A method and equipment for continuous industrial production of high-isotactic polybutene-1

Abstract

The present invention provides a method and equipment for continuous industrial production of high-isotactic polybutene-1. The method comprises the steps of polymerization, polymer separation, monomer recovery and polymer granulation. The equipment comprises a polymerization unit, a polymer separation unit, a monomer recovery unit and a polymer granulation unit. The method and equipment of the present invention are a continuous industrial production method and equipment for preparing high-isotactic polybutene-1 by liquid phase polymerization, and can prepare high-isotactic polybutene-1 with low monomer content.

Description

Technical Field

[0001] The invention relates to the field of petrochemical industry, and in particular to a method and equipment for continuous industrial production of high-isotactic polybutene-1. Background Art

[0002] Polybutene-1 is made by using butene-1 monomer as raw material and polymerizing in the presence of a catalyst by slurry method, gas phase method or liquid phase method. It is a semi-crystalline polyolefin thermoplastic resin with good mechanical properties; outstanding environmental stress cracking resistance and heat pressure resistance; excellent creep resistance, which can be repeatedly wound without breaking, and has good creep resistance even at elevated temperatures; good chemical corrosion resistance; and wear resistance similar to that of ultra-high molecular weight polyethylene; high filler filling capacity, etc. Therefore, polybutene-1 can be used to produce pipes, films, plates and various containers, etc., especially it can be used for a long time at a temperature of 90-100°C.

[0003] At present, the preparation methods of high isotactic polybutene-1 mainly include slurry method, liquid phase method and gas phase method. The slurry method for producing polybutene-1 is mainly the Huels process. US3944529 uses δ-TiCl3 / AlEt2Cl as the catalyst system and isobutane as the reaction medium to synthesize H-iPB (isotacticity 99.1%) at 50-70°C slurry polymerization. The particle size of polybutene-1 is 120μm. US5037908 uses TiCl4 / MgCl2 / dibutyl phthalate / AlEt3 / phenyltriethoxysilane catalyst system and isobutane as solvent to catalyze the slurry polymerization of butene-1 to obtain a bulk density of 0.30g / cm 3 The method uses an inert hydrocarbon solvent as the reaction medium, and has the characteristics of simple operation, easy extraction of polymerization heat and convenient reaction control; however, its disadvantages are also obvious. After the reaction is completed and the monomer is recovered, the inert diluent and the unreacted monomer must be separated. The boiling points of butene and isobutylene are very close, and the separation and refining process is complicated, inefficient and costly.

[0004] The catalysts used in the gas phase production of polybutene-1 are mostly SiO2-loaded Ti-based catalysts, polypropylene active particle catalysts, active poly-4-methyl-1-pentene polymer catalysts, etc. For example, in US4503203, SiO2-loaded Ti-based catalysts were used to polymerize in a fluidized bed for 7.8 hours to synthesize polybutene-1 with an isotacticity of 95.0%, a product particle size of 56 μm, and a bulk density of 0.29 g / cm 3 , but the catalyst residue in the product is high; EP0294767A1 uses polypropylene active particle catalyst to react in a fluidized bed to synthesize a product with an isotacticity of 98% and a bulk density of 0.36g / cm 3The pipe-grade high isotactic polybutene-1 was reported in CN1032172A. The catalyst activity of butene-1 was 386 kgPB / gTi, the isotacticity of the polymer was 99.0%, and the bulk density was 0.41 g / cm 3 , the chloride content in the product is only 44ppm, which shows that the use of active polymer catalysts can improve the fluidity of polymer particles, improve the adhesion of polymer particles to the reactor, and increase the bulk density of the product. However, compared with ethylene and propylene, butene-1 monomer has a better affinity for hydrocarbon solvents. Therefore, even if there is a very small amount of solvent in the gas phase polymerization system, the product itself will agglomerate, so the entire reaction will not be able to run stably on the equipment for a long time. Therefore, the gas phase polybutene-1 production process only exists in the research field, and there is no industrial production example.

[0005] The liquid phase method is to use liquid phase butene-1 monomer or hydrocarbon organic compound as solvent or reaction medium, and catalyze butene-1 polymerization under the action of catalyst. According to the form of polybutene-1 product, it is divided into homogeneous solution method, homogeneous bulk method and heterogeneous bulk method. US3944529 uses isobutylene inert solvent as diluent for solution polymerization, and US5237013 uses n-hexane as solvent to achieve butene-1 solution polymerization, and both obtain isotactic polybutene-1 with an isotactic content of more than 94%; CN1590417A uses metallocene catalyst solution polymerization to synthesize isotactic polybutene-1 with an isotactic content of more than 96%. The use of inert hydrocarbon solvents as reaction media has the characteristics of simple operation, easy extraction of polymerization heat, and convenient reaction control; however, its disadvantages are also obvious. Since polybutene-1 swells and dissolves in its monomers, the system becomes sticky, causing difficulties in mass transfer and heat transfer, which limits the polymerization process to only be terminated at low conversion rates or to use reactive extrusion technology to further improve the conversion rate and remove unreacted monomers. At the same time, it is also faced with the process of separation of inert diluents and unreacted monomers, which reduces production efficiency and increases the complexity and production cost of the production process. In order to avoid the complex process and high cost caused by the separation of inert solvents and monomers, CN101020728A uses a bulk precipitation method to prepare highly homogeneous polybutene-1, which overcomes the disadvantages of the solution method that requires solvent recovery and post-processing, but the technology only discloses the synthesis method and materials of bulk precipitation polymerization of polybutene-1, and does not involve the production method, process flow and implementation equipment of industrial production. CN103897080A discloses a method for producing high isotactic polybutene-1 and a device for implementing the method. The production process comprises the following steps: catalyzing the bulk polymerization of butene-1 to synthesize high isotactic polybutene-1 in a polymerization kettle at -10°C to 70°C in the presence of a supported Ti-based catalyst; after polymerization for 3-6 hours, partially unreacted butene-1 is recovered into a butene-1 gas cabinet through a reduced pressure; then, the high isotactic polybutene-1 is transferred from the polymerization kettle to a flash kettle; after reduced pressure flash evaporation, the unreacted butene-1 monomer is further recovered into the butene-1 gas cabinet; nitrogen and air are successively introduced into the flash kettle for replacement; and the granular high isotactic polybutene-1 product is discharged through a discharge valve at the bottom of the kettle and packaged; the product has a maximum bulk density of 0.418 g / cm 3The highest catalyst activity is 2666 gPB / (gcat·h), but the ash content of the product is relatively high. CN105482009A discloses a continuous process for producing polybutene-1, including prepolymerization, slurry polymerization, gas phase polymerization, gas-solid separation and other steps to obtain polybutene-1 powder. The process is to add a measured amount of butene-1 as a raw material, a titanium catalyst, an alkyl aluminum co-catalyst, a silane electron donor, and a hydrogen molecular weight regulator into a prepolymerization kettle, and enter the slurry polymerization reactor after 5-15 minutes of prepolymerization, and carry out slurry polymerization at 25-55°C and 0.6-1.6MPa for 3-5h, and then the slurry of the slurry polymerization enters the gas phase horizontal reactor by pressure difference, and carries out gas phase polymerization at 30-60°C and 0.5-1.5MPa for 3-5h, and condenses the vaporized butene-1 through a condenser and sends it back to the gas phase horizontal reactor; finally, the gas phase polymerization slurry enters the receiving tank, decompresses, separates to obtain polybutene-1 powder, and the butene-1 gas is filtered, washed, condensed into liquid, and then sent to the prepolymerization kettle for reuse. Although the production process of polybutene-1 by the heterogeneous liquid phase bulk method is simple, when the polymerization temperature is higher than 30°C, polybutene-1 swells in its monomer, making the system sticky, resulting in difficulties in heat and mass transfer. The temperature of each reaction stage needs to be strictly controlled, the reaction time is long, the production efficiency is low, and the product quality is difficult to guarantee.

