POLYMERIZATION INSTALLATION WITH INTEGRATED COMBINED ABSORPTION-DIFFUSSION AND ABSORPTION-CONDENSATION UNIT AND ITS APPLICATION FOR THE PREPARATION OF POLYMERS AND COPOLYMERS

Abstract

The invention relates to a polymerization plant with an integrated combined absorption-diffusion and absorption-condensation unit, and to its potential use for preparing various polymers and copolymers by addition, emulsion, suspension, or radical polymerization, which will have applications in the chemical industry. According to the invention, the plant has the following four structural units: a supply unit (A), a reaction unit (B), a combined absorption-diffusion and absorption-condensation unit (C), and a finished product discharge unit (D).

Description

POLYMERIZATION INSTALLATION WITH INTEGRATED COMBINED ABSORPTION-DIFFUSSION AND ABSORPTION-CONDENSATION UNIT AND ITS APPLICATION FOR THE PREPARATION OF POLYMERS AND COPOLYMERS FIELD OF INVENTION The invention relates to a polymerization installation with an integrated combined absorption-diffusion and absorption-condensation unit, as well as the possibility of its use for the preparation of various polymers and copolymers by various types of processes: addition polymerization, emulsion, suspension or radical polymerization. The installation of the present invention will have application in the chemical industry. BACKGROUND OF THE INVENTION The various structural systems and apparatus for the production of polymers and copolymers known from the literature and practice are distinguished mainly according to the polymerization method applied, as well as the method of providing maintenance of the introduction and continuous or periodic interaction between the basic and auxiliary reagents involved in the process. A large number of installations with different purposes are also known, in which Venturi-type structural elements are installed to intensify the impact on pressure and temperature. MA / a / ZUZZ / UUOl 1 z Ref. 331214 Patent RU2626614 presents a heating system that ensures savings in steam consumption, which is implemented in an installation comprising a heat exchanger, a supply device to feed steam to the heat exchanger with a control valve and a point for measuring the steam flow to a Venturi tube, a condensate trap and a secondary steam generator, from which the steam flow is taken to a low pressure zone within the Venturi tube and its connection to the main steam flow passing there. United States Patent Application No. 4,657,994 describes a method for the continuous production of EVA by emulsion polymerization using an aliphatic alcohol solvent, claiming improved removal of reaction heat, comprising a multi-tube heat exchanger and a polymerization vessel with a mixer, wherein, during heat exchange, and in order to raise the temperature of the incoming reactants fed into the top of the heat exchanger to a higher melting point, heat is extracted from another recirculating reactant with a lower boiling point and the vapors released from the reactor are introduced into the bottom of the heat exchanger, with simultaneous solubilization of the reactants in the heat exchanger. United States patent application 4,282,339 MA / a / ZUZZ / UUOl 1 z describes an ethylene polymerization process carried out in a reaction system consisting of two reactors connected in series (tubular or autoclave type) with an intermediate heat exchanger with a cooler installed between them, wherein the reaction flow from the first reactor passes through the heat exchanger at high pressure and temperature, and from there, the cooled reaction flow, the pressure of which has been reduced by means of a pressure relief valve, is introduced into the second reactor for further polymerization. United States patent application 4,035,329 relates to a method for emulsion polymerization of styrene and butadiene carried out in a system consisting of a reactor and a tubular heat exchanger above it, into the top of which butadiene vapor from the reactor is introduced and the cooled condensate is returned to the reactor to lower the temperature of the reaction mixture. Patent 6,831,139 describes a method for the production of poly(ethylene-vinyl acetate) (EVA) in a polymerization solution, in the presence of an initiator, carried out in an installation consisting of a polymerization reactor and a reflux condenser in which the vapors of at least one of the components of the polymerization solution are received and the cooled condensate is returned to the reactor by recirculation. ML / a / ZUZZ / UUO 11 