CN111359377B - Devolatilization method and devolatilization system - Google Patents
Devolatilization method and devolatilization system Download PDFInfo
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- CN111359377B CN111359377B CN201811604469.0A CN201811604469A CN111359377B CN 111359377 B CN111359377 B CN 111359377B CN 201811604469 A CN201811604469 A CN 201811604469A CN 111359377 B CN111359377 B CN 111359377B
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
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- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
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- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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Abstract
The invention discloses a devolatilization method and a system for realizing the same. The system comprises a main body part and an accessory device, wherein the main body part comprises a feeding section, a melting and mixing section connected with the feeding section, a conveying and exhausting section connected with the melting and mixing section and a cooling and granulating drying part connected with the conveying and exhausting section; the auxiliary device comprises a solvent introducing system, a vacuum devolatilization system and a volatile organic compound treatment system. The method is characterized in that the volatile matters in the copolymer are removed in a continuous feeding and discharging mode and a solvent entrainment mode under the vacuum or high vacuum condition, so that devolatilization of materials and environment in the devolatilization process and in an isolation state of operators is realized, the efficiency is increased, and the energy consumption is reduced. The invention mainly discloses a devolatilization method and a devolatilization system.
Description
Technical Field
The invention relates to the field of polymer devolatilization, in particular to a devolatilization method and a devolatilization system.
Background
Along with the improvement of living standard, people's environmental protection consciousness is strengthened gradually, and air pollution receives more and more attention of everyone, and the air quality requirement to the enclosure space is higher and higher. Interior materials are one of the main sources of air pollution in closed spaces, and low-molecular organic volatile matters emitted by the interior materials can cause serious harm to the liver, the kidney, the respiratory system, hematopoietic organs, immune functions and the like of a human body. The low molecular organic volatiles are derived from unpolymerized polymer monomers, solvents, low molecular weight polymers, uncrosslinked additives, reaction by-products, and the like. This has put new demands on interior materials, plastic products for automobiles, and the like.
The polymer polymethacrylic acid, polymethylmethacrylate, polypropylene, polyethylene, polyamide and the like are one of the main varieties of plastic products for automobiles and the like, and the dosage of the polymer polymethacrylic acid, polymethylmethacrylate, polypropylene, polyethylene, polyamide and the like accounts for more than one third of the dosage of the automobile plastic. Polypropylene is taken as an example. The polypropylene has narrow molecular weight distribution, low melt strength, unsatisfactory hydrophilicity, adhesiveness and group reaction activity due to the linear chain nonpolar molecular structure, and is difficult to blend and compound with polar polymers or fillers, so that the application range of the polypropylene is limited. In order to improve the performance, a modification method of grafting polar groups on a main chain by using a compatibilizer is often adopted to polarize a grafted product, wherein the research on grafting maleic acid or maleic anhydride is most extensive. The maleic anhydride graft is a polymer obtained by taking maleic anhydride as a monomer and grafting with other materials under a proper temperature condition, is different from physical blending toughening, has both polar group aldehyde and olefin nonpolar chain segments, can perfectly combine strength and toughness by chemical bonding with the polymer and a filler, and has wide application prospect. However, the odor emission of the maleic anhydride grafted polypropylene raw material produced by domestic manufacturers is very large, and the lowest value of the domestic raw material is as high as 300 mu gC/g calculated by converting small molecular substances into carbon content (total carbon emission), and the difference is very large compared with the international standard which is universal and is lower than 50 mu gC/g. How to develop materials such as automobile interior decoration with low odor and low volatility has become a major problem to be solved in the domestic material industry.
The traditional process method for preparing the low-odor and low-automobile interior decoration environment-friendly material at present comprises the following steps: (1) the method of adding inorganic porous adsorbent is to adsorb some low molecular volatile matters by utilizing the porous structure of inorganic particles, but the adsorption and desorption balance of the method is greatly influenced by external conditions, so that the odor and the content of the material are difficult to reduce for a long time; (2) the multi-stage vacuum, material drying and other enhanced devolatilization methods can improve the smell and reduce the content to a certain extent through a post-treatment process, but have the defects of poor stability, complex process route, high energy consumption, high cost, low efficiency and the like; (3) adopts a supercritical carbon dioxide extraction method. The supercritical fluid has the characteristics of high solubility of liquid to solute and easy diffusion and movement of gas. More importantly, the density of the supercritical fluid is close to that of liquid, the viscosity of the supercritical fluid is only a few times of that of gas, the supercritical fluid is far smaller than that of the liquid, and the diffusion coefficient of the supercritical fluid is larger than that of the liquid, so that mass transfer is facilitated. In addition, the material has very low surface tension and is easy to permeate through a medium material. At present, carbon dioxide, water and the like are more studied. However, the supercritical fluid only provides a function of permeating a medium material, has a weak ability of dissolving or entraining polar volatile organic compounds, and further, has a large investment in large-scale continuous production.
These methods have improved the odor problem of polypropylene-based modified materials to some extent, but it is difficult to solve the odor problem for a long time. Therefore, it is very important to develop a modified polypropylene material that can thoroughly solve the problems of odor and emission.
US patent No. 5380822(1995) discloses a process for water-assisted devolatilization. That is, the polymer melt can be devolatilized to less than 500ppm (ppm being defined as 10) by injecting water into the melt in an amount greater than the amount of residual volatiles in the melt-6Mass fraction), preferably less than 150ppm, of residual volatiles, a devolatilization flash chamber pressure of 8mmHg or less, and a temperature of 200 ℃ to 350 ℃.
U.S. patent No. 6410683(2002) describes a process for removing impurities from thermoplastic polymers by mixing water, a stripping agent comprising carbon dioxide, with the polymer in the molten state, in a vessel at a pressure lower than atmospheric pressure, and stripping the volatile impurities from the polymer into the stripping agent by flash evaporation, with the aim of removing the volatile impurities from the mixture.
Chinese patent publication No. CN 1733810a (2006) proposes an improved method for post-treating polypropylene powder, i.e. after the polypropylene powder leaving the continuous polymerizer is subjected to primary gas/solid separation, a degassing device is added before the polypropylene powder contacts nitrogen or water vapor, hydrocarbons in the powder are removed and recovered as much as possible, and then the polypropylene powder contacts nitrogen or a mixture of nitrogen and water vapor to perform deep devolatilization and deactivation.
