CN114437253A - Method for removing volatile components from polymer, device and application thereof - Google Patents
Method for removing volatile components from polymer, device and application thereof Download PDFInfo
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- CN114437253A CN114437253A CN202011131317.0A CN202011131317A CN114437253A CN 114437253 A CN114437253 A CN 114437253A CN 202011131317 A CN202011131317 A CN 202011131317A CN 114437253 A CN114437253 A CN 114437253A
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F6/00—Post-polymerisation treatments
- C08F6/06—Treatment of polymer solutions
- C08F6/10—Removal of volatile materials, e.g. solvents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F112/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F112/02—Monomers containing only one unsaturated aliphatic radical
- C08F112/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F112/06—Hydrocarbons
- C08F112/08—Styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
- C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to the field of polymer post-treatment, and discloses a method for removing volatile components from a polymer, and a device and application thereof. The method comprises the following steps: conveying the polymer melt to a first heat exchanger for primary heating treatment, and then entering a first flash tank for primary devolatilization to obtain a first flash vapor phase and a first polymer melt; conveying the first polymer melt to a second heat exchanger for secondary heating treatment, and then entering a second flash tank for secondary devolatilization to obtain a second flash vapor phase; conveying the second flash evaporation gas phase to a first condenser for cooling, and conveying to a layering tank for oil-water layering to obtain an oil phase; and conveying the first flash vapor phase and the oil phase to a heavy component removing tower for three-stage devolatilization to obtain a light component and a heavy component. The method is adopted to treat the polymer, the volatile content in the product is low, the aggregation of oligomer and high-boiling organic compound in circulating liquid is avoided, and the quality and the performance stability of the product are ensured.
Description
Technical Field
The invention relates to the field of post-treatment of polymers, and particularly discloses a method for removing volatile components from a polymer, and a device and application thereof.
Background
In the polymer industry, aromatic olefin monomers are continuously produced as polymers by bulk polymerization in liquid phase monomers, and the polymer melt is then fed to a devolatilization unit where undesirable compounds such as unreacted monomers, solvents, dimers, and trimers can be removed from the polymer. For example, volatile components can be removed by vacuum distillation, heat flashing, stripping, or a combination of these. The gas discharged from the devolatilization device is condensed and recycled.
US5540813A describes a process for removing volatiles from aromatic olefinic compounds in which the polymer solution is heated to above 230 ℃ by a heat exchanger and removed by a two-stage vacuum devolatilizer, wherein the top of the first stage flash column is a downflow heat exchanger and the top of the second stage flash column is a multi-nozzle insert ring comprising a plurality of loop tubes directed downwardly through small orifice nozzles to form thin strands of molten polymer falling vertically, the resulting polymer having a residual monomer content of less than 500 ppm.
In US5380822A a process for increasing the devolatilization efficiency is described wherein 1 wt.% or more of water is injected into a polymer or polymer composition containing residual monomer at a pressure of 3-10MPa at 200-270 ℃ and then injected into a flash devolatilizer with distributor tray assemblies at a pressure of 0.6KPa to remove volatiles and obtain a polymer with a minimum residual monomer content of 150 ppm.
The existing method for removing the volatile components is focused on the removal efficiency and effect, and oligomers which have great influence on resin performance, such as dimers and trimers, in components of circulating liquid after the volatile components are condensed are not treated in a targeted manner, so that the oligomers are aggregated in the circulating liquid and are recycled along with the circulating liquid to return to the polymer preparation process, the content of polymer oligomers is higher, and the resin performance, such as flexural modulus, impact strength, light transmittance and the like, is influenced. On the other hand, specific additives, such as certain ester compounds, relatively high boiling hydrocarbons (such as mineral oil), and pigments or colorants, stabilizers, etc., must be added during the polymerization process. Although many additives are essentially non-volatile, the high temperature and low pressure conditions prevalent in the development process can result in the vaporization of certain long chain fatty acids, esters and waxes, as well as high boiling hydrocarbons (e.g., mineral oil). In order to meet the requirements of product quality control, it is desirable to minimize these compounds during the devolatilization and recycling processes.
Disclosure of Invention
The invention aims to solve the problem that additives such as oligomer, high-boiling-point hydrocarbon and the like are difficult to remove in a polymer when the volatile components are removed in the prior art, and provides a method for removing the volatile components from the polymer and a device and application thereof.
In order to achieve the above object, a first aspect of the present invention provides a method for removing volatile components from a polymer, comprising the steps of:
s1, conveying the polymer melt from the polymerization reaction to a first heat exchanger E-1 for primary heating treatment, and then entering a first flash tank DV-1 for primary devolatilization to obtain a first flash vapor phase and a first polymer melt;
s2, conveying the first polymer melt to a second heat exchanger E-2 for secondary heating treatment, and then entering a second flash tank DV-2 for secondary devolatilization to obtain a second flash vapor phase and a second polymer melt;
s3, conveying the second flash evaporation gas phase to a first condenser E-3 for cooling, conveying the liquid obtained by cooling to a layering tank V-1 for oil-water layering to obtain an oil phase and a water phase;
s4, conveying the first flash vapor phase in the step S1 and the oil phase in the step S3 to a heavy component removing tower T-1 for three-stage devolatilization to obtain light components and heavy components containing low-boiling-point compounds.