z However, the best-known design solutions provide equipment methods for the production of copolymers in which, in addition to the main components (primary polymers), several other reagents are used to accompany the polymerization. BRIEF DESCRIPTION OF THE INVENTION A problem of the present invention is the creation of an installation for the production of polymers and copolymers, ensuring the performance of various types of polymerization and copolymerization processes, i.e., addition, emulsion, suspension or radical polymerization, using primary and secondary polymers as basic starting components, and with the maximum limited participation of additional reagents in relation to the polymerization process. The problem of the invention is solved by means of a polymerization installation with an integrated combined absorption-diffusion and absorption-condensation unit, wherein four design units are structurally differentiated as follows: A) A supply unit (A) (Figure 1), comprising: a) a thermal helical conveyor 1 equipped with a heat-resistant metal tubular housing 2 comprising and driven by an electric motor and a reduction gear, a metal rod shaft (4) on which a non-uniform pitch spiral is installed, and the middle part of the metal housing 2 of the thermal helical conveyor 1 is equipped with electric heaters 3 and temperature sensors; b) an intermediate vessel 5 for pouring the melt from the thermal helical conveyor 1, equipped with a cover 6, in which a degasser 7 and an explosion-proof valve 8 are mounted, and in the middle part of the intermediate vessel 5 there are valves 9 for feeding other main and / or auxiliary reagents for the polymerization process; c) a screw feeder 10, driven by an electric motor and a reduction gear, with an integrated single-step monolithic conveying coil 11, which receives the melt from the intermediate vessel 5 and feeds it to an autoclave-type reactor with a mixer, which is also equipped with temperature sensors and a pressure sensor. B) A reaction unit (B) (Figure 1), comprising: a) a reactor body 12 with a mixer 18 and a heating coil 23 built into the reactor body 12, which is equipped with temperature and pressure sensors, and on the top of which is installed a fixed outlet pipe 24 for the installation of a diffuser 25; b) a reactor cover 13 fixed over the reactor body 12, in which inlet openings are located laterally and opposite each other, to which the retainer 20 is fixed, the inlet tube of which is fixed to a lateral inlet in the cover 13. E) A unit for the discharge of finished polymer (D), which includes: (a) outlet pipe 31 fixed at one end to the bottom of the reactor body 12 and at the other end to the screw outlet conveyor 32; (b) the outgoing helical conveyor 32 driven by an electric motor and reduction gear, and terminating with an outgoing helical screw head 33 to seal the system and to allow the finished product to pass through it. BRIEF DESCRIPTION OF THE FIGURES Figure 1 is a drawing of a general arrangement of the polymerization installation; Figure 2 is a longitudinal section of the combined absorption-diffusion and absorption-condensation unit. DETAILED DESCRIPTION OF THE INVENTION The supply of primary or secondary polymer used as the main starting reagent in the supply unit is carried out via a heated helical conveyor 1 equipped with a heat-resistant tubular metal housing 2, in the middle of which annular electric heaters 3 are installed. The number and power of the electric heaters 3 are determined by the MA / a / ZUZZ / UUOl 1 z capacity of the thermal helical conveyor 1 and the temperature to which the starting polymer undergoing melting will be heated. The working area of ​​the thermal helical conveyor 1 consists of a rod shaft 4 driven by an electric motor and reduction gear, on which a three-step helical screw is installed. The connection between the reduction gear and the shaft of the helical conveyor 4 is fixed. The thermal helical conveyor 1 is arranged horizontally with a free outlet, from which the polymer melt enters the intermediate vessel 5 located below, which is tubular, vertically arranged, heat-resistant, and resistant to high pressures. The intermediate vessel 5 serves as a tank after the outlet of the thermal helical conveyor 1 and as a dosing system for the polymerization installation according to the present invention.At the top of the intermediate vessel 5 is a cover 6 installed to seal the vessel and the working area of ​​the installation after the melt has been fed from the heated screw conveyor 1. The degasser 7 