[0006] US3944529 and US6306996 disclose a liquid phase bulk polymerization process using a titanium catalyst system containing an electron donor and butene-1 monomer as a reaction medium, to obtain polybutene-1 with an isotactic content of more than 99% under optimized conditions, and a catalyst activity of 14000 gPB / gcat. CN106832070A discloses a continuous production method for polybutene-1. The production method uses 1-butene monomer as a raw material to carry out a polymerization reaction in the presence of a catalyst, an auxiliary agent, etc., and then removes a mixture containing unreacted 1-butene monomer from the reaction material to obtain polybutene-1, wherein the auxiliary agent is preliminarily dissolved with a solvent before being added to a polymerization reactor, and the solvent is recovered from the mixture containing unreacted butene-1 monomer, and the mixture containing unreacted 1-butene monomer is subjected to rectification and separation, and the obtained first tower bottom component is subjected to rectification and separation, and the obtained second tower top component is subjected to liquid-liquid extraction and cleaning to obtain a recovered solvent, and the recovered solvent is returned to dissolve the auxiliary agent, thereby solving the problem of the influence of the solvent brought into the product due to the addition of the auxiliary agent during the polymerization process. However, this process does not completely deash the product, resulting in yellowing of the product, and it is difficult to ensure the product quality.

[0007] Most of the above prior arts only disclose the polymerization synthesis method, materials and recovery process of butene-1 bulk homogeneous method, and there are few documents related to the production method, process flow and implementation equipment of the industrial production of polybutene-1, especially the method and equipment of the devolatilization process of the product after butene-1 polymerization. Therefore, the development of a new method and equipment for continuous industrial production of high-specification polybutene-1 has become one of the problems to be solved in this field. Summary of the invention

[0008] In order to solve the above technical problems, the purpose of the present invention is to provide a method and equipment for continuous industrial production of high-isotactic polybutene-1. The method and equipment of the present invention are a continuous industrial production method and equipment for preparing high-isotactic polybutene-1 by liquid phase polymerization, which can prepare high-isotactic polybutene-1 with low monomer content.

[0009] In order to achieve the above object, the first aspect of the present invention provides a method for continuous industrial production of high isotactic polybutene-1, which comprises the following steps:

[0010] (1) Polymerization: In a polymerization reactor, a monomer containing liquid butene-1 is used as a raw material, and a polymerization reaction is carried out in the presence of a catalyst system to obtain a polymer solution;

[0011] (2) polymer separation: the polymer solution flows out of the polymerization kettle and enters a deactivation tank, where it is mixed with a terminator to deactivate the catalyst; then, the polymer solution is pressurized to a first pressure and heated to a first temperature, and then enters a first monomer stripping tower to remove monomers to obtain a polybutene-1 melt after the first monomer stripping, and is discharged from the first monomer stripping tower; then, the polymer solution is heated to a second temperature and then enters a second monomer stripping tower to remove monomers at a second pressure to obtain a polybutene-1 melt after the second monomer stripping, and the separated monomer-containing gas flows out from the first monomer stripping tower and the second monomer stripping tower;

[0012] (3) Monomer recovery: the monomer-containing gas flowing out of the first monomer stripping tower and the second monomer stripping tower enters a monomer recovery unit for recovery to obtain monomer gas;

[0013] (4) Polymer granulation: The polybutene-1 melt after the second demolymerization is extruded and granulated to obtain the highly isotactic polybutene-1.

[0014] In the above method, preferably, in step (1), the monomer containing liquid butene-1 may also include an α-olefin comonomer; more preferably, the α-olefin comonomer includes a C2-C10 α-olefin; further preferably, the α-olefin comonomer may include ethylene and / or propylene, etc.

[0015] In the above method, preferably, in step (1), the catalyst system comprises a main catalyst, a co-catalyst and an external electron donor compound.

[0016] In step (1), more preferably, the main catalyst includes a titanium solid catalyst, such as but not limited to a magnesium halide-supported titanium solid catalyst and / or an alkoxy magnesium-supported titanium solid catalyst. Further preferably, the main catalyst is used in an amount of 30,000-140,000 g of liquid butene-1 / g of main catalyst. The magnesium halide-supported titanium solid catalyst can be selected from various magnesium halide-supported titanium solid catalysts disclosed in the prior art, which are based on magnesium halide or magnesium halide alcoholate as a carrier, loaded with Ti as an active component, and can also be selectively loaded with an internal electron donor compound, and the internal electron donor compound can include one or more combinations of carboxylic acid esters, ethers, succinates, 1,3-alcohol esters and sulfonamide compounds, etc.; for example, a spherical magnesium chloride (or anhydrous magnesium chloride)-supported titanium solid catalyst. The alkoxymagnesium-supported titanium-based solid catalyst can be selected from various alkoxymagnesium-supported titanium-based solid catalysts disclosed in the prior art, which are based on alkoxymagnesium or alkoxymagnesium alcoholate as a carrier, loaded with Ti as an active component, and can also be selectively loaded with an internal electron donor compound, the type of the internal electron donor compound is as described above; for example, ethoxymagnesium-supported titanium-based solid catalyst.

[0017] In step (1), more preferably, the cocatalyst may include an alkyl aluminum compound; particularly preferably, the cocatalyst includes one or a combination of triethyl aluminum, triisobutyl aluminum, tri-n-butyl aluminum, tri-n-hexyl aluminum and tri-n-octylaluminum; further preferably, the alkyl aluminum compound is triethyl aluminum. Further preferably, the amount of the cocatalyst is: 850-14000 g liquid butene-1 / g cocatalyst.

[0018] In step (1), more preferably, the external electron donor compound may include an alkoxysilane compound; further preferably, the external electron donor compound includes one or a combination of dicyclopentyldimethoxysilane, cyclohexylmethyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexyltriethoxysilane, methyltriethoxysilane, methylcyclopentyldimethoxysilane, isobutylisopropyldimethoxysilane, isopropylcyclopentyldimethoxysilane and isobutyltriethoxysilane. Further preferably, the amount of the external electron donor compound is: 40000-250000 g liquid butene-1 / g external electron donor compound.

[0019] In the above method, preferably, in step (1), the polymerization reaction is carried out in the presence of hydrogen and an inert gas. The hydrogen can be used as a molecular weight regulator. More preferably, the amount of hydrogen is: 1500-300000 g liquid butene-1 / g hydrogen. The inert gas can be used as a protective gas and a booster gas. More preferably, the inert gas includes nitrogen.