The invention provides a device for removing volatile components from a polymer, which is characterized by comprising a polymerization reactor R, a first flash tank DV-1, a second flash tank DV-2, a first heat exchanger E-1, a second heat exchanger E-2, a first condenser E-3, a layering tank V-1 and a heavy component removing tower T-1;
the first heat exchanger E-1 is communicated with the polymerization reactor R and is used for carrying out primary heating treatment on the polymer melt from the polymerization reactor R;
the top of the first flash tank DV-1 is communicated with the first heat exchanger E-1 and is used for carrying out primary devolatilization on the polymer melt subjected to primary heating treatment, and a first flash vapor phase and the first polymer melt are discharged from the top and the bottom of the first flash tank DV-1 respectively;
the mixer X-1 is communicated with the bottom of the first flash tank DV-1 and is used for mixing a first flash vapor phase discharged from the bottom of the first flash tank DV-1 with a stripping agent to obtain a mixture;
the second heat exchanger E-2 is communicated with the bottom of the first flash tank (DV-1) and is used for carrying out secondary heating treatment on the first polymer melt discharged from the bottom of the first flash tank (DV-1);
the top of the second flash tank DV-2 is communicated with the second heat exchanger E-2 and is used for performing secondary devolatilization on the mixture subjected to secondary heating treatment, and a second flash vapor phase and a second polymer melt are respectively discharged from the top and the bottom of the second flash tank DV-2;
the first condenser E-3 is communicated with the top of the second flash tank DV-2 and is used for cooling a second flash vapor phase discharged from the top of the second flash tank DV-2 to obtain liquid;
the layering tank V-1 is communicated with the first condenser E-3 and is used for carrying out oil-water separation on the liquid to obtain an oil phase and a water phase;
the heavy component removing tower T-1 is respectively communicated with the top of the first flash tank DV-1 and the layering tank V-1 and is used for carrying out three-stage devolatilization on a first flash vapor phase discharged from the top of the first flash tank DV-1 and an oil phase discharged from the layering tank V-1, a light component is obtained at the top of the heavy component removing tower, and a heavy component containing a low-boiling-point compound is obtained at the bottom of the heavy component removing tower.
In a third aspect the invention provides the use of a method or apparatus as described above for the removal of volatile components from a polymer.
Through the technical scheme, the method for removing the volatile components from the polymer, the device and the application thereof provided by the invention have the following beneficial effects:
in the invention, a polymer melt obtained through polymerization reaction passes through at least two stages of devolatilization flash evaporators connected in series, a first gas phase flow separated by a first flash tank is conveyed to a heavy component removing tower, light components separated from the top of the tower mainly comprise monomers and solvents, the light components are condensed and then returned to a polymerization section for reuse, and heavy components such as enriched oligomers and the like are discharged from the bottom of the tower. And adding a stripping agent into the melt before the melt enters a second flash tank to improve the devolatilization efficiency, carrying out deep cooling and grading on a second gas phase flow separated by the second flash tank, conveying an oil phase part to a heavy component removing tower in a continuous or intermittent mode, separating a light component from the heavy component and recovering from the top of the removing tower.
The method provided by the invention has simple process flow and easy operation, the product obtained by the process has low content of volatile matters, and the recovered circulating liquid is purified to avoid the aggregation of oligomers and certain high-boiling-point organic compounds in the circulating liquid, thereby ensuring the stable quality and performance of the product. And the heavy component removal treatment is carried out on the circulating liquid on the basis of not obviously increasing the energy consumption and the material consumption, so that the performance of the product is improved.
Drawings
FIG. 1 is a schematic diagram of a process for removing volatile components from a polymer of the present invention.
FIG. 2 is a schematic diagram of a prior art polymer devolatilization process.
Description of the reference numerals
F1, a comprehensive feeding pipeline; r-1 is a CSTR reactor; r-2 is a PFR reactor; DV-1 is a first flash tank; DV-2 is a second flash tank; v-1, a layering tank; v-2: a first condensate receiving tank; e-1, a first heat exchanger; e-2, a second heat exchanger; e-3, a first condenser; e-4, a second condenser; e-5, a reboiler; x-1 is a mixer; x-2 is a material distributor; p-1/2/3 polymer melt pump; p-4, an oil phase delivery pump; p-5, a condensate pump; p-6 is a discharge pump; t-1: a heavy component removal column; v-3, a flash evaporation gas phase buffer tank; v-4, a condensate receiving tank; e-6: a third condenser; p-7, circulating liquid delivery pump.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In a first aspect, the present invention provides a process for devolatilizing a polymer, the process comprising the steps of:
s1, conveying the polymer melt from the polymerization reaction to a first heat exchanger E-1 for primary heating treatment, and then entering a first flash tank DV-1 for primary devolatilization to obtain a first flash vapor phase and a first polymer melt;
s2, conveying the first polymer melt to a second heat exchanger E-2 for secondary heating treatment, and then entering a second flash tank DV-2 for secondary devolatilization to obtain a second flash vapor phase and a second polymer melt;
s3, conveying the second flash evaporation gas phase to a first condenser E-3 for cooling, conveying the liquid obtained by cooling to a layering tank V-1 for oil-water layering to obtain an oil phase and a water phase;
s4, conveying the first flash vapor phase in the step S1 and the oil phase in the step S3 to a heavy component removing tower T-1 for three-stage devolatilization to obtain light components and heavy components containing low-boiling-point compounds.