and explosion relief valve 8 are installed on the cover 6 of the intermediate vessel 5. Valves 9 are installed in the middle section of the intermediate vessel 5 to feed other main and / or auxiliary reagents for the polymerization process. The bottom of the intermediate vessel 5 is attached to a horizontally mounted screw feeder 10, which has a heat-resistant and high-pressure resistant tubular metal housing containing a single-pass monolithic conveying coil (11).The screw feeder 10 is driven by an electric motor with a reduction gear, whose power is determined by the capacity and supply speed of the vertically arranged autoclave-type polymerization reactor, which is resistant to high temperature and pressure. At the top of reactor body 12 is a fixed cover 13. Pipe 14 permanently connects the screw feeder 10 to an inlet opening located laterally in the cover 13, through which the reaction mixture enters the reactor body 12. At the top of the cover 13, along the central axis of the reactor body 12, is a fixed pipe 15 for mounting the electric motor 16 and reduction gear 17 to drive the mixer 18 in the reactor body 12, which is located at the bottom of the reactor body 12 and is connected to the reduction gear 17 by means of a high-temperature resistant metal rod 19. Laterally and opposite pipe 14, a pipe with a fixed check valve 20 is fixed to the cover 13, which is fixed to pipe 21 for taking condensate from the absorption-condensation zone of the heat exchanger. MA / a / ZUZZ / UUOl 1 z double-shelled heat 22, and return it to the inner part of the reactor body 12. Also mounted on the cover 13 of the reactor body 12 are couplings for the installation of temperature and pressure sensors, as well as a coupling for the installation of an explosion-proof valve. The reactor body 12 is also equipped with temperature and pressure sensors, as well as an integrated heating coil 23. At the top of the reactor body 12, under the fixed cover 13, a tube 24 is fixed, located at the beginning of the combined absorption-diffusion and absorption-condensation unit and designed to provide a fixed support for the diffuser 25, with an integrated fixed check valve 26 which is intended to provide rectilinear motion in the direction of the diffuser 25 to a multicomponent, mainly gaseous, mixture formed above the reaction zone at the bottom of the reactor body 12. A high-strength, temperature-resistant pipe 27 fixes the diffuser 25 to the rectification plate 28 mounted on and extending into the inner part of the outer housing 29 of the double-shelled heat exchanger 22.The pipe 27, which facilitates absorption-diffusion interaction and the movement of the multicomponent thermodynamic flow of a primarily gaseous mixture at high temperature, is initially arranged horizontally at a length comparable to the dimensions of the double-shelled heat exchanger 22. It then rises vertically to its connection fixed to the rectification plate 28. The heat exchanger 22 is a horizontally arranged hollow double-shelled vessel. A hollow conical tubular body 30, functioning as a Venturi tube, is located in the outer cylindrical housing 29 of the double-shelled heat exchanger 22. This tube connects to the top of the rectification plate 28, thus forming an absorption-condensation zone and an intense heat exchange zone within the double-shelled heat exchanger 22.One end of the condensate drain line 21 is fixed to the outlet of the double-shell heat exchanger 22, and the other end of the pipe 21 is fixed to the inlet pipe with a check valve 20 fixed inside, allowing the pressure reduction and the straight movement of the condensate from the absorption-condensation zone of the double-shell heat exchanger 22, and its return to the inner part of the reactor body 12, through a side opening in the cover 13, to which it is fixedly attached. The outlet pipe 31 is fixed to the bottom of the reactor body 12, which at its other end is fixed to the screw outlet conveyor 32, terminating with a screw outlet head 33 to seal the working area of ​​the installation and allow the resulting polymer to MA / a / ZUZZ / UUOl 1 z pass through it. Temperature sensors are mounted on the output helical screw head 33 to carry out temperature control in the finished product. Fixed connections in the polymerization installation and the absorption-diffusion and absorption-condensation unit integrated therein shall preferably be made as flange connections. The polymerization installation with the integrated combined absorption-diffusion and absorption-condensation unit, in