[0020] In the above method, preferably, in step (1), the polymerization reaction temperature is 50-80°C, the reaction pressure is 2.0-2.5 MPa, and the reaction time is 2-5 hours. More preferably, the polymerization reaction temperature is 65-75°C, the reaction pressure is 2.0-2.2 MPa, and the reaction time is 3-4 hours.

[0021] In the above method, preferably, in step (1), the weight concentration of the polymer in the polymer solution is 20-25%.

[0022] In the above method, preferably, step (1) further comprises: allowing the monomer, and / or the catalyst system, and / or the hydrogen, and / or the inert gas to enter the polymerization kettle through metering devices respectively.

[0023] In the above method, preferably, step (1) further comprises: subjecting the raw material butene-1 from outside to refining before entering the polymerization reactor. The refining can be carried out by a conventional refining system in the art to remove trace amounts of impurities such as water and oxygen present in the raw material butene-1, so that the content of impurities such as water and oxygen in the raw material butene-1 is less than 2 ppm.

[0024] In step (2) of the above method, the deactivation tank can be a stirred kettle type device or a static mixer. The terminator can be a conventional polymerization terminator in the art, such as but not limited to water, oxygen, carbon dioxide, carbon monoxide or alcohols, and the amount of the terminator can be 0.1-1.0% of the weight of the polymer solution. After the polymerization reaction, the present invention uses a terminator to deactivate the active center in the polymer solution, effectively terminate the polymerization reaction, and prevent the problem of continued polymerization or implosion in the subsequent treatment process.

[0025] In the above method, preferably, in step (2), the first pressure is 2.8-3.2 MPa, and the first temperature is 195-205° C. More preferably, step (2) comprises: using a pump to increase the pressure of the polymer solution flowing out of the deactivation tank to the first pressure, and then using a heat exchanger to increase the temperature of the pressurized polymer solution to the first temperature. More specifically, the pump comprises a gear pump or a screw pump, preferably a gear pump.

[0026] In the above method, preferably, in step (2), the second temperature is 205-215° C., and the second pressure is 0.001-0.003 MPa. More preferably, step (2) comprises: using a heat exchanger to heat the polybutene-1 melt after the first stripper to the second temperature, and then entering the second stripper tower, and using a vacuum pump arranged outside the top of the second stripper tower to control the operating pressure of the second stripper tower at the second pressure.

[0027] In the above method, preferably, in step (2), the monomer (mainly butene-1) content in the polybutene-1 melt after the second stripping is less than 35 ppm (weight).

[0028] In the above method, preferably, in step (2), the tower bodies of the first and second monomer stripping towers are provided with several layers of conical surfaces in the vertical direction, and the several layers of conical surfaces include dispersion surfaces with openings downward and receiving surfaces with openings upward that are adjacently arranged in the vertical direction; a feed port and a gas outlet are provided at the top of the tower; and a discharge port is provided at the bottom of the tower. More preferably, the cone angles of the several layers of conical surfaces are 130°-150°. More preferably, the number of conical surfaces inside the tower body is an odd number between 5 and 9, and the first layer of conical surfaces in the vertical direction is a dispersion surface with openings downward. Further preferably, the number of conical surfaces inside the tower body is seven layers, and the first layer of conical surfaces in the vertical direction is a dispersion surface with openings downward. More preferably, the side walls of the tower bodies of the first and second monomer stripping towers may also be provided with sight glasses, respectively.

[0029] In a specific embodiment of the present invention, after the catalyst is deactivated, the polymer solution from the polymerization kettle is pressurized by a pump and then heated by a heat exchanger to reach the operating pressure and temperature of the first stripper tower, and then enters the first stripper tower for monomer removal. In the first stripper tower, the polymer solution passes through several layers of conical surfaces arranged in the tower by gravity to make it flat and thin, so that the monomer (mainly butene-1 gas) and the molten polybutene-1 are fully separated, and the polybutene-1 melt settles to the first stripper tower. The bottom of the monomer tower is discharged from the bottom outlet of the tower with the help of a pump, and the gas containing the monomer flows out from the gas outlet at the top of the tower; then a heat exchanger is used to heat the polybutene-1 melt after the first monomer stripping to the operating temperature in the second monomer stripping tower, and the melt enters the second monomer stripping tower, and a vacuum pump is used to control the operating pressure of the second monomer stripping tower in a vacuum state to remove the monomer, so as to obtain the polybutene-1 melt after the second monomer stripping and discharge it from the bottom outlet of the tower with the help of a pump, and the gas containing the monomer flows out from the gas outlet at the top of the tower.

[0030] In the above method, preferably, in step (3), the monomer recovery unit comprises at least a separation tower; step (3) comprises: separating the monomer gas and the terminator by subjecting the monomer-containing gas flowing out of the first monomer stripping tower and the second monomer stripping tower to at least separation in the separation tower.

[0031] In the above method, preferably, in step (3), the monomer recovery unit also includes a buffer tank; step (3) further includes: allowing the monomer-containing gas flowing out of the first monomer stripping tower and the second monomer stripping tower to first pass through the buffer tanks respectively, and then enter the separation tower for separation.

[0032] In the above method, preferably, in step (3), the monomer recovery unit further comprises one or a combination of a condenser, a scrubber and a drying tower; step (3) further comprises: subjecting the monomer gas separated by the separation tower to one or a combination of condensation, scrubbing and drying to obtain treated monomers. The present invention does not specifically limit the order of condensation, scrubbing and drying, which can be routinely adjusted by those skilled in the art.

[0033] In the above method, preferably, in step (3), the monomer recovery unit further comprises a monomer storage tank; step (3) further comprises: allowing the treated monomer to enter the monomer storage tank for storage. More specifically, the monomer storage tank can be a liquid butene-1 storage tank.

[0034] In the above method, preferably, step (3) further comprises: allowing the treated monomer or the monomer stored in the monomer storage tank to enter the polymerization reactor in step (1) for reuse.

[0035] In the above method, preferably, step (3) further comprises: allowing the terminator separated by the separation tower to enter the deactivation tank in step (2) for reuse.

[0036] In the above method, preferably, in step (4), the extrusion adopts a screw extruder, and more preferably, the screw extruder has a vacuum degassing device. The vacuum degassing device includes but is not limited to a vacuum pump. More preferably, step (4) further comprises: in the process of extruding the polybutene-1 melt after the second demomonomerization through the screw extruder, the residual monomer (mainly butene-1) is further removed through the vacuum degassing device of the screw extruder. More preferably, step (4) further comprises: in the process of extruding the polybutene-1 melt after the second demomonomerization through the screw extruder, an additive is added to obtain a mixture of polybutene-1 and the additive, and then granulation is performed. The additive can be an additive conventionally used in the art, such as a light stabilizer, an antioxidant, a colorant, a filler, etc.

[0037] In the above method, preferably, in step (4), the granulation is carried out using an underwater granulator.