In the invention, a polymer melt obtained through polymerization reaction passes through at least two stages of devolatilization flash evaporators connected in series, a first gas phase flow separated by a first flash tank is conveyed to a heavy component removing tower, light components separated from the top of the tower mainly comprise monomers and solvents, the light components are condensed and then returned to the polymerization reaction for reuse, and heavy components such as enriched oligomers and the like are discharged from the bottom of the tower. And (3) carrying out deep cooling and grading on the second gas phase separated by the second flash tank, conveying the oil phase part to a heavy component removing tower in a continuous or intermittent mode, separating the light component from the heavy component and recovering the light component from the top of the removing tower.
In the present invention, the second polymer melt obtained after devolatilization according to the above-described process has a low content of volatiles. Furthermore, after the first flash vapor phase and the second flash vapor phase are treated by the heavy component removal tower, the aggregation of oligomers and certain high-boiling-point organic compounds in circulating liquid is avoided, and the quality and the stable performance of products are ensured.
In the present invention, the polymer melt is an aromatic olefin polymer, preferably an aromatic olefin homopolymer and/or an aromatic olefin copolymer containing at least 50% by weight of an aromatic olefin component.
The aromatic olefins are generally referred to as vinylaromatic monomers, in particular styrene monomers, such as styrene, alpha-methylstyrene or p-methylstyrene, etc., and the copolymeric composition can be a copolymer of an aromatic alkene with a nitrile, in particular acrylonitrile, such as a copolymer of styrene with acrylonitrile (SAN) or acrylonitrile-butadiene-styrene (ABS), or a copolymer of styrene with acrylic acid or methacrylic acid esters, or else, in particular, a styrene copolymer ("HIPS") with high impact strength modified by grafting a natural or synthetic rubber, such as a diene polymer, in particular a 1, 3-conjugated diene polymer, for example polybutadiene or polyisoprene.
In the present invention, the aromatic olefin monomer, the comonomer, the conjugated diene, the initiator, and other additives such as a solvent, an antioxidant and other additives are generally fed to the polymerization system through a feed line or a composite feed line (denoted by F1) to carry out polymerization. The polymerization system generally consists of one or more fully mixed reactors (CSTR) or/and Plug Flow Reactors (PFR) in series. The reactor combination of a CSTR and a PFR is only briefly described in FIG. 1 of the present patent application and the specific reactor composition of the polymerization system is not a limitation of the present patent.
According to the invention, the content of the volatile constituents in step S1 is from 0.5 to 40% by weight, preferably from 0.5 to 40% by weight, based on the total weight of the polymer melt.
In the present invention, the volatilizable component includes unreacted monomers, solvents, oligomers, and low-boiling organic compounds. The oligomers are typically formed during polymerization, but also before or during devolatilization when the polymer is at an elevated temperature. Oligomers are typically dimers and trimers of aromatic olefins. In the case of typical polymerization of styrene, the oligomers are essentially dimers and trimers of styrene and exist in both cyclic and acyclic forms. The low-boiling organic compounds, including compounds generated by decomposition of the initiator, which accumulate in the circulating liquid for a long time to inhibit polymerization, and other additives, such as white oil, which volatilize in a small amount at a high temperature under vacuum.
According to the invention, in step S1, the first heat exchanger E-1 is a downflow heat exchanger, located above the first flash tank DV-1.
In the invention, preferably, the first heat exchanger E-1 is a shell-and-tube heat exchanger, the polymer melt passes through the tube side, and the diameter of the inner wall of the tube array is 5-40mm, preferably 10-25 mm. And (3) allowing high-temperature heat conduction oil as a heat exchange medium to flow away from the shell pass of the heat exchanger, and allowing the polymer melt to flow out of the bottom of the heat exchanger and enter the first flash tank DV-1 after being heated once by the first heat exchanger E-1. Preferably, the once heat-treated polymer melt enters the interior of the first flash tank DV-1 in the form of strands and/or elongated droplets.
According to the invention, the heating temperature of the primary heating treatment is 150-.
According to the invention, said stage oneThe devolatilization pressure is less than atmospheric pressure, preferably 0.05X 103To 20X 103Pa, more preferably 0.1X 103To 10X 103Pa。
In the present invention, the pressures are absolute pressures unless otherwise specified.
According to the invention, the content of the volatile constituents is from 0.05 to 1% by weight, preferably from 0.1 to 0.3% by weight, based on the total weight of the first polymer melt.
According to the invention, the method further comprises: in step S2, the first polymer melt is sent to a step of mixing with a stripping agent in a mixer (X-1) before the second heat treatment.
In the invention, before the first polymer melt is subjected to secondary addition treatment, the first polymer melt is mixed with the stripping agent before entering the second flash tank, so that the devolatilization efficiency can be further improved.
In the present invention, the stripping agent is preferably a compound different from (or immiscible in) the monomer, for example selected from carbon dioxide and/or deionized water, preferably deionized water. The stripping agent is used in an amount of 0.1 to 5 wt.%, preferably 0.5 to 3 wt.%, based on the total weight of the first polymer melt.