accordance with the invention, allows the performance of different types of polymerization processes, i.e., addition, emulsion, suspension or radical polymerization. As a result of the above, it is also possible to prepare various polymers and / or copolymers, such as: poly(ethylene-vinyl acetate) copolymers by addition polymerization; latex products, for example, butadiene styrene by addition, emulsion or radical polymerization; methyl methacrylate and its copolymers by emulsion or suspension polymerization; styrene acrylonitrile copolymers by addition polymerization, emulsion or suspension; styrene carboxylate copolymers for modifications of concrete by emulsion or suspension polymerization; low-density polyethylene (LDPE, for short) MA / a / ZUZZ / UUOl 1 z English) or high-density polyethylene (HDPE) by a free radical mechanism. Both primary and secondary polymers or the residue from the primary process can be used as starting reagents in the polymerization installation with the integrated combined absorption-diffusion and absorption-condensation unit according to the present invention. The advantages of the polymerization installation with integrated combined absorption-diffusion and absorption-condensation unit according to the invention are: its wide applicability for obtaining different types of polymers and / or copolymers; the possibility of carrying out different types of polymerization processes, including the production of identical or similar polymers and / or copolymers through different types of polymerization processes; Its low energy consumption, due to the elimination of the need to remove the excess heat of reaction obtained during the polymerization processes and its direct use to maintain the performance of the chemical and physicochemical processes within the polymerization facility in accordance with the invention. Modality of the Invention The invention is illustrated by the following examples, which clarify it without limitation. MA / a / ZUZZ / UUOl 1 z protection range. Preparation of poly(ethylene-vinyl acetate) copolymer Example 1 Primary low-density polyethylene (LDPE) is fed to the heated screw conveyor and heated to melting. It is then mixed with vinyl acetate and sodium persulfate in the intermediate vessel, and the reaction mixture is fed into the reactor body. The temperature in the reaction zone is gradually raised to 190 °C with continuous mixing of the reaction medium at 20 rpm until the pressure increases and a gas recirculation process begins. The resulting fluid mixture passes through the diffuser at high speed through the absorption-diffusion section of the high-strength, temperature-resistant pipe, then enters the rectification plate and condenses in the double-walled heat exchanger. The condensate from the absorption-condensation section of the heat exchanger returns to the reactor through the check valve.The recirculation cycle continues until the addition copolymerization process is complete after 2 hours, after which the resulting product is discharged from the reactor through the outlet pipe, the outlet screw conveyor, and the outlet screw conveyor. Example 2 Secondary polyethylene (HDPE) is fed in and heated to melting on the heated helical conveyor, followed by processes similar to those described in Example 1, except that the temperature in the reaction zone is raised to 250 °C while mixing at 10 rpm until the end of the 4.5-hour copolymerization process. Preparation of maleated polypropylene Example 3 Polypropylene homopolymer is fed into the reactor and heated on the heated screw conveyor. In the intermediate vessel, it is mixed with maleic anhydride with a density of 1.48 g / cm³. Processes similar to those described in Example 1 are carried out, except that the temperature on the feed screw conveyor is raised to 210 °C. Complete melting and homogenization of the polymer melt takes place in the reactor, while the reaction medium is mixed at 10 rpm at 230 °C. The time required to carry out and complete the polymerization process is 3 hours, after which the modified melt is discharged via the outlet screw conveyor, cooled, and granulated. Example 4 Secondary polypropylene with a density of 0.86 g / cm³ is fed in and heated on the heated screw conveyor, and mixed with maleic anhydride in the intermediate vessel. Processes similar to those described in Example 1 take place, except that the temperature in the MA / a / ZUZZ / UUOl 1 z helical screw feeder raises the temperature to 220 °C, and then to 240 °C in the reaction zone, while the reaction