[0038] The second aspect of the present invention provides a device for continuous industrial production of high-isotactic polybutene-1, which is used to implement the above-mentioned method for continuous industrial production of high-isotactic polybutene-1, the device comprising: a polymerization unit, a polymer separation unit, a monomer recovery unit and a polymer granulation unit;

[0039] The polymerization unit comprises a polymerization kettle, which is at least provided with a reaction system inlet and a polymer solution outlet;

[0040] The polymer separation unit comprises a deactivation tank, a booster pump, a first heat exchanger, a first monomer stripping tower, a second heat exchanger, a second monomer stripping tower and a vacuum pump; the deactivation tank is at least provided with a polymer inlet, a terminator inlet and a discharge port; the first monomer stripping tower and the second monomer stripping tower are at least respectively provided with a feed port, a gas outlet and a discharge port;

[0041] The polymer granulation unit comprises an extruder and a granulator;

[0042] The polymer solution outlet of the polymerization kettle is connected to the polymer inlet of the deactivation tank through a pipeline; the discharge port of the deactivation tank is connected to the feed port of the first monomer removal tower through a pipeline, a booster pump and a first heat exchanger; the discharge port of the first monomer removal tower is connected to the feed port of the second monomer removal tower through a pipeline and a second heat exchanger, and the vacuum pump is connected to the gas outlet of the second monomer removal tower through a pipeline;

[0043] The gas outlet of the first monomer removal tower is connected to the monomer recovery unit through a pipeline; the gas outlet of the second monomer removal tower is connected to the monomer recovery unit through a pipeline and the vacuum pump;

[0044] The discharge port of the second monomer removal tower is sequentially connected to the extruder and the granulator through pipelines.

[0045] In the above-mentioned equipment, preferably, the reaction system inlet of the polymerization kettle includes: a monomer inlet, a catalyst system inlet, a hydrogen inlet and an inert gas inlet; more preferably, the monomer inlet includes a liquid butene-1 inlet and an α-olefin comonomer inlet which can be optionally set.

[0046] In the above-mentioned equipment, the polymerization kettle may be a conventional polymerization reaction kettle in the art, and a stirring device may be provided inside the polymerization kettle. The present invention does not limit its specific structure.

[0047] In the above-mentioned equipment, preferably, the polymerization unit further comprises one or more metering devices for allowing the monomer, and / or the catalyst system, and / or hydrogen, and / or the inert gas to enter the polymerization kettle through the metering devices respectively.

[0048] In the above-mentioned equipment, preferably, the polymerization unit further comprises: a refining system, which is connected to the monomer inlet of the polymerization kettle and is used to purify the raw material butene-1 from the outside. The refining system can adopt a conventional refining system in the art to remove trace impurities such as water and oxygen in the raw material butene-1, so that the content of impurities such as water and oxygen in the raw material butene-1 is less than 2ppm.

[0049] In the above-mentioned equipment, the deactivation tank can be a kettle-type equipment with stirring, or a static mixer, which can adopt a conventional mixing device in the art, and the present invention does not limit its specific structure.

[0050] In the above-mentioned device, preferably, the tower bodies of the first and second monomer-removing towers are provided with several layers of conical surfaces in the vertical direction, and the several layers of conical surfaces include a dispersion surface with an opening downward and a receiving surface with an opening upward, which are adjacently arranged in the vertical direction; the feed port and the gas outlet are provided at the top of the tower; and the discharge port is provided at the bottom of the tower. More preferably, the cone angles of the several layers of conical surfaces are 130°-150°. More preferably, the number of conical surfaces inside the tower body is an odd number between 5 and 9, and the first layer of conical surfaces in the vertical direction is a dispersion surface with an opening downward. Further preferably, the number of conical surfaces inside the tower body is seven layers, and the first layer of conical surfaces in the vertical direction is a dispersion surface with an opening downward. More preferably, the side walls of the tower bodies of the first and second monomer-removing towers can also be provided with sight glasses, respectively. The structures of the first and second monomer-removing towers of the present invention can be completely the same or different, as long as they meet the above-mentioned definition of the present invention.

[0051] In the above-mentioned device, preferably, the booster pump comprises a gear pump or a screw pump, more preferably a gear pump.

[0052] In the above-mentioned device, preferably, the first heat exchanger and the second heat exchanger include multi-tube heat exchangers respectively.

[0053] In the above device, preferably, the discharge port of the first monomer removal tower is provided with a delivery pump for discharging the tower bottom material from the discharge port and delivering it to the second heat exchanger. More specifically, the delivery pump comprises a gear pump or a screw pump, preferably a gear pump.

[0054] In the above-mentioned device, preferably, the discharge port of the second monomer removal tower is provided with a delivery pump for discharging the tower bottom material from the discharge port and delivering it to the extruder. More specifically, the delivery pump comprises a gear pump or a screw pump, preferably a gear pump.

[0055] In the above-mentioned equipment, preferably, the monomer recovery unit at least includes a separation tower, and the separation tower is provided with a material inlet, a monomer gas outlet and a terminator outlet; the gas outlet of the first monomer stripping tower is connected to the material inlet of the separation tower through a pipeline, and the gas outlet of the second monomer stripping tower is connected to the material inlet of the separation tower through a pipeline and the vacuum pump; and the monomer-containing gas flowing out of the first monomer stripping tower and the second monomer stripping tower is separated into the monomer gas and the terminator after being separated by at least the separation tower.

[0056] In the above-mentioned equipment, preferably, the monomer recovery unit also includes a buffer tank, which is respectively arranged on the pipeline connecting the gas outlet of the first monomer stripping tower and the separation tower, and on the pipeline connecting the outlet of the vacuum pump outside the second monomer stripping tower and the separation tower; and is used to allow the monomer-containing gas flowing out of the first monomer stripping tower and the second monomer stripping tower to pass through the buffer tank respectively, and then enter the separation tower for separation.

[0057] In the above-mentioned equipment, preferably, the monomer recovery unit further comprises one or more combinations of a condenser, a scrubber and a drying tower; one or more combinations of a condenser, a scrubber and a drying tower are arranged behind the separation tower, and are used to treat the monomer gas separated by the separation tower by one or more combinations of condensation, scrubbing and drying to obtain treated monomers. The present invention does not specifically limit the front and rear positions of the condenser, the scrubber and the drying tower, and can be conventionally adjusted by those skilled in the art.

[0058] In the above-mentioned equipment, preferably, the monomer recovery unit further comprises a monomer storage tank, which is arranged behind one or a combination of the condenser, the scrubber and the drying tower, and is used to store the treated monomer. More preferably, the monomer storage tank can be a liquid butene-1 storage tank.

[0059] In the above-mentioned equipment, preferably, the monomer recovery unit also includes a monomer circulation pipeline, one end of which is connected to the reaction system inlet (monomer inlet) of the polymerization kettle, and the other end is connected to the outlet of the scrubber, or the outlet of the condenser, or the outlet of the drying tower, or the outlet of the monomer storage tank; and is used for recycling the monomer.

[0060] In the above-mentioned equipment, preferably, the monomer recovery unit also includes a terminator circulation pipeline, one end of which is connected to the terminator inlet of the deactivation tank, and the other end is connected to the terminator outlet of the separation tower, for reusing the terminator separated by the separation tower.