According to the present invention, in step S2, the heating temperature of the secondary heating treatment is 400 ℃, preferably 280 ℃ at 180 ℃.
According to the present invention, in step S2, the devolatilization pressure of the secondary devolatilization is less than the devolatilization pressure of the primary devolatilization. When the devolatilization pressure of the secondary devolatilization is less than that of the primary devolatilization, a better volatile component removal effect can be obtained.
According to the present invention, the devolatilization pressure of the secondary devolatilization is 1X 10 times lower than that of the primary devolatilization3To 20X 103Pa, preferably 1X 10 lower3To 10X 103Pa。
According to the present invention, the devolatilization pressure of the secondary devolatilization is 0.05X 103To 10X 103Pa, preferably 0.1X 103To 5X 103Pa。
According to the invention, the content of the volatile constituents is 800ppm or less, preferably 300ppm or less, more preferably 100ppm or less, based on the total weight of the second polymer melt.
According to the invention, in step S2, the first polymer melt, preferably the mixture comprising the first polymer melt and the stripping agent, is passed via the material distributor X-2 into the second flash tank DV-2. The mixture comprising the first polymer melt and the stripping agent is extruded from the fine orifices of the material distributor X-2 and falls in the form of threads or drops into the bottom of the second flash tank DV-2. The diameter of the spray holes of the material distributor is 1-30mm, preferably 3-10 mm. On the premise of ensuring the fluidity of the polymer, the thinner spray holes can increase the contact surface area of the polymer melt and the vacuum environment contained in the second flash tank, and the devolatilization efficiency is improved.
In the present invention, in order to sufficiently cool and recover the second flash vapor phase, the second flash vapor phase is cooled to 0 to 25 ℃, preferably 0 to 15 ℃ by the first condenser E-3 in step S3. If special low-boiling comonomers, such as styrene and methyl methacrylate, are added for copolymerization, the second flash vapor phase is cooled to 0-10 ℃ by a first condenser E-3. The condensed liquid is subjected to oil-water stratification in a layering tank V-1, the water phase is discharged to remove sewage, and the oil phase is intermittently or continuously discharged into a heavy component removal tower T-1 to be subjected to three-stage removal.
According to the invention, the theoretical plate number of the heavies removal column is from 4 to 50, preferably from 6 to 30.
According to the invention, the temperature at the top of the stripping column is from 10 to 100 ℃ and preferably from 30 to 80 ℃.
According to the invention, the bottom temperature of the heavies removal column is from 30 to 200 ℃, preferably from 60 to 180 ℃.
According to the invention, the overhead reflux ratio R of the heavies removal column is from 0.6 to 2, preferably from 0.6 to 1.
According to the invention, the reflux temperature of the heavies removal column is from 10 to 80 ℃ and preferably from 20 to 50 ℃.
According to the invention, the heavies removal column is operated at a pressure of 0.05X 103To 20X 103Pa, preferably 0.1X 103To 10X 103Pa。
In the present invention, the operating pressure of the heavies removal column is preferably at or substantially at the pressure of the first flash drum DV-1.
According to the invention, in step S4, the first flash vapor phase is sent to the bottom of heavies removal column T-1 and the oil phase is sent to the middle of heavies removal column T-1.
According to the invention, the first flash vapor phase is passed to the stripping column at trays 1-3.
According to the invention, the oil phase is passed to the heavies removal column T-1 at trays 3-10.
In the invention, the light component discharged from the top of the heavy component removing tower T-1 is conveyed out of the system by a condensate pump P-5 and is conveyed to a polymerization section for recycling. Wherein the oligomer content in the light fraction is less than 1000ppm, preferably less than 500ppm, more preferably less than 200 ppm.
According to the invention, in step S4, the oligomer content in the light fraction is less than 1000ppm, preferably less than 500ppm, more preferably less than 200 ppm.
Preferably, the method further comprises returning the light components to the polymerization reaction of step S1 after condensing.
In the invention, the heavy component containing low boiling point compounds is discharged from the bottom of the heavy component removing tower T-1, and the low boiling point compounds are reaction monomers and solvents. The content of the low boilers is 40% by weight, preferably less than 10% by weight, based on the total weight of the heavy components.
