymerization reactor and a fluidization loop, wherein the polymerization reactor comprises a diameter section and an expansion section, the diameter section comprises a gas-phase distribution plate positioned at the bottom of the diameter section, the top of the polymerization reactor is provided with a circulating gas outlet, and the bottom of the polymerization reactor is provided with a raw material gas inlet and a circulating gas inlet;
The cryogenic liquefier is connected with an ethylene pipeline of the cracking device and is used for liquefying ethylene prepared by the cracking device to form liquefied ethylene;
The liquefied ethylene tank is connected with the cryogenic liquefier and is used for storing liquefied ethylene cooled by the cryogenic liquefier;
A liquefied ethylene pump connected to the liquefied ethylene tank for delivering the liquefied ethylene stored in the liquefied ethylene tank to a reaction fluidization loop of the polymerization reactor;
An ethylene ejector connected to the liquefied ethylene pump and the fluidization circuit of the gas-phase fluidized bed reactor, respectively, for ejecting liquefied ethylene to the fluidization circuit of the gas-phase fluidized bed reactor to participate in the polymerization of polyolefin elastomer, and
The circulating gas heat exchanger is positioned in the fluidization loop and connected with the top and the bottom of the polymerization reactor through a pipeline, and is used for exchanging heat of circulating gas in the fluidization loop in the gas-phase fluidized bed reactor and removing reaction heat in the fluidization loop.
2. The apparatus for producing polyolefin elastomer by gas phase process according to claim 1, wherein the cryogenic liquefier comprises a compressor and a liquid nitrogen heat exchanger.
3. The apparatus according to claim 1, wherein the ethylene ejector is installed in a pipe of the fluidization circuit, and the direction of a nozzle of the ethylene ejector is in the same direction as the direction of the circulating gas in the fluidization circuit, and the nozzle is provided as a bell mouth of 15 ° to 45 °.
4. A plant for the gas phase process production of polyolefin elastomers according to claim 3, characterised in that said ethylene injector is installed at the outlet of said recycle gas heat exchanger at a distance above 10m of the line into the polymerisation reactor.
5. The apparatus for producing polyolefin elastomer by gas phase process according to claim 4, wherein the ethylene ejector is located within 3m before and after the inlet of the fluidization circuit and at a position where the inner diameter of the fluidization line of the fluidization circuit is 1.1 to 1.5 times the inner diameter of the fluidization line of the other fluidization circuit.
6. A process for the gas phase production of a polyolefin elastomer, characterized in that it employs a gas phase production apparatus of a polyolefin elastomer according to any one of claims 1 to 5, and a polymerization reaction is carried out in the presence of a metallocene catalyst, said process comprising the steps of:
1) The polymerization reaction is carried out by establishing a gas phase state by virtue of a seed bed, and after the gas phase in a fluidization loop is compressed by a compressor, the gas phase is injected from the bottom of the polymerization reactor, so that powder in the polymerization reactor is in a fluidization state;
2) Injecting low-temperature liquefied ethylene treated by a cryogenic liquefier into a fluidization loop through an ethylene injector, exchanging heat between the low-temperature liquefied ethylene and circulating gas in the fluidization loop, and liquefying gaseous condensing agent and comonomer in the circulating gas to form a mixed liquid-phase raw material comprising liquefied ethylene, condensing agent and comonomer;
3) Introducing hydrogen into a fluidization loop, mixing liquid-phase raw materials and hydrogen in the fluidization loop to form raw material mixed gas, and introducing the raw material mixed gas into a polymerization reactor to provide fluidization power for powder in the polymerization reactor;
4) The metallocene catalyst is injected into the polymerization reactor to initiate the polymerization reaction.
7. A process for the vapor phase production of a polyolefin elastomer according to claim 6, wherein,
The comonomer comprises alpha-olefin with 4-18 carbon atoms.
8. A process for the vapor phase production of a polyolefin elastomer according to claim 7, wherein,
The addition amount of the comonomer is 20-400 kg/t.
9. A process for the vapor phase production of a polyolefin elastomer according to claim 6, wherein,
The temperature of the liquefied ethylene injected into the reaction loop is-50 to-90 ℃.
10. A process for the vapor phase production of a polyolefin elastomer according to claim 6, wherein,
The seed bed accounts for 20-45% of the fluidized powder in the polymerization reactor by mass.
11. A process for the vapor phase production of a polyolefin elastomer according to claim 6, wherein,
The ethylene content in the liquefied ethylene is 98.3 wt% -99.98 wt%, and the acetylene content is not higher than 1wt%.
12. A process for the vapor phase production of a polyolefin elastomer according to claim 6, wherein,
The partial pressure of ethylene in the raw material mixture is 550-950 kPa, and the partial pressure ratio of hydrogen to ethylene is 0.0001-0.004:1.
13. A process for the vapor phase production of a polyolefin elastomer according to claim 6, wherein,
The metallocene catalyst comprises a single metallocene catalyst.
14. A process for the gas phase production of a polyolefin elastomer according to any of claims 6 to 13, characterized in that,
During the polymerization reaction, the temperature of the polymerization reaction is 30-90 ℃ and the pressure is 1400-2600 kPa.
15. A process for the vapor phase production of a polyolefin elastomer according to claim 14,
The temperature of the lower part of the distribution plate of the polymerization reactor is 5-25 ℃.
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