[0061] In the above-mentioned equipment, preferably, the extruder comprises a screw extruder; more preferably, the screw extruder has a vacuum degassing device. The vacuum degassing device includes but is not limited to a vacuum pump.

[0062] In the above-mentioned device, preferably, the pelletizer comprises an underwater pelletizer.

[0063] The present invention provides a method and equipment for continuous industrial production of high-isotactic polybutene-1, more specifically, a method and equipment for continuous industrial production of high-isotactic polybutene-1 by liquid phase polymerization. The method and equipment of the present invention include a process method and equipment device for stripping (devolatilizing) the product after polymerization, which fills the gap in the prior art; at the same time, the present invention uses liquid butene-1 monomer as the reaction medium, does not have a solvent removal process, has the advantages of simple process, easy operation, high monomer recovery efficiency, high polymer product quality, stable equipment operation, etc.; therefore, the method and equipment of the present invention can continuously produce high-isotactic polybutene-1 industrially, and prepare high-isotactic polybutene-1 with low monomer content.

[0064] The method and equipment for continuous industrial production of high-isotactic polybutene-1 provided by the present invention have at least the following beneficial technical effects:

[0065] (1) The technical solution of the present invention can effectively remove unreacted butene-1 from a polymer containing butene-1 monomer, and realizes efficient and sufficient separation of butene-1 monomer and molten polybutene-1 by performing a monomer removal treatment using two monomer removal towers with a plurality of conical surfaces disposed therein, and further removes residual butene-1 by using a screw extruder with a vacuum degassing device, ultimately making the monomer content in the polymer product less than 35 ppm, or even less than 30 ppm, significantly reducing the explosive problem caused by the release of butene-1 in the finished polymer particles;

[0066] (2) The technical solution of the present invention adopts liquid butene-1 monomer as the reaction medium, and there is no process of removing the solvent. It has the advantages of simple process, easy operation, high monomer recovery efficiency, high heat removal efficiency, stable operation, etc. At the same time, it has the advantages of high production capacity, high catalyst utilization rate, and the polymer product pellets have the advantages of balanced discharge speed, uniform size, full appearance, and high quality. BRIEF DESCRIPTION OF THE DRAWINGS

[0067] Figure 1A schematic diagram of the structure of an apparatus for continuous industrial production of highly isotactic polybutene-1 provided in one specific embodiment of the present invention.

[0068] Explanation of the reference numerals: 1-polymerization kettle, 2-catalyst system mixer, 3-refining system, 4-deactivation tank, 5-boosting pump, 6-first heat exchanger, 7-first stripping tower, 71-conical surface, 711-dispersion surface, 712-receiving surface, 8-first conveying pump, 9-second heat exchanger, 10-second stripping tower, 11-second conveying pump, 12-vacuum pump, 13-first buffer tank, 14-second buffer tank, 15-separation tower, 16-drying tower, 17-condenser, 18-monomer storage tank, 19-screw extruder, 191-vacuum degassing device, 20-underwater granulator. DETAILED DESCRIPTION

[0069] In order to have a clearer understanding of the technical features, purposes and beneficial effects of the present invention, the technical solution of the present invention is now described in detail below, but it should not be construed as limiting the applicable scope of the present invention.

[0070] Example 1

[0071] This embodiment provides a device for continuous industrial production of high-isotactic polybutene-1, the structure of which is as follows: Figure 1 As shown, the equipment includes: a polymerization unit, a polymer separation unit, a monomer recovery unit and a polymer granulation unit;

[0072] The polymerization unit comprises a polymerization kettle 1, a catalyst system mixer 2 and a refining system 3;

[0073] The polymerization kettle 1 is at least provided with a reaction system inlet and a polymer solution outlet; the reaction system inlet includes a monomer inlet, a catalyst system inlet, a hydrogen inlet and an inert gas inlet;

[0074] The catalyst system mixer 2 is connected to the catalyst system inlet of the polymerization kettle 1 through a pipeline;

[0075] The refining system 3 is connected to the monomer inlet of the polymerization reactor 1 and is used to purify the raw material butene-1 from the outside;

[0076] The polymerization unit also includes one or more meters ( Figure 1 ), used to allow monomers, and / or catalyst system, and / or hydrogen, and / or inert gas to enter the polymerization reactor 1 through metering devices respectively;

[0077] The polymer separation unit comprises a deactivation tank 4, a booster pump 5, a first heat exchanger 6, a first monomer stripping tower 7, a first delivery pump 8, a second heat exchanger 9, a second monomer stripping tower 10, a second delivery pump 11 and a vacuum pump 12; the deactivation tank 4 is at least provided with a polymer inlet, a terminator inlet and a discharge port; the first monomer stripping tower 7 and the second monomer stripping tower 10 are at least provided with a feed port, a gas outlet and a discharge port, respectively;

[0078] The monomer recovery unit includes a first buffer tank 13, a second buffer tank 14, a separation tower 15, a drying tower 16, a condenser 17 and a monomer storage tank 18; the separation tower 15 is provided with a material inlet, a monomer gas outlet and a terminator outlet;

[0079] The polymer granulation unit comprises a screw extruder 19 having a vacuum degassing device 191 and an underwater granulator 20; wherein the vacuum degassing device 191 is a vacuum pump;

[0080] The polymer solution outlet of the polymerization kettle 1 is connected to the polymer inlet of the deactivation tank 4 through a pipeline; the discharge port of the deactivation tank 4 is connected to the feed port of the first monomer removal tower 7 through a pipeline, a booster pump 5 and a first heat exchanger 6; the discharge port of the first monomer removal tower 7 is connected to the feed port of the second monomer removal tower 10 through a pipeline, a first delivery pump 8 and a second heat exchanger 9, and the vacuum pump 12 is connected to the gas outlet of the second monomer removal tower 10 through a pipeline; the discharge port of the second monomer removal tower 10 is connected to the feed port of the screw extruder 19 with a vacuum degassing device 191 through a pipeline and a second delivery pump 11; the discharge port of the screw extruder 19 with a vacuum degassing device 191 is connected to the underwater granulator 20;

[0081] The gas outlet of the first monomer removal tower 7 is connected to the inlet of the first buffer tank 13 through a pipeline, the gas outlet of the second monomer removal tower 10 is connected to the inlet of the second buffer tank 14 through a pipeline and a vacuum pump 12, the outlets of the first buffer tank 13 and the second buffer tank 14 are connected to the material inlet of the separation tower 15 through a pipeline, the monomer gas outlet of the separation tower 15 is connected to the drying tower 16 and the condenser 17 in sequence through a pipeline, the outlet of the condenser 17 is connected to the inlet of the monomer storage tank 18, the outlet of the monomer storage tank 18 is connected to the monomer inlet of the polymerization kettle 1 through a monomer circulation pipeline, and the terminator outlet of the separation tower 15 is connected to the terminator inlet of the deactivation tank 4 through a terminator circulation pipeline;

[0082] The structures of the first monomer removal tower 7 and the second monomer removal tower 10 are completely the same; the first monomer removal tower 7 and the second monomer removal tower 10 are provided with seven layers of conical surfaces 71 in the vertical direction inside the tower body, and the seven layers of conical surfaces 71 include a dispersion surface 711 with an opening downward and a receiving surface 712 with an opening upward arranged adjacently in the vertical direction, and the first layer of conical surface 71 in the vertical direction is a dispersion surface 711 with an opening downward, and the cone angles of the seven layers of conical surfaces 71 are all 135°; the feed port and the gas outlet are provided at the tower top; the discharge port is provided at the tower bottom; and the side wall of the tower body may also be provided with a sight glass;

[0083] Wherein, the booster pump 5 is a gear pump;

[0084] Wherein, the first heat exchanger 6 and the second heat exchanger 9 are both multi-tube heat exchangers;

[0085] Wherein, the first delivery pump 8 and the second delivery pump 11 are both gear pumps.