Chinese patent publication No. CN 101143946A (2008) discloses a method for preparing maleated polypropylene by supercritical reaction extrusion, wherein polypropylene, maleated series, auxiliary agent and initiator are added into a screw extruder, and supercritical fluid is injected into the system by a supercritical generation device to obtain the maleated polypropylene with high grafting rate and high grafting efficiency.
Chinese patent publication No. CN 201287457Y (2009) discloses a system for removing small molecule volatiles, which solves the problem that the existing devolatilization system cannot efficiently remove small molecule volatiles generated in the extrusion process of polypropylene blend, and provides a system for removing small molecule volatiles, which improves the devolatilization efficiency of polypropylene blend in the screw extrusion process and efficiently removes small molecule volatiles. A multi-stage vacuum devolatilization system and an inert gas leading-in device are arranged on the main body part of a double-screw extruder.
Chinese patent publication No. CN 103571054a (2014) discloses a low VOC polypropylene composite material, and a preparation method and an application thereof, using a novel high boiling point odor remover, having the characteristics of uniform dispersion, clean vacuum devolatilization and no residue in the melt extrusion process.
Chinese patent publication No. CN 107090128A (2017) discloses a method for preparing a supercritical low-odor and low-emission polypropylene material, which comprises mixing polypropylene materials, adding the mixture into a twin-screw extruder with a vacuum pump, introducing supercritical carbon dioxide into the middle of the twin-screw extruder, and melting and extruding the supercritical carbon dioxide and the polypropylene materials in a closed high-pressure screw cylinder to obtain the supercritical low-odor and low-emission polypropylene material.
However, with the upgrading of national industrial policies, the improvement of environmental standards and the revision of indoor air quality pollution limits in vehicles, the disclosed technology has no effective continuous removal capability for maleated polymers, i.e., low molecular weight volatiles with both polar groups and nonpolar segments in hydrophobic polymers.
Disclosure of Invention
The technical problem underlying the present invention is therefore to provide a process for the efficient devolatilization of maleated graft copolymers/blends, which addresses the above-mentioned deficiencies of the prior art. Another technical problem to be solved by the present invention is to provide a treatment system for the efficient removal of maleated graft copolymers/blends.
The technical scheme of the invention is that the copolymer devolatilization method comprises the following steps:
step one, polymerizing a component with stronger polarity and a grafted polymer with weaker polarity to obtain a copolymer, and pretreating the copolymer to be treated to remove entrained air;
step two, introducing the copolymer into a feed section of a processing device in a volatile removal system;
step three, the copolymer enters a melting and mixing section after passing through a feeding section, and is mixed with an extraction medium added in the melting and mixing section at the same time so as to extract volatile components in the molten copolymer; the extraction medium is selected from a solvent, or the solvent is mixed with an inert gas; the mass ratio of the solvent to the copolymer is 5-50: 100, respectively;
step four, feeding the melted copolymer mixed with the extraction medium into the conveying and exhausting section, wherein the conveying and exhausting section is connected with a vacuum devolatilization system, and a devolatilization port of the vacuum devolatilization system is connected with a vacuum pump system; the absolute pressure of the vacuum pressure value is less than 0.1 MPa;
step five, the extraction medium with the volatile components enters a volatile organic matter treatment system, the solvent or inert gas is recycled, and the volatile components removed from the polymer are removed;
and step six, the melt enters a cooling part, a grain cutting part and a drying part after passing through a conveying and exhausting section, and a low-volatile-component product prepared from the copolymer is obtained.
In the third step, preferably, when the solvent is mixed with inert gas, the ratio of solvent: the mass ratio of the inert gas is 10: 0.5-1.5.
In the fourth step, the absolute pressure of the vacuum pressure value is less than 0.1MPa and is close to 0 MPa.
According to a devolatilization method of the present invention, preferably, the first step comprises negative pressure or inert gas purging, or negative pressure and inert gas purging are performed simultaneously; in the third step, the device for introducing the solvent or the inert gas is arranged at the melting and mixing section of the processing equipment.
According to a devolatilization method of the present invention, preferably, the solvent in the third step is a mixture of a polar solvent and a non-polar solvent; the molar ratio range of the polar solvent to the non-polar solvent is as follows: 0.05-50: 1.
the addition of solvent serves two purposes, one being to swell the swellable portion of the blend and the other being to entrain volatile components of the blend.
The added solvent can be a mixed solvent, wherein the components respectively play roles of swelling and entrainment, or the same component has larger property change along with the change of operating conditions and respectively plays roles of swelling and entrainment in different stages.
Further, the polar solvent is selected from one or more of the following components: dimethylformamide, dimethylacetamide, acetone, butanone, N-methyl-2-pyrrolidone, methyl isobutyl ketone, methanol, ethanol, tetrahydrofuran and water;
the nonpolar solvent is selected from one or more of the following components: toluene, xylene, benzene, ethyl acetate, butyl acetate, diethyl ether, cyclohexanone, ethylene glycol, pyridine, n-butanol, n-hexane and cyclohexane;
the inert gas is selected from one of nitrogen, carbon dioxide, helium and argon.
According to a devolatilization method of the present invention, it is preferable that the solvent or the inert gas recovered by the volatile organic compound processing system is communicated with a solvent or inert gas delivery device.
According to a devolatilization method of the present invention, it is preferable that the highly polar component is one or more selected from the group consisting of polymethacrylic acid, polymethylmethacrylate, maleic acid, and maleic anhydride. More preferably, the highly polar component is selected from one or more of maleic acid and maleic anhydride.
Preferably, the weakly polar polymer is selected from one of polyethylene, polypropylene, and polyamide.
One aspect of the present application relates to a process for preparing low volatile maleated graft copolymers from maleated graft copolymers containing high volatile. Wherein maleation refers to grafting the polymer with maleic acid or maleic anhydride, or mixtures thereof; the polymer comprises polyethylene, or polypropylene, or polyamide, or mixtures thereof; volatiles means that low molecular organic volatiles originate from unpolymerized polymer monomers, solvents, low molecular weight polymers, uncrosslinked additives and reactions. Byproducts, and the like.