The invention provides a device for removing volatile components from a polymer, which is characterized by comprising a polymerization reactor R, a first flash tank DV-1, a second flash tank DV-2, a first heat exchanger E-1, a second heat exchanger E-2, a first condenser E-3, a layering tank V-1 and a heavy component removing tower T-1;
the first heat exchanger E-1 is communicated with the polymerization reactor R and is used for carrying out primary heating treatment on the polymer melt from the polymerization reactor R;
the top of the first flash tank DV-1 is communicated with the first heat exchanger E-1 and is used for carrying out primary devolatilization on the polymer melt subjected to primary heating treatment, and a first flash vapor phase and the first polymer melt are discharged from the top and the bottom of the first flash tank DV-1 respectively;
the mixer X-1 is communicated with the bottom of the first flash tank DV-1 and is used for mixing a first flash vapor phase discharged from the bottom of the first flash tank DV-1 with a stripping agent to obtain a mixture;
the second heat exchanger E-2 is communicated with the bottom of the first flash tank (DV-1) and is used for carrying out secondary heating treatment on the first polymer melt discharged from the bottom of the first flash tank (DV-1);
the top of the second flash tank DV-2 is communicated with the second heat exchanger E-2 and is used for performing secondary devolatilization on the mixture subjected to secondary heating treatment, and a second flash vapor phase and a second polymer melt are respectively discharged from the top and the bottom of the second flash tank DV-2;
the first condenser E-3 is communicated with the top of the second flash tank DV-2 and is used for cooling a second flash vapor phase discharged from the top of the second flash tank DV-2 to obtain liquid;
the layering tank V-1 is communicated with the first condenser E-3 and is used for carrying out oil-water separation on the liquid to obtain an oil phase and a water phase;
the heavy component removing tower T-1 is respectively communicated with the top of the first flash tank DV-1 and the layering tank V-1 and is used for carrying out three-stage devolatilization on a first flash vapor phase discharged from the top of the first flash tank DV-1 and an oil phase discharged from the layering tank V-1, a light component is obtained at the top of the heavy component removing tower, and a heavy component containing a low-boiling-point compound is obtained at the bottom of the heavy component removing tower.
According to the invention, the device also comprises a mixer X-1, wherein the mixer X-1 is respectively communicated with the bottom of the first flash tank DV-1 and the second heat exchanger E-2 and is used for carrying out secondary heating treatment on a mixture obtained after the first polymer melt discharged from the bottom of the first flash tank DV-1 is mixed with the stripping agent.
According to the invention, the apparatus also comprises a material distributor X-2, said material distributor X-2 being located at the top inside the second flash tank DV-2 for introducing the mixture in the form of lines and/or drops into the second flash tank DV-2.
According to the invention, the top of the first flash tank DV-1 and the layering tank V-1 are respectively connected with different tower plates of the heavy component removing tower.
According to the invention, the top of the first flash tank DV-1 is connected to the heavies removal column at trays 1-3.
According to the invention, the stratified tank V-1 is connected to the heavies removal column at trays 3-10.
In a third aspect the invention provides the use of a method or apparatus as described above for the removal of volatile components from a polymer.
The method and apparatus of the present invention are further described with reference to FIG. 1.
Comprises aromatic olefin monomer, comonomer, conjugated diene, initiator and other additives such as solvent, antioxidant and other additives are fed into a full-mixing type reactor R-1 and a plug flow type reactor R-1 through a feed line F1 for polymerization reaction, and polymer melt obtained by polymerization is conveyed to a first heat exchanger E-1 through a polymer melt pump P-2 to be heated to 150-400 ℃ for one time, and is preferably 200-280 ℃; the polymer melt after the primary heat treatment flows into the first flash tank DV-1 from the bottom of the first heat exchanger E-1 in the form of strands and/or elongated droplets, and undergoes a primary devolatilization to obtain a first flash vapor phase and a first polymer melt. Wherein the devolatilization pressure of the first stage devolatilization is 0.05 × 103To 20X 103Pa, preferably 0.1X 103To 10X 103Pa. The first flash vapor phase is conveyed to the bottom of a heavy component removing tower T-1 for three-stage devolatilization.
The first polymer melt is conveyed to a mixer X-1 by a polymer melt pump P-3 and is mixed with 0.1 to 5 weight percent, preferably 0.5 to 3 weight percent of stripping agent of the first polymer melt to obtain a mixture, and the mixture is heated to the temperature of 400 ℃ by 180 ℃ by a second heat exchanger E-2, preferably to the temperature of 280 ℃ by 220 ℃; the mixture after the second heating treatment enters a second flash tank DV-2 and drops into the flash tank in a linear and/or drop shape through a material distributor X-2And performing secondary devolatilization at the bottom to obtain a second flash vapor phase and a second polymer melt. Wherein the devolatilization pressure of the secondary devolatilization is 0.05 × 103To 10X 103Pa, preferably 0.1X 103To 5X 103Pa. The second polymer melt was used for polymer pelletization.
Conveying the second flash evaporation gas phase to a first condenser E-3, cooling to 0-25 ℃, preferably 0-15 ℃, more preferably 0-10 ℃, conveying the liquid obtained by cooling to a layering tank V-1 for oil-water separation to obtain an oil phase and a water phase; and (5) discharging the water phase from the system to perform sewage treatment.
The oil phase is intermittently or continuously conveyed to the middle part of a heavy component removing tower T-1 by an oil phase conveying pump P-4 to carry out three-stage devolatilization. Heavy components containing low boiling point compounds are obtained at the bottom of the heavy component removing tower T-1, and light components are obtained at the top of the tower.
And the light component is condensed and conveyed to a first condensation receiving tank V-2 by a second condenser E-4 and is sent to the polymerization reaction for recycling by a condensate pump P-5. One part of the heavy components is conveyed to the oligomer tank through a discharge pump P-6, and the rest part of the heavy components is returned to the heavy component removing tower T-1 or is cooled by a third condenser E-7 and then returned to the heavy component removing tower T-1.
The present invention will be described in detail below by way of examples.
These examples are provided only for illustrating and explaining the present invention and are not intended to limit the present invention.