[0086] Example 2

[0087] This embodiment provides a method for continuous industrial production of high-isotactic polybutene-1. The method uses the equipment provided in Example 1 of Embodiment 5 to continuously industrially produce high-isotactic polybutene-1. The method comprises the following steps:

[0088] (1) Polymerization:

[0089] The raw material butene-1 from outside is metered and sent to the refining unit 3 for refining to remove trace impurities such as water and oxygen in the raw material butene-1, so that the content of impurities such as water and oxygen in the raw material butene-1 is less than 2ppm and the purity meets the polymerization requirement, and then the refined butene-1 enters the polymerization reactor 1;

[0090] In a polymerization kettle, 4160 kg of refined liquid butene-1 monomer is added as a raw material, and a catalyst system is added, wherein the catalyst system comprises 0.07 kg of a conventional spherical anhydrous magnesium chloride supported titanium solid catalyst (7 kg of a catalyst solution, the solvent is hexane, wherein the solid content is 1 wt%), 2.8 kg of triethylaluminum and 0.035 kg of dicyclopentyldimethoxysilane, which are mixed in a catalyst system mixer 2 and then added to the polymerization kettle 1, and the catalyst system is added to the polymerization kettle 1.

[0091] 0.018 kg of hydrogen was added, and then the reaction pressure was maintained at 2.1 MPa with nitrogen, and the polymerization reaction was carried out at 70° C. for 3.55 hours, maintaining the polymer concentration of the polymer solution in the polymerization kettle at 20% by weight;

[0092] (2) Polymer separation:

[0093] The polymer solution flows out of the polymerization kettle 1 and enters the deactivation tank 4, where it is mixed with the terminator to deactivate the catalyst; the polymer solution flowing out of the deactivation tank 4 is then fed to the booster pump 5, where the pressure is increased to 3.0 MPa, and then

[0094] The first heat exchanger 6 is used to raise the temperature to 200°C, so that the polymer solution reaches the operating pressure and temperature of the first monomer removal tower 7, and then enters the first monomer removal tower 7 for monomer removal. In the first monomer removal tower 7, the polymer solution relies on gravity to pass through the seven-layer conical surface 71 (including the dispersion surface 711 and the receiving surface 712) set in the tower to make it flat and thin, so that the butene-1 gas and the molten polybutene-1 are fully separated. The polybutene-1 melt settles to the bottom of the first monomer removal tower 7 and is discharged from the bottom outlet of the tower with the help of the first delivery pump 8, while the monomer-containing gas flows out from the gas outlet at the top of the tower.

[0095] out; then, the second heat exchanger 9 is used to heat the polybutene-1 melt after the first monomer stripping to the operating temperature in the second monomer stripping tower 5 10, and the melt enters the second monomer stripping tower 10, and the vacuum pump 12 arranged outside the top of the second monomer stripping tower 10 is used to control the operating pressure of the second monomer stripping tower 10 in a vacuum state, and the monomer stripping is carried out under the vacuum conditions of 210° C. and 0.002 MPa to obtain the polybutene-1 melt after the second monomer stripping and discharge it from the bottom outlet of the tower with the help of the second delivery pump 11, and the gas containing the monomer flows out from the gas outlet at the top of the tower; the content of butene-1 in the polybutene-1 melt after the second monomer stripping is 30 ppm (by weight);

[0096] (3) Monomer recovery:

[0097] The monomer-containing gas flowing out of the first monomer-removing tower 7 and the second monomer-removing tower 10 passes through the first buffer tank 13 and the second buffer tank 14 respectively and then enters the separation tower 15 for separation, so as to separate the butene-1 gas and the terminator; the butene-1 gas flowing out of the monomer gas outlet at the top of the separation tower 15 passes through the drying tower 16 and the condenser 17 for treatment and then enters the monomer storage tank 18 for liquid butene-1; the liquid butene-1 stored in the monomer storage tank 18 enters the polymerization kettle 1 in step (1) for reuse; the terminator flowing out of the terminator outlet at the top of the separation tower 15 enters the deactivation tank 4 in step (2) for reuse;

[0098] (4) Polymer granulation:

[0099] The polybutene-1 melt after the second demolymerization is discharged from the bottom discharge port of the tower by means of the second delivery pump 11 and then enters the screw extruder 19 with a vacuum degassing device 191. During the extrusion of the polybutene-1 melt after the second demolymerization by the screw extruder 19, the residual butene-1 is further removed by the vacuum degassing device 191 of the screw extruder 19, and additives are added during the extrusion process to obtain a mixture of polybutene-1 and additives, wherein the additives are 1.6 kg of 1010, 1.8 kg of 1076 and 1.4 kg of 168; the mixture of polybutene-1 and additives discharged from the discharge port of the screw extruder 19 is conveyed to an underwater granulator 20 and cut into pellets to obtain the high-isotactic polybutene-1.

[0100] The results of this example are as follows: the catalyst activity is 16000 gPB / gcat, the isotacticity of the product polybutene-1 is 98.5%, the melt flow rate is 0.6 g / 10 min, and the density is 0.930 g / cm 3 , tensile strength is 29MPa, nominal strain is 300%, and cantilever beam impact strength (23℃) is 42kJ / m 2 .

[0101] Comparative Example 1

[0102] The present comparative example provides a method for continuous industrial production of high-isotactic polybutene-1. The steps included in the method are substantially the same as those in Example 2, except that: in step (2), the polymer solution flowing out of the deactivation tank 4 is fed to the booster pump 5, the pressure is increased to 4.0 MPa, and then the temperature is increased to 180° C. by the first heat exchanger 6, so that the polymer solution reaches the operating pressure and temperature of the first monomer stripping tower 7, and then enters the first monomer stripping tower 7 for monomer stripping, and the polybutene-1 melt settles to the bottom of the first monomer stripping tower 7 and is discharged from the bottom outlet of the tower by means of the first delivery pump 8, while the polymer solution containing The monomer gas flows out from the gas outlet at the top of the tower; then the second heat exchanger 9 is used to heat the polybutene-1 melt after the first stripper to the operating temperature in the second stripper tower 10, and the melt enters the second stripper tower 10. The vacuum pump 12 arranged outside the top of the second stripper tower 10 is used to control the operating pressure of the second stripper tower 10 in a vacuum state, and the monomer is removed under the vacuum conditions of 190°C and 0.010MPa to obtain the polybutene-1 melt after the second stripper and discharged from the bottom outlet of the tower with the help of the second delivery pump 11, and the monomer-containing gas flows out from the gas outlet at the top of the tower.