Different from physical blending toughening, the maleated graft has both polar group aldehyde group and olefin nonpolar chain segment, can perfectly realize the perfect combination of strength and toughness through the chemical bonding between the maleated graft and polymer and filler, and has wide application prospect.
The maleated graft is a polymer obtained by grafting maleic anhydride or maleic acid as a monomer with other materials under a proper temperature condition. In general, the grafting method mainly includes a solution method, a melting method, a radiation method, a solid phase method, and the like. Among them, the melting method is the most common and important method.
Because the maleated graft has the aldehyde group of a polar group and the olefin nonpolar chain segment, the maleated graft can be widely applied to the industries of modification of materials such as PA (nylon, Polyamide), PP (polypropylene), PE (polyethylene) and the like, wire and cable master batch, wood-plastic industry, encapsulated TPE (Thermoplastic Elastomer, English full name Thermoplastic Elastomer) and hot melt adhesive, and the like, and mainly plays a role in coupling compatibility.
The maleic anhydride graft toughened PA is taken as an example. In the maleated graft, an anhydride group can perform a generalized dehydration reaction with a polar group (-NH2, -OH) under the action of high temperature and screw shearing and form a chemical bond, so that incompatible polar and nonpolar substances are chemically coupled. PA has excellent mechanical properties but poor toughness at low temperatures, whereas olefins have good processing and low temperature toughness. However, since PA is a polar polymer and olefin is a nonpolar polymer, compatibility between the two is difficult. In this case, when the maleic anhydride graft is used, the both can be favorably bonded. The principle of action of the maleated grafts is similar when used in other applications.
Several key factors to consider in judging a quality maleated graft include: odor, grafting rate, yellowing index and whether ungrafted maleic anhydride or maleic acid is separated in the later reaction stage. It should be noted that in the grafting reaction, the grafting rate is generally low because much of the added maleic anhydride or acid is not grafted to the backbone. Thus, the product of the grafting reaction is not isolated and the final product will be a mixture containing the grafts. That is, there is a large deviation in the grafting ratio of maleic anhydride or maleic acid tested before and after the separation. Generally, high quality maleated grafts have the physical characteristics of low pungent odor, high grafting yield, and low yellowing index.
According to a devolatilization method of the present invention, it is preferable that the total carbon value of the obtained low-volatile copolymer is from 1. mu. gC/g to 100. mu. gC/g. More preferably 10-50. mu.gC/g.
The measuring method adopts the 'evaluation guidance of the quality of air in the passenger car' issued by science and technology standards of the department of environmental protection in 2014, and the GB// T26730-2011 measuring method is revised.
Another technical problem to be solved by the present invention is to provide a method for devolatilizing a blend, the method comprising:
step one, polymerizing a component with stronger polarity and a grafted polymer with weaker polarity to obtain a copolymer, and blending the copolymer with other raw materials to obtain a blend, so that the blend to be treated is pretreated to remove air carried in the blend;
step two, introducing the blend into a feed section of a processing device in a volatile removal system;
step three, the blend enters a melting mixing section after passing through a feeding section, and is mixed with an extraction medium added in the melting mixing section during melting so as to extract volatile components in the melting blend; the extraction medium is selected from a solvent, or the solvent is mixed with an inert gas; the mass ratio of the solvent to the blend is 5-50: 100, respectively;
step four, feeding the melted blend mixed with the extraction medium into the conveying and exhausting section, wherein the conveying and exhausting section is connected with a vacuum devolatilization system, and a devolatilization port of the vacuum devolatilization system is connected with a vacuum pump system; the absolute pressure of the vacuum pressure value is less than 0.1 MPa;
step five, the extraction medium with the volatile components enters a volatile organic matter treatment system, the solvent or inert gas is recycled, and the volatile components removed from the polymer are removed;
and step six, the melt enters a cooling part, a grain cutting part and a drying part after passing through a conveying and exhausting section, and a low-volatile-component product prepared from the blend is obtained.
In the third step, preferably, when the extraction medium is a solvent mixed with an inert gas, the ratio of the solvent: the mass ratio of the inert gas is 10: 0.5-1.5.
Preferably, the other raw materials in the step one are various additives. Such additives include, but are not limited to, fillers, scratch resistance agents, as well as antioxidants, weathering agents, lubricants, and the like.
The method also comprises the following steps:
according to the devolatilization method of the blend, the first step preferably comprises negative pressure or inert gas purging, or the negative pressure and the inert gas purging are carried out simultaneously; in the third step, the device for introducing the solvent or the inert gas is arranged at the melting and mixing section of the processing equipment.
According to the devolatilization method of the blend of the present invention, preferably, the solvent of the third step is a mixture of a polar solvent and a non-polar solvent; the molar ratio range of the polar solvent to the non-polar solvent is as follows: 0.05-50: 1.
the addition of solvent serves two purposes, one being to swell the swellable portion of the blend and the other being to entrain volatile components of the blend.
The added solvent can be a mixed solvent, wherein the components respectively play roles of swelling and entrainment, or the same component has larger property change along with the change of operating conditions and respectively plays roles of swelling and entrainment in different stages.
Further, the polar solvent is selected from one or more of the following components: dimethylformamide, dimethylacetamide, acetone, butanone, N-methyl-2-pyrrolidone, methyl isobutyl ketone, methanol, ethanol, tetrahydrofuran and water;
the nonpolar solvent is selected from one or more of the following components: toluene, xylene, benzene, ethyl acetate, butyl acetate, diethyl ether, cyclohexanone, ethylene glycol, pyridine, n-butanol, n-hexane and cyclohexane;
the inert gas is selected from one of nitrogen, carbon dioxide, helium and argon.
According to the devolatilization method of the blend of the present invention, it is preferable that the solvent or the inert gas recovered by the volatile organic compound processing system is communicated with a conveying device for the solvent or the inert gas.