In the following examples and comparative examples, the polymer-related data were obtained according to the following test methods:
the impact strength of the gap of the simply supported beam is tested according to GB/T1043-2008;
flexural strength/flexural modulus were tested in accordance with GB/T1040-;
the light transmittance is tested according to GB/T2410-
Heat distortion temperature was measured according to ASTM D648;
the raw materials used in the examples and comparative examples are all commercially available products.
Example 1
In this example, polystyrene (GPPS) was prepared using styrene as a monomer and ethylbenzene as a solvent to dilute the reaction system using the apparatus shown in FIG. 1.
The polystyrene melt obtained through the polymerization process has the volatile component of 12.3 wt%, and after being heated to 235 ℃ by a first heat exchanger E-1, the polystyrene melt falls into a first flash tank DV-1 with the absolute pressure of 5.6kPa, the diameter of the inner wall of a heat exchanger tube array is 20mm, and the volatile component content in the first polymer melt obtained through first-stage devolatilization reaches 0.15 wt%. Before the melt enters a second flash tank DV-2, 2 wt% of deionized water is injected and is uniformly mixed with the melt through a mixer X-1, the melt is heated to 240 ℃ through a second heat exchanger E-2, and then the melt is injected into a material distributor X-32, the diameter of spray holes of the distributor is 6mm, and the absolute pressure of the second flash tank is 0.3 kPa.
The first flash vapor phase withdrawn from the top of the first flash tank DV-1 is fed to the bottom (at tray 1) of the heavies removal column T-1. The second flash vapor phase discharged from the top of the second flash tank DV-2 is cooled to 12 ℃ through a first condenser E-3, is layered in a layering tank V-1, the upper oil phase is continuously sent to the middle section (the 6 th tower plate) of a heavy component removal tower T-1, and the lower water phase is used for sewage treatment. The second polymer melt, discharged from the bottom of the second flash tank DV-2, has the content of volatile components as shown in table 1.
The temperature of the top of the heavy component removal tower is 56 ℃, the temperature of the bottom of the heavy component removal tower is 160 ℃, the reflux ratio is 0.71, and the reflux temperature is 35 ℃. And condensing the light components obtained at the tower top to obtain a recycle liquid, conveying the recycle liquid to a polymerization reaction for recycling, and treating the heavy components obtained at the tower bottom as waste liquid, wherein the total content of styrene and ethylbenzene in the heavy components is lower than 12 wt%. The content of oligomer in the circulating liquid is shown in table 1.
Example 2
The treatment was carried out in the same manner as in example 1 except that deionized water was not injected, and the other conditions were the same.
Example 3
A High Impact Polystyrene (HIPS) was prepared in the same manner as in example 1, except that 8% by weight of polybutadiene rubber was added to the polymerization raw materials.
Example 4
The same procedure as in example 1 was conducted, except that 30% by weight of methyl methacrylate and styrene were copolymerized (MS resin) to the polymerization monomer raw materials.
The reflux temperature of the heavy component removal tower is 26 ℃, the condensation temperature of the second flash vapor phase is 8 ℃, and other conditions are the same.
Comparative example 1
In this comparative example, polystyrene (GPPS) was prepared using styrene as a monomer and the reaction system was diluted with ethylbenzene as a solvent using the apparatus shown in fig. 2.
The polystyrene melt obtained by the polymerization process has the volatile component of 12.3 wt%, and falls into a first flash tank DV-1 with the absolute pressure of 5.6kPa after being heated to 235 ℃ by a first heat exchanger E-1, the diameter of the inner wall of a heat exchanger tube array is 20mm, and the volatile component content of the first polymer melt obtained by primary devolatilization reaches 0.1 wt%. The first polymer melt is heated to 240 ℃ by a second heat exchanger E-2 before entering a second flash tank, and then injected into a material distributor X-2, wherein the diameter of spray holes of the distributor is 6mm, and the absolute pressure of the second flash tank DV-2 is 0.6 kPa. And (3) mixing the first flash vapor phase and the second flash vapor phase obtained from the top of the first flash tank DV-1 and the top of the second flash tank DV-2, cooling and collecting the mixture by a flash vapor phase buffer tank V-3, a third condenser E-6 and a condensate receiving tank V-4, and conveying the mixture to a polymerization section for recycling, wherein the content of the oligomer in the circulating liquid obtained by cooling is shown in Table 1. The volatile content of the second polymer melt obtained at the bottom of the second flash tank DV-2 is shown in table 1.
Comparative example 2
A High Impact Polystyrene (HIPS) was prepared in the same manner as in comparative example 1, except that 8% by weight of polybutadiene rubber was added to the polymerization raw materials.
Example 5
The treatment was carried out in the same manner as in example 1 except that the devolatilization pressure of the primary devolatilization was 12.4 kPa.
Example 6
The treatment was carried out in the same manner as in example 1 except that the devolatilization pressure of the primary devolatilization was 22.4 kPa.
Example 7
The treatment was carried out in the same manner as in example 1 except that the devolatilization pressure of the secondary devolatilization was 8.4 kPa.
Example 8
The treatment was carried out in the same manner as in example 1 except that the devolatilization pressure of the secondary devolatilization was 5.1 kPa.
Example 9
The treatment was carried out in the same manner as in example 1 except that the devolatilization pressure of the secondary devolatilization was 12.4 kPa.