[0103] It was detected that the butene-1 content in the polybutene-1 melt after the second demolymerization was 89 ppm by weight.

[0104] Comparative Example 2

[0105] This comparative example provides a device for continuous industrial production of high-isotactic polybutene-1, which is basically the same as the device in Example 1, except that the first devolatilization tower 7 and the second devolatilization tower 10 are replaced by conventional devolatilization devices in the art, such as conventional flash tanks.

[0106] This comparative example also provides a method for continuous industrial production of high-isotactic polybutene-1. The method uses the equipment provided in this comparative example to carry out continuous industrial production of high-isotactic polybutene-1. The steps included in the method are the same as those in Example 2. The operating pressure and temperature of the two devolatilization devices in this comparative example are also the same as the operating pressure and temperature of the first devolatilization tower 7 and the second devolatilization tower 10 in Example 2, respectively.

[0107] It was detected that the butene-1 content in the polybutene-1 melt after being treated by the second devolatilization device was 112 ppm by weight.

Claims

1. A method for continuous industrial production of high isotactic polybutene-1, comprising the following steps: (1) Polymerization: In a polymerization reactor, a monomer containing liquid butene-1 is used as a raw material, and a polymerization reaction is carried out in the presence of a catalyst system to obtain a polymer solution; (2) polymer separation: the polymer solution flows out of the polymerization kettle and enters a deactivation tank, where it is mixed with a terminator to deactivate the catalyst; then, the polymer solution is pressurized to a first pressure and heated to a first temperature, and then enters a first monomer stripping tower to remove monomers to obtain a polybutene-1 melt after the first monomer stripping, and is discharged from the first monomer stripping tower; then, the polymer solution is heated to a second temperature and then enters a second monomer stripping tower to remove monomers at a second pressure to obtain a polybutene-1 melt after the second monomer stripping, and the separated monomer-containing gas flows out from the first monomer stripping tower and the second monomer stripping tower; The first pressure is 2.8-3.2 MPa, and the first temperature is 195-205°C; a booster pump is used to boost the polymer solution flowing out of the deactivation tank to the first pressure, and then a heat exchanger is used to heat the boosted polymer solution to the first temperature; The second temperature is 205-215° C., and the second pressure is 0.001-0.003 MPa; a heat exchanger is used to heat the polybutene-1 melt after the first stripping to the second temperature, and then the melt enters the second stripping tower, and a vacuum pump is used to control the operating pressure of the second stripping tower at the second pressure. The tower bodies of the first and second monomer-removing towers are provided with a plurality of conical surfaces in the vertical direction, wherein the plurality of conical surfaces include a dispersion surface with an opening downward and a receiving surface with an opening upward that are adjacently arranged in the vertical direction; a feed port and a gas outlet are provided at the top of the tower; and a discharge port is provided at the bottom of the tower; the cone angles of the plurality of conical surfaces are 130°-150°; the number of conical surfaces inside the tower body is an odd number between 5 and 9, and the first conical surface in the vertical direction is a dispersion surface with an opening downward; In the first and second monomer-eliminating towers, the polymer solution passes through several layers of conical surfaces arranged in the towers by gravity, so that the polymer solution is flattened and thinned, and the monomer and the molten polybutene-1 are fully separated. The polybutene-1 melt is discharged from the discharge port at the bottom of the tower, and the gas containing the monomer flows out from the gas outlet at the top of the tower; The monomer content in the polybutene-1 melt after the second stripping is less than 35 ppm; (3) Monomer recovery: the monomer-containing gas flowing out of the first monomer stripping tower and the second monomer stripping tower enters a monomer recovery unit for recovery to obtain monomer gas; The monomer recovery unit comprises at least a separation tower, a buffer tank and a monomer storage tank, and also comprises one or a combination of a condenser, a scrubber and a drying tower; the monomer-containing gas flowing out of the first monomer stripping tower and the second monomer stripping tower is firstly passed through a buffer tank, and then enters a separation tower for separation, so as to separate the monomer gas and the terminator; the monomer gas separated by the separation tower is treated by one or a combination of condensation, washing and drying to obtain the treated monomer; the treated monomer is entered into the monomer storage tank for storage; the monomer stored in the monomer storage tank is entered into the polymerization kettle in step (1) for reuse; the terminator separated by the separation tower is entered into the deactivation tank in step (2) for reuse; (4) Polymer granulation: The polybutene-1 melt after the second demolymerization is extruded and granulated to obtain the highly isotactic polybutene-1.

2. The method for continuous industrial production of high isotactic polybutene-1 according to claim 1, wherein: In step (1), the monomer containing liquid butene-1 also includes an α-olefin comonomer.

3. The method for continuous industrial production of high isotactic polybutene-1 according to claim 2, wherein: In step (1), the α-olefin comonomer comprises a C2-C10 α-olefin.

4. The method for continuous industrial production of high isotactic polybutene-1 according to claim 3, wherein: In step (1), the α-olefin comonomer includes ethylene and / or propylene.

5. The method for continuous industrial production of high isotactic polybutene-1 according to claim 1, wherein: In step (1), the catalyst system comprises a main catalyst, a co-catalyst and an external electron donor compound.

6. The method for continuous industrial production of high isotactic polybutene-1 according to claim 5, wherein: In step (1), the main catalyst comprises a titanium-based solid catalyst; the amount of the main catalyst used is: 30,000-140,000 g liquid butene-1 / g main catalyst.

7. The method for continuous industrial production of high isotactic polybutene-1 according to claim 6, wherein: In step (1), the main catalyst comprises a magnesium halide-supported titanium-based solid catalyst and / or an alkoxymagnesium-supported titanium-based solid catalyst.

8. The method for continuous industrial production of high isotactic polybutene-1 according to claim 5, wherein: In step (1), the co-catalyst comprises an alkyl aluminum compound; the amount of the co-catalyst used is: 850-14000 g liquid butene-1 / g co-catalyst.

9. The method for continuous industrial production of high isotactic polybutene-1 according to claim 8, wherein: In step (1), the co-catalyst includes one or a combination of triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum and tri-n-octylaluminum.

10. The method for continuous industrial production of high isotactic polybutene-1 according to claim 5, wherein: In step (1), the external electron donor compound comprises an alkoxysilane compound; the amount of the external electron donor compound is: 40,000-250,000 g liquid butene-1 / g external electron donor compound.

11. The method for continuous industrial production of high isotactic polybutene-1 according to claim 10, wherein: In step (1), the external electron donor compound includes one or a combination of dicyclopentyldimethoxysilane, cyclohexylmethyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexyltriethoxysilane, methyltriethoxysilane, methylcyclopentyldimethoxysilane, isobutylisopropyldimethoxysilane, isopropylcyclopentyldimethoxysilane and isobutyltriethoxysilane.

12. The method for continuous industrial production of high isotactic polybutene-1 according to claim 1, wherein: In step (1), the polymerization reaction is carried out in the presence of hydrogen and an inert gas; the amount of hydrogen used is: 1500-300000 g liquid butene-1 / g hydrogen.

13. The method for continuous industrial production of high isotactic polybutene-1 according to claim 12, wherein: In step (1), the inert gas includes nitrogen.