According to the devolatilization method of the blend of the present invention, preferably, the highly polar component is one or more selected from polymethacrylic acid, polymethylmethacrylate, maleic acid and maleic anhydride. More preferably, the highly polar component is selected from one or more of maleic acid and maleic anhydride.
Preferably, the weakly polar polymer is selected from one of polyethylene, polypropylene, and polyamide.
According to a blend devolatilization process of the present invention, it is preferred that the resulting low volatile copolymer have an overall carbon value of from 1. mu. gC/g to 100. mu. gC/g. More preferably 10-50. mu.gC/g.
The measuring method adopts the 'evaluation guidance of the quality of air in the passenger car' issued by science and technology standards of the department of environmental protection in 2014, and the GB// T26730-2011 measuring method is revised.
The invention also provides a devolatilization system, which comprises a main body part and an auxiliary device, wherein the main body part comprises a feeding section, a melting and mixing section connected with the feeding section, a conveying and exhausting section connected with the melting and mixing section and a cooling, granulating and drying part connected with the conveying and exhausting section; the accessory device comprises a solvent introducing system, a vacuum devolatilization system and a volatile organic compound treatment system; the volatile organic compound processing system is communicated with the conveying device.
The conveying exhaust section is connected with a vacuum devolatilization system, and a devolatilization port of the vacuum devolatilization system is connected with a vacuum pump system.
The system solvent or inert gas introducing device is arranged at the melting and mixing section of the processing equipment.
The system is a double-screw extruder or sectional equipment, and the sectional functions of the system are feeding, melting and mixing, conveying and exhausting, cooling, granulating and drying respectively.
The length-diameter ratio of the double-screw extruder is 35-42, the rotating speed is 200-.
The invention has the beneficial effects that:
the invention adopts a double-screw extruder or sectional equipment with similar functions, a natural exhaust system and a vacuum-pumping exhaust system are opened on the main body of the equipment, and volatile organic compounds carried in added composite solvent or inert gas are removed, so as to prepare the maleated graft copolymer containing low volatile components or the blend containing the maleated graft copolymer.
The method and the system can effectively remove the low-molecular-weight volatile components in the copolymer or the copolymer-containing blend to be treated to obtain the low-volatile-component-containing copolymer or the copolymer-containing blend. In particular, the present application provides a method and system for producing a low volatile product from a high volatile containing copolymer.
Drawings
FIG. 1 is a schematic diagram of the system of the present invention.
In the figure, 11. power equipment; 12. a feed section of the devolatilization system; 13. a melting and mixing section of the devolatilization system; 14. a conveying and exhausting section of the devolatilization system; 15. a cooling, pelletizing and drying section of the devolatilization system; 16. a feed deoxygenation system; 17. a volatile organic treatment system; 18. solvent or inert gas is injected into the system.
101. The connection systems 11 and 12; 201. the connection systems 12 and 13; 301. the connection systems 13 and 14; 401. connecting systems 14 and 15.
The material 601 enters a feeding section 12 of a devolatilization system through a feeding deoxidation system 16 and then through 602, a solvent 801 enters a melting and mixing section 13 of the devolatilization system through a solvent or inert gas injection system 18 and through 802, tail gas which is discharged from the melting and mixing section 13 of the devolatilization system and a conveying and exhausting section 14 of the devolatilization system and is carried with volatile components and mixed solvents enters a volatile organic matter treatment system 17 through an exhaust port 302 and a vacuum degassing port 402 respectively, the tail gas is treated and discharged after reaching the standard 701, and the recovered solvent is recovered and stored by 702.
Detailed Description
In certain embodiments, the method comprises subjecting the maleated graft copolymer to be treated to remove entrained air while blending with other feedstocks to obtain a pretreated blend; the blend comprises the maleated graft copolymer, a filler, a scratch resistant agent, an antioxidant, a weather resistant agent, a lubricant and the like.
In certain embodiments, the degassing step is not necessarily independent during the pretreatment, and may be performed, for example, by providing an open section in the feed section. The main body part of the devolatilization equipment consists of a feeding section, a melting and mixing section, a conveying and exhausting section and a cooling, granulating and drying part; the accessory equipment consists of a solvent introducing system, a vacuum devolatilization system and a volatile organic compound treatment system.
In certain embodiments, the blend is introduced into a feed section of a volatiles removal system where it is melted by shear heating, mixed, and simultaneously mixed with a solvent or inert gas added in this section to extract volatiles from the molten blend. The introduction device for the solvent or inert gas is installed at the initial stage of the melting zone of the processing apparatus.
In certain embodiments, the addition of a solvent serves two purposes, one being to swell the swellable portion of the blend and the other being to entrain volatiles from the blend from another solvent upon swelling. The added solvent can be a mixed solvent, wherein different components respectively play roles in swelling and entrainment, or the same component has larger property change along with the change of operating conditions and respectively plays roles in swelling and entrainment at different stages.
In certain embodiments, the molten solvent-mixed blend enters the melt conveying vent section of the processing equipment and the vacuum devolatilization system is mounted at the open devolatilization port of the melt conveying vent section and connected to a vacuum pump system at the devolatilization port.
In certain embodiments, solvent and/or inert gas entrained with volatiles collected in the melt delivery vent section is passed to a volatile organic processing system, where the solvent or inert gas is recovered while removing the volatiles removed from the polymer. The solvent or inert gas recovered by the volatile organic compound treatment system is communicated with a conveying device of the solvent or inert gas.
In certain embodiments, the melt is passed through a conveying vent section and then into a cooling, pelletizing and drying section to obtain a low volatile product made from the maleated graft copolymer.
Further, in certain embodiments, the devolatilizer body is a twin screw extruder.
In some embodiments, the devolatilizer body is a separate body, such as by melt mixing in an extruder, and the molten material is degassed as it enters a batch kettle and is transported to the next extruder.
In certain embodiments, the solvent employed is a complex solvent or an inert gas.
In certain embodiments, the solvent employed comprises nitrogen, carbon dioxide, toluene, xylene, benzene, dimethylformamide, dimethylacetamide, acetone, butanone, N-methyl-2-pyrrolidone, methyl isobutyl ketone, ethyl acetate, butyl acetate, diethyl ether, cyclohexanone, ethylene glycol, methanol, ethanol, pyridine, N-butanol, N-hexane, cyclohexane, tetrahydrofuran, water, or mixtures thereof.