Comparative example 3
The treatment was carried out in the same manner as in example 1, except that: only one flash distillation is carried out, and the secondary flash distillation is not carried out.
TABLE 1
It can be seen from table 1 that with the decrease of the pressure of the two-stage devolatilizer, the polymer volatile content gradually decreases, and after the circulating liquid is treated by the de-weighting tower, the oligomer content is significantly decreased, so that the oligomer is not accumulated in the circulating liquid.
Test example
The second polymer melts obtained in the examples and comparative examples were sampled according to the test standards and tested for their properties, the results of which are shown in Table 2.
TABLE 2
| Numbering | Polymer and method of making same | Simply supported beam (with gap) KJ/m2 | Flexural modulus of elasticity GPa | Light transmittance% | Heat distortion temperature DEG C |
| Example 1 | GPPS | 1.87 | 2.92 | 90.2 | 89.1 |
| Example 2 | GPPS | 1.71 | 2.81 | 88.5 | 87.3 |
| Example 3 | HIPS | 12.11 | 2.45 | / | 83.6 |
| Example 4 | MS resin | 2.22 | 2.87 | 92.3 | 91.3 |
| Comparative example 1 | GPPS | 1.69 | 2.76 | 86.2 | 85.6 |
| Comparative example 2 | HIPS | 11.7 | 2.33 | / | 82.8 |
| Example 5 | GPPS | 1.85 | 2.77 | 88.6 | 87.1 |
| Example 6 | GPPS | 1.86 | 2.74 | 88.5 | 87.2 |
| Example 7 | GPPS | 1.84 | 2.69 | 87.2 | 86.1 |
| Example 8 | GPPS | 1.82 | 2.71 | 87.6 | 86.3 |
| Example 9 | GPPS | 1.85 | 2.67 | 87.1 | 84.8 |
| Comparative example 3 | GPPS | 1.84 | 2.61 | 86.8 | 84.2 |
From the results of tables 1 and 2, it can be seen that examples 1 (GPPS), 2(HIPS), and 3(MS resin) using the devolatilization process of the present invention all have better impact resistance, rigidity, light transmittance, and heat resistance.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (16)
1. A method for devolatilizing a polymer, said method comprising the steps of:
s1, conveying the polymer melt from the polymerization reaction to a first heat exchanger (E-1) for primary heating treatment, and then entering a first flash tank (DV-1) for primary devolatilization to obtain a first flash vapor phase and a first polymer melt;
s2, conveying the first polymer melt to a second heat exchanger (E-2) for secondary heating treatment, and then entering a second flash tank (DV-2) for secondary devolatilization to obtain a second flash vapor phase and a second polymer melt;
s3, conveying the second flash evaporation gas phase to a first condenser (E-3) for cooling, conveying the liquid obtained by cooling to a layering tank (V-1) for oil-water layering to obtain an oil phase and a water phase;
s4, conveying the first flash vapor phase in the step S1 and the oil phase in the step S3 to a heavy component removing tower (T-1) for three-stage devolatilization to obtain a light component and a heavy component containing low-boiling-point compounds.
2. The process according to claim 1, wherein in step S1, the content of the volatile components is 0.5 to 40 wt. -%, preferably 0.5 to 40 wt. -%, based on the total weight of the polymer melt.
3. The process according to claim 1 or 2, wherein in step S1, the first heat exchanger (E-1) is a downflow heat exchanger, preferably a shell-and-tube heat exchanger, the shell-and-tube heat exchanger having a tube inside wall diameter of 5 to 40nm, preferably 10 to 25 nm;
preferably, the heating temperature of the primary heating treatment is 150-400 ℃, preferably 200-280 ℃;
preferably, the devolatilization pressure of the first stage devolatilization is less than atmospheric pressure, preferably 0.05X 103To 20X 103Pa, more preferably 0.1X 103To 10X 103Pa。
4. A process according to any one of claims 1 to 3, wherein the amount of volatizable material is from 0.05 to 1 weight percent, preferably from 0.1 to 0.3 weight percent, based on the total weight of the first polymer melt.
5. The method according to any one of claims 1-4, wherein the method further comprises: a step of conveying the first polymer melt to a mixer (X-1) to be mixed with a stripping agent before the second heat treatment in step S2;
preferably, the stripping agent is selected from carbon dioxide and/or deionized water, preferably deionized water;
preferably, the stripping agent is used in an amount of 0.1 to 5 wt.%, preferably 0.5 to 3 wt.%, based on the total weight of the first polymer melt;
preferably, in step S2, the heating temperature of the secondary heating treatment is 180-;
preferably, in step S2, the devolatilization pressure of the secondary devolatilization is less than the pressure of the primary devolatilization, and preferably, the devolatilization pressure of the secondary devolatilization is 1 × 10 lower than the devolatilization pressure of the primary devolatilization3-20×103Pa, preferably 1X 10 lower3-10×103Pa；
More preferably, the devolatilization pressure of the secondary devolatilization is 0.05X 103To 10X 103Pa, more preferably 0.1X 103To 5X 103Pa。
6. The method according to any one of claims 1 to 5, wherein the content of volatizable material is 800ppm or less, preferably 300ppm or less, more preferably 100ppm or less, based on the total weight of the second polymer melt.