14. The method for continuous industrial production of high isotactic polybutene-1 according to claim 1, wherein: In step (1), the polymerization reaction temperature is 50-80° C., the reaction pressure is 2.0-2.5 MPa, and the reaction time is 2-5 hours.

15. The method for continuous industrial production of high isotactic polybutene-1 according to claim 14, wherein: In step (1), the polymerization reaction temperature is 65-75° C., the reaction pressure is 2.0-2.2 MPa, and the reaction time is 3-4 hours.

16. The method for continuous industrial production of high isotactic polybutene-1 according to claim 1, wherein: In step (1), the weight concentration of the polymer in the polymer solution is 20-25%.

17. The method for continuous industrial production of high isotactic polybutene-1 according to claim 1, wherein: In step (2), the number of conical surfaces inside the tower bodies of the first and second monomer-removing towers is seven, and the first conical surface in the vertical direction is a dispersion surface opening downward.

18. The method for continuous industrial production of high isotactic polybutene-1 according to claim 1, wherein: In step (4), the extrusion is carried out using a screw extruder; the screw extruder is provided with a vacuum degassing device; step (4) further comprises: during the process of extruding the polybutene-1 melt after the second demolymerization through the screw extruder, the residual monomer is further removed through the vacuum degassing device of the screw extruder.

19. The method for continuous industrial production of high isotactic polybutene-1 according to claim 18, wherein: Step (4) further comprises: adding additives during the extrusion of the polybutene-1 melt after the second demolymerization through a screw extruder to obtain a mixture of polybutene-1 and the additives, and then granulating.

20. The method for continuous industrial production of high isotactic polybutene-1 according to claim 1, wherein: In step (4), the granulation is carried out using an underwater granulator.

21. An apparatus for continuous industrial production of high-isotactic polybutene-1, which is used to implement the method for continuous industrial production of high-isotactic polybutene-1 according to any one of claims 1 to 20, the apparatus comprising: polymerization unit, polymer separation unit, monomer recovery unit and polymer granulation unit; The polymerization unit comprises a polymerization kettle, which is at least provided with a reaction system inlet and a polymer solution outlet; The polymer separation unit comprises a deactivation tank, a booster pump, a first heat exchanger, a first monomer stripping tower, a second heat exchanger, a second monomer stripping tower and a vacuum pump; the deactivation tank is at least provided with a polymer inlet, a terminator inlet and a discharge port; the first monomer stripping tower and the second monomer stripping tower are at least respectively provided with a feed port, a gas outlet and a discharge port; The polymer granulation unit comprises an extruder and a granulator; The polymer solution outlet of the polymerization kettle is connected to the polymer inlet of the deactivation tank through a pipeline; the discharge port of the deactivation tank is connected to the feed port of the first monomer removal tower through a pipeline, a booster pump and a first heat exchanger; the discharge port of the first monomer removal tower is connected to the feed port of the second monomer removal tower through a pipeline and a second heat exchanger, and the vacuum pump is connected to the gas outlet of the second monomer removal tower through a pipeline; The gas outlet of the first monomer removal tower is connected to the monomer recovery unit through a pipeline; the gas outlet of the second monomer removal tower is connected to the monomer recovery unit through a pipeline and the vacuum pump; The discharge port of the second monomer removal tower is sequentially connected to the extruder and the granulator through pipelines; Wherein, the tower bodies of the first and second monomer-removing towers are provided with a plurality of conical surfaces in the vertical direction, and the plurality of conical surfaces include a dispersion surface with an opening downward and a receiving surface with an opening upward, which are adjacently arranged in the vertical direction; the feed port and the gas outlet are provided at the top of the tower; the discharge port is provided at the bottom of the tower; the cone angles of the plurality of conical surfaces are 130°-150°; the number of conical surfaces inside the tower body is an odd number between 5 and 9, and the first conical surface in the vertical direction is a dispersion surface with an opening downward; The monomer recovery unit comprises at least a separation tower, a buffer tank and a monomer storage tank, and also comprises one or a combination of a condenser, a scrubber and a drying tower; The separation tower is provided with a material inlet, a monomer gas outlet and a terminator outlet; the gas outlet of the first monomer-removing tower is connected to the material inlet of the separation tower through a pipeline, and the gas outlet of the second monomer-removing tower is connected to the material inlet of the separation tower through a pipeline and the vacuum pump, so that the monomer-containing gas flowing out of the first monomer-removing tower and the second monomer-removing tower is separated into the monomer gas and the terminator after being separated by at least the separation tower; The buffer tank is respectively arranged on the pipeline connecting the gas outlet of the first monomer stripping tower and the separation tower, and on the pipeline connecting the outlet of the vacuum pump outside the second monomer stripping tower and the separation tower, so that the monomer-containing gas flowing out of the first monomer stripping tower and the second monomer stripping tower first passes through the buffer tank respectively, and then enters the separation tower for separation; The condenser, scrubber and drying tower or a combination thereof is arranged at the rear of the separation tower, and is used to treat the monomer gas separated by the separation tower by condensation, scrubbing and drying or a combination thereof to obtain treated monomers; The monomer storage tank is arranged behind one or a combination of the condenser, the scrubber and the drying tower, and is used to store the treated monomer; The monomer recovery unit further comprises a monomer circulation pipeline, one end of which is connected to the reaction system inlet of the polymerization kettle, and the other end is connected to the outlet of the monomer storage tank, for recycling the monomer; The monomer recovery unit also includes a terminator circulation pipeline, one end of which is connected to the terminator inlet of the deactivation tank, and the other end is connected to the terminator outlet of the separation tower, for reusing the terminator separated by the separation tower.

22. The apparatus for continuous industrial production of high isotactic polybutene-1 according to claim 21, wherein: The reaction system inlet of the polymerization kettle includes: a monomer inlet, a catalyst system inlet, a hydrogen inlet and an inert gas inlet; the monomer inlet includes a liquid butene-1 inlet and an α-olefin comonomer inlet which can be optionally set.

23. The apparatus for continuous industrial production of high isotactic polybutene-1 according to claim 21, wherein: The number of conical surfaces inside the tower bodies of the first and second monomer-removing towers is seven, and the first conical surface in the vertical direction is a dispersion surface opening downward.

24. The apparatus for continuous industrial production of high isotactic polybutene-1 according to claim 21, wherein: The booster pump comprises a gear pump or a screw pump; The first heat exchanger and the second heat exchanger each include a multi-tube heat exchanger; The discharge port of the first monomer removal tower is provided with a delivery pump for discharging the tower bottom material from the discharge port and delivering it to the second heat exchanger; the delivery pump comprises a gear pump or a screw pump; The discharge port of the second monomer removal tower is provided with a delivery pump for discharging the tower bottom material from the discharge port and delivering it to the extruder; the delivery pump comprises a gear pump or a screw pump.

25. The apparatus for continuous industrial production of high isotactic polybutene-1 according to claim 21, wherein: The extruder comprises a screw extruder; the screw extruder is provided with a vacuum degassing device.

26. The apparatus for continuous industrial production of high isotactic polybutene-1 according to claim 21, wherein: The pelletizer includes an underwater pelletizer.

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