In certain embodiments, the devolatilization system has a vacuum pressure value of less than 0.1MPa absolute, from 1 Pa to 1000Pa, preferably from 10 Pa to 100 Pa.
In certain embodiments, the voc treatment system recovery process employs condensation, adsorption, absorption, or a combination thereof.
In some embodiments, the voc treatment system recovery process employs a condensation, adsorption process.
In certain embodiments, the voc treatment system recovery process employs absorption, condensation, adsorption processes.
In certain embodiments, the voc treatment system recovery process employs an absorption, adsorption process.
In another aspect, the present application relates to a system for preparing a low volatile maleated graft copolymer from a maleated graft copolymer containing a high volatile. Wherein maleation refers to grafting the polymer with maleic acid or maleic anhydride, or mixtures thereof; the polymer comprises polyethylene, or polypropylene, or polyamide, or mixtures thereof; volatile components mean that low molecular organic volatiles are derived from unpolymerized polymer monomers, solvents, low molecular weight polymers, uncrosslinked additives, reaction byproducts, and the like.
In certain embodiments, the method comprises subjecting the maleated graft copolymer to be treated to remove entrained air while blending with other feedstocks to obtain a pretreated blend; the blend comprises the maleated graft copolymer, a filler, a scratch resistant agent, an antioxidant, a weather resistant agent, a lubricant and the like.
In certain embodiments, the degassing step is not necessarily independent during the pretreatment, and may be performed, for example, by providing an open section in the feed section. The main body part of the devolatilization equipment consists of a feeding section, a melting and mixing section, a conveying and exhausting section and a cooling, granulating and drying part; the accessory equipment consists of a solvent introducing system, a vacuum devolatilization system and a volatile organic compound treatment system.
In certain embodiments, the blend is introduced into a feed section of a volatiles removal system where it is melted by shear heating, mixed, and simultaneously mixed with a solvent or inert gas added in this section to extract volatiles from the molten blend. The introduction device for the solvent or inert gas is installed at the initial stage of the melting zone of the processing apparatus.
In certain embodiments, the addition of a solvent serves two purposes, one being to swell the swellable portion of the blend and the other being to entrain volatiles from the blend from another solvent upon swelling. The added solvent can be a mixed solvent, wherein different components respectively play roles in swelling and entrainment, or the same component has larger property change along with the change of operating conditions and respectively plays roles in swelling and entrainment at different stages.
In certain embodiments, the molten solvent-mixed blend enters the melt conveying vent section of the processing equipment and the vacuum devolatilization system is mounted at the open devolatilization port of the melt conveying vent section and connected to a vacuum pump system at the devolatilization port.
In certain embodiments, solvent and/or inert gas entrained with volatiles collected in the melt delivery vent section is passed to a volatile organic processing system, where the solvent or inert gas is recovered while removing the volatiles removed from the polymer. The solvent or inert gas recovered by the volatile organic compound treatment system is communicated with a conveying device of the solvent or inert gas.
In certain embodiments, the melt is passed through a conveying vent section and then into a cooling, pelletizing and drying section to obtain a low volatile product made from the maleated graft copolymer.
Further, in certain embodiments, the devolatilizer body is a twin screw extruder.
In some embodiments, the devolatilizer body is a separate body, such as by melt mixing in an extruder, and the molten material is degassed as it enters a batch kettle and is transported to the next extruder.
In certain embodiments, the solvent employed is a complex solvent or an inert gas.
In certain embodiments, the solvent employed comprises nitrogen, carbon dioxide, toluene, xylene, benzene, dimethylformamide, dimethylacetamide, acetone, butanone, N-methyl-2-pyrrolidone, methyl isobutyl ketone, ethyl acetate, butyl acetate, diethyl ether, cyclohexanone, ethylene glycol, methanol, ethanol, pyridine, N-butanol, N-hexane, cyclohexane, tetrahydrofuran, water, or mixtures thereof.
In certain embodiments, the devolatilization system has a vacuum pressure value of less than 0.1MPa absolute, from 1 Pa to 1000Pa, preferably from 10 Pa to 100 Pa.
In certain embodiments, the voc treatment system recovery process employs condensation, adsorption, absorption, or a combination thereof.
In some embodiments, the voc treatment system recovery process employs a condensation, adsorption process.
In certain embodiments, the voc treatment system recovery process employs absorption, condensation, adsorption processes.
In certain embodiments, the voc treatment system recovery process employs an absorption, adsorption process.
Other aspects and advantages of the present disclosure will be readily apparent to those skilled in the art from the following detailed description. Only exemplary embodiments of the present disclosure have been shown and described in the following detailed description. As those skilled in the art will recognize, the disclosure enables those skilled in the art to make changes to the specific embodiments disclosed without departing from the spirit and scope of the invention as claimed in the present application. Accordingly, the descriptions in the drawings and the specification of the present application are illustrative only and not limiting.
The embodiments of the invention are described below with reference to specific embodiments, and other advantages and effects of the invention will be apparent to those skilled in the art from the disclosure in the specification.
In this application, "ppm" generally refers to parts per million, i.e., a concentration expressed in parts per million of the mass of a substance or parts per million of the volume of the entire system, also referred to as a parts per million concentration. For example, when the entire system is a solution system, 1ppm may equal 1 mg/L. As another example, when the entire system is solid, 1ppm may equal 1. mu.g/g.
In the application, the working mechanism of the screw extruder is that materials can be fully plasticized and uniformly mixed by means of pressure and shearing force generated by screw rotation, and the materials are molded through a neck mold; therefore, a series of processes such as mixing, plasticizing, and molding can be simultaneously performed using one extruder, and continuous production can be performed.
In the present application, "melting" refers to the process in which the kinetic energy of the thermal motion of molecules increases as the temperature increases, resulting in the destruction of crystals and the change of the substance from a crystalline phase to a liquid phase.
In this application, "fluid" generally refers to objects, such as liquids and gases, that have a fixed mass and no fixed shape.