7. The process according to any one of claims 1 to 6, wherein in step S2, the first polymer melt is passed through a material distributor (X-2) into a second flash tank (DV-2);
preferably, the diameter of the spray holes of the top material distributor (X-2) is 1-30nm, preferably 3-10 nm.
8. The process according to any one of claims 1 to 7, wherein in step S3, the second flashed vapour phase is cooled to 0-25 ℃, preferably 0-15 ℃, more preferably 0-10 ℃.
9. The process according to any one of claims 1 to 8, wherein the theoretical plate number of the heavies removal column is from 4 to 50, preferably from 6 to 30;
preferably, the temperature at the top of the removal tower is 10-100 ℃, preferably 30-80 ℃;
preferably, the bottom temperature of the heavy component removal tower is 30-200 ℃, preferably 60-180 ℃;
preferably, the overhead reflux ratio R of the heavy component removal column is 0.6-2, preferably 0.6-1;
preferably, the temperature of the reflux liquid of the heavy component removing tower is 10-80 ℃, preferably 20-50 ℃;
preferably, the heavies removal column is operated at a pressure of 0.05X 103To 20X 103Pa, preferably 0.1X 103To 10X 103Pa。
10. The process according to any one of claims 1 to 9, wherein in step S4 the first flash vapor phase is sent to the bottom of the heavies removal column (T-1) and the oil phase is sent to the middle of the heavies removal column (T-1);
preferably, the first flash vapor phase is passed to trays 1-3 of a heavies removal column (T-1);
preferably, the oil phase is sent to trays 3-10 of the heavies removal column (T-1).
11. The process according to any one of claims 1 to 10, wherein in step S4, the content of oligomers in the light fraction is below 1000ppm, preferably below 500ppm, more preferably below 200 ppm;
preferably, the method further comprises returning the light components to the polymerization reaction of step S1 after condensing.
12. The process according to any one of claims 1 to 11, wherein the polymer melt is an aromatic olefin polymer, preferably an aromatic olefin homopolymer and/or an aromatic olefin copolymer containing at least 50 wt% of an aromatic olefin component;
preferably, the aromatic olefin polymer is selected from at least one of styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene copolymer, styrene- (meth) acrylate copolymer, polystyrene, and high impact polystyrene.
13. A device for removing volatile components from polymers is characterized by comprising a polymerization reactor (R), a first flash tank (DV-1), a second flash tank (DV-2), a first heat exchanger (E-1), a second heat exchanger (E-2), a first condenser (E-3), a layering tank (V-1) and a heavy component removing tower (T-1);
the first heat exchanger (E-1) is communicated with the polymerization reactor R and is used for carrying out primary heating treatment on the polymer melt from the polymerization reactor R;
the top of the first flash tank (DV-1) is communicated with the first heat exchanger (E-1) and is used for carrying out primary devolatilization on the polymer melt subjected to primary heating treatment, and a first flash vapor phase and the first polymer melt are respectively discharged from the top and the bottom of the first flash tank DV-1;
the second heat exchanger (E-2) is communicated with the bottom of the first flash tank (DV-1) and is used for carrying out secondary heating treatment on the first polymer melt discharged from the bottom of the first flash tank (DV-1);
the top of the second flash tank (DV-2) is communicated with the second heat exchanger (E-2) and is used for carrying out secondary devolatilization on the mixture after secondary heating treatment, and a second flash vapor phase and a second polymer melt are respectively discharged from the top and the bottom of the second flash tank (DV-2);
the first condenser (E-3) is communicated with the top of the second flash tank (DV-2) and is used for cooling the second flash vapor phase discharged from the top of the second flash tank (DV-2) to obtain liquid;
the layering tank (V-1) is communicated with the first condenser (E-3) and is used for carrying out oil-water separation on the liquid to obtain an oil phase and a water phase;
the heavy component removing tower (T-1) is communicated with the top of the first flash tank (DV-1) and the layering tank (V-1) respectively and is used for carrying out three-stage devolatilization on a first flash vapor phase discharged from the top of the first flash tank (DV-1) and an oil phase discharged from the layering tank (V-1), a light component is obtained at the top of the heavy component removing tower, and a heavy component containing a low-boiling-point compound is obtained at the bottom of the heavy component removing tower.
14. The apparatus according to claim 13, further comprising a mixer (X-1), said mixer (X-1) being in communication with the bottom of the first flash tank (DV-1) and with the second heat exchanger (E-2), respectively, for subjecting the mixture obtained after mixing the first polymer melt discharged from the bottom of the first flash tank (DV-1) with the stripping agent to a further secondary heating treatment;
preferably, the plant also comprises a material distributor (X-2), said material distributor (X-2) being located at the top inside said second flash tank (DV-2) for feeding said mixture in the form of lines and/or drops into said second flash tank (DV-2).
15. The apparatus according to claim 13 or 14, wherein the top of the first flash tank (DV-1) and the layering tank (V-1) are connected to different trays of the heavies removal column, respectively;
preferably, the top of the first flash tank (DV-1) is connected with the tower stages 1-3 of the heavy component removing tower;
preferably, the layering tank (V-1) is connected to the heavies removal column at trays 3-10.
16. Use of a method according to any one of claims 1 to 12 or an apparatus according to any one of claims 13 to 15 for devolatilizing a polymer.
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