In the present application, "condensing medium" generally refers to a substance that can condense the gas and/or liquid to be treated by cooling it by heat exchange.
In this application, "adsorption treatment" generally refers to a process of achieving separation by differences in the adsorption capacity of an adsorbent for different components in a mixture, utilizing the physical adsorption and/or chemisorption properties of the adsorbent. Without wishing to be bound by theory, the spent adsorbent may be regenerated (e.g., by adjusting pressure and/or temperature) during the adsorption process to achieve a cyclic operation. For example, the adsorption process may include pressure swing adsorption, temperature swing adsorption, and/or temperature swing adsorption, among others.
In this application, "condensation treatment" is used interchangeably with "condensation" and generally refers to a process in which some or all of the components in a gas and/or liquid to be treated are condensed upon cooling by heat exchange between a cryogenic condensing medium and the gas and/or liquid to be treated.
In the present application, the term "about" generally means varying from 0.5% to 10% above or below the stated value, for example, varying from 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, or 10% above or below the stated value.
In this application, "fluid communication" generally means that fluid in one device can be introduced into another device between two or more devices.
In this application, "compression" generally refers to the process of decreasing the volume and/or increasing the pressure of a fluid by applying pressure. Compression may be achieved by various suitable means, for example, compression may be achieved by a blower, suction fan and/or compressor.
In this application, "deoxygenation" generally refers to a process of reducing the oxygen content in an object being treated (e.g., a gas mixture) or removing oxygen from an object being treated.
In this application, "substantially does not affect" generally means that there is no substantial change in the result, purpose, appearance, or other aspect that may be observed.
In the present application, "substantially free" generally means that the amount is not detected by conventional means, or the amount does not affect the desired characteristics or objectives. For example, "substantially free" may refer to a content of less than about 5%, less than about 4.5%, less than about 4%, less than about 3.5%, less than about 3%, less than about 2.5%, less than about 2%, less than about 1.5%, less than about 1%, less than about 0.5%, less than about 0.4%, less than about 0.3%, less than about 0.2%, less than about 0.1%, less than about 0.05%, or less.
In this application, "operational flexibility range" generally refers to a range of values above or below a specified value or set point within a certain range that does not substantially affect the operational effectiveness.
In the present application, "rough treatment" generally refers to a process of preliminary treatment of a gas mixture to be treated.
In the present application, "swelling" refers to a phenomenon in which a high molecular polymer expands in volume in a solvent. The swelling stage is not only temperature dependent but also the molecular weight and branching of the polymer and also the solvent. The higher the molecular weight, the higher the branching degree, and the slower the swelling, and the three-dimensional molecules can only swell but can not dissolve due to the constraint of grid nodes.
Where a single solvent is used, solubility or selectivity is often limited, and where a component having a strong affinity for the component to be extracted is added to increase its selectivity and solubility for the component to be extracted, this is known as an entrainer, the "entrainer" and in this application this process is referred to as "entrainment".
In the present application, "off-gas" generally refers to a gas or gas mixture produced in a production process that is to be further processed, discharged, and/or recovered.
In this application, "ambient gas" generally refers to a gas or mixture of gases, such as air, present in the external environment surrounding the system and/or device.
In this application, "design load flow" generally refers to a reasonable load flow that is predetermined or computationally determined for a particular device, system or equipment, thereby ensuring that the device, system or equipment is operating properly at the load flow.
Example 1:
the blends to be treated were:
as shown in FIG. 1, the blend to be treated was fed from 601 into the feed deoxygenation system 16 and then fed 602 into the feed zone 12 of the twin-screw extruder, and the total carbon emission measured at a temperature of 30 ℃ and a total VOCs of 260kg/hr, about 4200. mu.g C/g and about 1092g/hr, into the feed zone 12 was measured. The system 12, the system 13 and the system 14 form a double-screw extruder, the length-diameter ratio of the extruder is L/d-40, the rotating speed is 400r/min, the temperature is controlled at 180 ℃ and 230 ℃, and the melt pressure is 2.2 MPa.
The mixed solvent 801 is composed of polar ethanol and nonpolar n-hexane, and the molar ratio is 1: 10, the mass flow rate is 30 kg/hr. Is injected into the melting and mixing section 13 of the twin screw extruder through 802 via solvent injection system 18. Shearing and stretching a double-screw extruder screw, mixing the molten blend with a mixed solvent, wherein the PP polymer is swelled by n-hexane, the polar ethanol is mixed with the molten blend, removing volatile matters in the PP polymer, discharging the PP polymer from a 302 exhaust port and a 402 vacuum degassing port, and treating the PP polymer in a 17 volatile organic matter treatment system.
The vacuum was 0.01bar (absolute). The volatile organic compound treatment system adopts an active carbon adsorption-mechanical refrigeration condensation system for treatment. The tail gas is firstly adsorbed by active carbon, the tail gas reaching the standard is directly discharged, and the active carbon adopts double towers, one is used for standby, and the continuous production is realized. And (3) desorbing by adopting hot nitrogen at 160 ℃, condensing the concentrated desorbed tail gas by a condensing system, recycling the condensate, and returning the non-condensable gas to the adsorption system for treatment.
The blend after the devolatilization treatment is cooled, granulated and dried or is a low volatile component product. The total carbon emission, i.e., VOCs, was determined to be about 35 μ gC/g.
Example 2:
the blends to be treated were:
as shown in FIG. 1, the blend to be treated was fed from 601 into the feed deoxygenation system 16 and then fed 602 into the feed zone 12 of the twin-screw extruder, the blend entering the feed zone 12 was 280kg/hr, the temperature was 30 ℃ and the total carbon emissions, i.e., VOCs, were measured to be about 5000. mu.gC/g and about 1400 g/hr. The system 12, the system 13 and the system 14 form a double-screw extruder, the length-diameter ratio of the extruder is L/d-40, the rotating speed is 420r/min, the temperature is controlled at 190 ℃ and 230 ℃, and the melt pressure is 2.0 MPa.
The mixed solvent 801 is composed of polar ethanol and nonpolar n-hexane, and the molar ratio is 1: 10, the mass flow rate is 25 kg/hr. Is injected into the melting and mixing section 13 of the twin screw extruder through 802 via solvent injection system 18. Shearing and stretching a double-screw extruder screw, mixing the molten blend with a mixed solvent, wherein the PP polymer is swelled by n-hexane, the polar ethanol is mixed with the molten blend, removing volatile matters in the PP polymer, discharging the PP polymer from a 302 exhaust port and a 402 vacuum degassing port, and treating the PP polymer in a 17 volatile organic matter treatment system.
The degree of vacuum was 0.001MPa (absolute). The volatile organic compound treatment system adopts an active carbon adsorption-mechanical refrigeration condensation system for treatment. The tail gas is firstly adsorbed by active carbon, the tail gas reaching the standard is directly discharged, and the active carbon adopts double towers, one is used for standby, and the continuous production is realized. And (3) desorbing by adopting hot nitrogen at 160 ℃, condensing the concentrated desorbed tail gas by a condensing system, recycling the condensate, and returning the non-condensable gas to the adsorption system for treatment.
The blend after the devolatilization treatment is cooled, granulated and dried or is a low volatile component product. The total carbon emission, i.e., VOCs, was determined to be about 45 μ gC/g.
Example 3:
the blends to be treated were:
as shown in FIG. 1, the blend to be treated was fed from 601 into the feed deoxygenation system 16 and fed via 602 into the feed zone 12 of the twin-screw extruder at a temperature of 30 ℃ and a total carbon emission value of about 3800. mu.g C/g and about 1216g/hr as measured for the blend entering the feed zone 12 of 320 kg/hr. The system 12, the system 13 and the system 14 form a double-screw extruder, the length-diameter ratio of the extruder is L/d-40, the rotating speed is 450r/min, the temperature is controlled at 180 ℃ and 230 ℃, and the melt pressure is 1.5 MPa.
The mixed solvent 801 is composed of polar ethanol and nonpolar n-hexane, and the molar ratio is 1: 10, the mass flow rate is 40 kg/hr. Is injected into the melting and mixing section 13 of the twin screw extruder through 802 via solvent injection system 18. Shearing and stretching a double-screw extruder screw, mixing the molten blend with a mixed solvent, wherein the PP polymer is swelled by n-hexane, the polar ethanol is mixed with the molten blend, removing volatile matters in the PP polymer, discharging the PP polymer from a 302 exhaust port and a 402 vacuum degassing port, and treating the PP polymer in a 17 volatile organic matter treatment system.
The degree of vacuum was 0.001MPa (absolute). The volatile organic compound treatment system adopts an active carbon adsorption-mechanical refrigeration condensation system for treatment. The tail gas is firstly adsorbed by active carbon, the tail gas reaching the standard is directly discharged, and the active carbon adopts double towers, one is used for standby, and the continuous production is realized. And (3) desorbing by adopting hot nitrogen at 160 ℃, condensing the concentrated desorbed tail gas by a condensing system, recycling the condensate, and returning the non-condensable gas to the adsorption system for treatment.
The blend after the devolatilization treatment is cooled, granulated and dried or is a low volatile component product. The total carbon emission, i.e., VOCs, was determined to be about 37 μ gC/g.
Example 4
The copolymer to be treated was a polypropylene PP resin grafted with maleic anhydride (grafting ratio of about 1.0%).
As shown in FIG. 1, the copolymer to be treated was fed from 601 into the feed deoxygenation system 16 and then fed 602 into the feed zone 12 of the twin-screw extruder, and the blend entering the feed zone 12 was 260kg/hr at a temperature of 30 ℃ and the total carbon emission, i.e., VOCs, was measured at about 4200. mu.g C/g and about 1092 g/hr. The system 12, the system 13 and the system 14 form a double-screw extruder, the length-diameter ratio of the extruder is L/d-40, the rotating speed is 440r/min, the temperature is controlled at 180 ℃ and 230 ℃, and the melt pressure is 2.2 MPa.
The extraction medium consists of a mixed solvent and inert gas, the mixed solvent 801 consists of polar methanol and nonpolar toluene, and the molar ratio is 1: 5, the mass flow rate is 30 kg/hr. The inert gas being CO2And (3) mixing a solvent: the ratio of the inert gas was 10:1.5 (mass ratio). Is injected into the melting and mixing section 13 of the twin screw extruder through 802 via solvent injection system 18. Shearing and stretching by a screw of a double-screw extruder, mixing the molten copolymer with a mixed solvent, wherein the molten copolymer is swelled by toluene, mixed with polar methanol and the molten copolymer, and then volatile matters in the molten copolymer are removed, discharged from a 302 exhaust port and a 402 vacuum degassing port, and enter a 17 volatile organic matter treatment system for treatment.
The degree of vacuum was 0.001MPa (absolute). The volatile organic compound treatment system adopts an active carbon adsorption-mechanical refrigeration condensation system for treatment. The tail gas is firstly adsorbed by active carbon, the tail gas reaching the standard is directly discharged, and the active carbon adopts double towers, one is used for standby, and the continuous production is realized. And (3) desorbing by adopting hot nitrogen at 160 ℃, condensing the concentrated desorbed tail gas by a condensing system, recycling the condensate, and returning the non-condensable gas to the adsorption system for treatment.
The copolymer after devolatilization treatment is cooled, granulated and dried or is a product with low volatile component. The total carbon emission, i.e., VOCs, was determined to be about 30 μ gC/g.
Example 5
The copolymer to be treated was a polypropylene PP resin grafted with maleic acid (grafting yield about 1.3%).
The extraction medium is a mixed solvent, and the mixed solvent 801 consists of polar dimethylformamide and nonpolar diethyl ether in a ratio of 20: 1. The rest is the same as example 4.
The copolymer after devolatilization treatment is cooled, granulated and dried or is a product with low volatile component. The total carbon emission, i.e., VOCs, was determined to be approximately 36 μ gC/g.
The invention removes the volatile matters in the copolymer under the vacuum or high vacuum condition in a continuous feeding and discharging way and a solvent entrainment way, realizes devolatilization of materials and environment in the devolatilization process and under the isolation state of operators, increases the efficiency and reduces the energy consumption.
Claims (8)
1. A method of devolatilizing a copolymer, comprising: the method comprises the following steps:
step one, polymerizing a component with stronger polarity and a grafted polymer with weaker polarity to obtain a copolymer, and pretreating the copolymer to be treated to remove entrained air; the component with stronger polarity is selected from one or more of polymethacrylic acid, polymethyl methacrylate, maleic acid and maleic anhydride; the polymer with weak polarity is selected from one of polyethylene, polypropylene and polyamide;
step two, introducing the copolymer into a feed section of a processing device in a volatile removal system;
step three, the copolymer enters a melting and mixing section after passing through a feeding section, and is mixed with an extraction medium added in the melting and mixing section at the same time so as to extract volatile components in the molten copolymer; the extraction medium is selected from a solvent, or the solvent is mixed with an inert gas; the mass ratio of the solvent to the copolymer is 5-50: 100, respectively; the solvent is a mixture of a polar solvent and a non-polar solvent; the molar ratio range of the polar solvent to the non-polar solvent is as follows: 0.05-50: 1; the polar solvent is selected from one or more of the following components: dimethylformamide, dimethylacetamide, acetone, butanone, N-methyl-2-pyrrolidone, methyl isobutyl ketone, methanol, ethanol, tetrahydrofuran and water;
the nonpolar solvent is selected from one or more of the following components: toluene, xylene, benzene, ethyl acetate, butyl acetate, diethyl ether, cyclohexanone, ethylene glycol, pyridine, n-hexane, cyclohexane;
the inert gas is selected from one or more of nitrogen, carbon dioxide, helium and argon;
step four, feeding the melted copolymer mixed with the extraction medium into a conveying exhaust section, wherein the conveying exhaust section is connected with a vacuum devolatilization system, and a devolatilization port of the vacuum devolatilization system is connected with a vacuum pump system; the absolute pressure of the vacuum pressure value is less than 0.1 MPa;
step five, the extraction medium with the volatile components enters a volatile organic matter treatment system, the solvent or inert gas is recycled, and the volatile components removed from the polymer are removed;
and step six, the melt enters a cooling part, a grain cutting part and a drying part after passing through a conveying and exhausting section, and a low-volatile-component product prepared from the copolymer is obtained.
2. A devolatilization process as claimed in claim 1 wherein: the first step comprises negative pressure or inert gas purging, or the negative pressure and the inert gas purging are carried out simultaneously; in the third step, the device for introducing the solvent or the inert gas is arranged at the melting and mixing section of the processing equipment.
3. A devolatilization process as claimed in claim 1 wherein: and the solvent or the inert gas recovered by the volatile organic compound treatment system is communicated with a conveying device of the solvent or the inert gas.
4. A devolatilization process as claimed in claim 1 wherein: the total carbon value of the obtained copolymer with low volatile matter is 1 mu gC/g-100 mu gC/g.
5. A method of devolatilizing a blend characterized by: the method comprises the following steps:
step one, polymerizing a component with stronger polarity and a grafted polymer with weaker polarity to obtain a copolymer, and blending the copolymer with other raw materials to obtain a blend, so that the blend to be treated is pretreated to remove air carried in the blend; the component with stronger polarity is selected from one or more of polymethacrylic acid, polymethyl methacrylate, maleic acid and maleic anhydride; the polymer with weak polarity is selected from one of polyethylene, polypropylene and polyamide;
step two, introducing the blend into a feed section of a processing device in a volatile removal system;
step three, the blend enters a melting mixing section after passing through a feeding section, and is mixed with an extraction medium added in the melting mixing section during melting so as to extract volatile components in the melting blend; the extraction medium is selected from a solvent, or the solvent is mixed with an inert gas; the mass ratio of the solvent to the blend is 5-50: 100, respectively; the solvent is a mixture of a polar solvent and a non-polar solvent; the molar ratio range of the polar solvent to the non-polar solvent is as follows: 0.05-50: 1; the polar solvent is selected from one or more of the following components: dimethylformamide, dimethylacetamide, acetone, butanone, N-methyl-2-pyrrolidone, methyl isobutyl ketone, methanol, ethanol, tetrahydrofuran and water;
the nonpolar solvent is selected from one or more of the following components: toluene, xylene, benzene, ethyl acetate, butyl acetate, diethyl ether, cyclohexanone, ethylene glycol, pyridine, n-hexane, cyclohexane;
the inert gas is selected from one or more of nitrogen, carbon dioxide, helium and argon;
step four, feeding the melted blend mixed with the extraction medium into a conveying exhaust section, wherein the conveying exhaust section is connected with a vacuum devolatilization system, and a devolatilization port of the vacuum devolatilization system is connected with a vacuum pump system; the absolute pressure of the vacuum pressure value is less than 0.1 MPa;
step five, the extraction medium with the volatile components enters a volatile organic matter treatment system, the solvent or inert gas is recycled, and the volatile components removed from the polymer are removed;
and step six, the melt enters a cooling part, a grain cutting part and a drying part after passing through a conveying and exhausting section, and a low-volatile-component product prepared from the blend is obtained.
6. A devolatilization process as claimed in claim 5 wherein: the first step comprises negative pressure or inert gas purging, or the negative pressure and the inert gas purging are carried out simultaneously; in the third step, the device for introducing the solvent or the inert gas is arranged at the melting and mixing section of the processing equipment.
7. A devolatilization process as claimed in claim 5 wherein: and the solvent or the inert gas recovered by the volatile organic compound treatment system is communicated with a conveying device of the solvent or the inert gas.
8. A devolatilization process as claimed in claim 5 wherein: the total carbon value of the obtained copolymer with low volatile matter is 1 mu gC/g-100 mu gC/g.
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| CN114130303B (en) * | 2021-11-27 | 2023-11-14 | 南京创博机械设备有限公司 | TGIC efficient devolatilization and melt extrusion granulation integrated processing method |
| CN115122527A (en) * | 2022-06-09 | 2022-09-30 | 万华化学集团股份有限公司 | Polyolefin granulation process |
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