medium is mixed at 20 rpm. The time to carry out and complete the polymerization process is 2 hours, after which the finished product is removed via the outfeed screw conveyor, cooled, and granulated. Preparation of low and high density polyethylene with improved resistance to UV rays and oxidative thermal degradation Example 5 Primary polyethylene with a density of 0.92 g / cm3 (HDPE) is fed and heated on the heated screw conveyor. In the intermediate vessel, it is mixed with Irganox 1010, CAS No. 6683-19-8, with a melting point of 110-125 °C, chemically named tetraoxypentaerythritol (3(3,5-di-tert-butyl-4-hydroxyphenyl) propionate), with a molecular weight of 1178 g / mol, as a weight percentage versus polymer equal to 0.4% by weight as an antioxidant, and UVASORB HA7 7 DF, CAS No. 52829-07-9, a light stabilizer with the chemical formula C28H52N2O4, with a molecular weight of 480.73 g / mol and a melting point of 82-85 °C, in a polymer weight ratio of 0.5 to 1.5. % by weight as a photostabilizer additive. Similar processes to those described in Example 1 are carried out, except that the temperature of the reaction mixture in the MA / a / ZUZZ / UUOl 1 z helical feed conveyor is raised to 150 °C, and to 190 °C in the reactor, while the reaction medium is mixed at 10 rpm. The homogenization time is 1 hour. The homogeneous and stabilized melt is removed from the reactor by means of the screw conveyor outlet. Example 6 Primary polyethylene with a density of 0.97 g / cm3 (LOPE) is fed and heated on the heated screw conveyor. In the intermediate vessel, it is mixed with Irganox 1010, CAS No. 6683-19-8, with a melting point of 110-125 °C, chemically known as tetraoxypentaerythritol (3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate), and a molecular weight of 1178 g / mol, at a weight percentage of 0.4% by weight of the polymer as an antioxidant, and UVASORB HA7 7 DF, CAS No. 52829-07-9, a light stabilizer with the chemical formula C28H52N2O4, with a molecular weight of 480.73 g / mol and a melting point of 82-85 °C, at a polymer weight ratio of 0.5 to 1.5% by weight as a photostabilizing additive. Similar processes to those described in Example 1 are carried out, except that the temperature in the screw feed conveyor is raised to 150 °C, and then to 190 °C in the reaction zone, while the reaction medium is mixed at 15 rpm.The homogenization time is 1 hour. The homogeneous and stabilized melt is removed from the reactor by. MA / a / ZUZZ / UUOl 1 z middle of the outgoing helical conveyor. Preparation of polystyrene, styrene-acrylate latex Example 7 In this case, the feed from the helical conveyor to the reactor is eliminated and its supply is only carried out through dosing valves of the intermediate vessel until the formation of a reaction mixture of styrene© with a molar mass of 104.15 g / mol, a density of 909 kg / m3, and a boiling point of 145 °C, water as an emulsifier, sodium persulfate with a molecular weight of 238.03 g / mol, a density of 2.4 g / cm3 and a solubility in water of 55.6 g / 100 ml (20 °C) as an initiator, and acrylic acid with a molecular mass of 72.06 g / mol, a density of 1.05 g / cm3 and a boiling point of 139 °C. The process is carried out with continuous mixing at 30 rpm, at temperatures up to 100 °C. The processes are carried out in a similar manner to those described in Example 1 until the monomer is completely exhausted and converted to polystyrene polymer, which after its removal from the reactor is separated from the aqueous phase by centrifugation and dried. Example 8 The reactor is fed as in example 7, through dosing valves from the intermediate vessel until a reaction mixture of styrene and water is formed. MA / a / ZUZZ / UUOl 1 z emulsifier, benzoyl peroxide with a density of 1.3 g / cm3 and a melting point of 103 °C as an initiator and methacrylic acid. The process is carried out with continuous mixing at 40 rpm until the monomer is completely exhausted, at a temperature of up to 110 °C, but the styrene acrylate particles remain in the liquid medium and the finished latex product is characterized by a dry content of 50 to 60% by weight. It is hereby stated that, as of this date, the best method known to the applicant for putting the aforementioned invention into practice is the conventional method for manufacturing the objects to which it refers.

Claims

1. A polymerization installation with an integrated combined absorption-diffusion and absorption-condensation unit comprising an autoclave-type polymerization reactor installed within the reactor body, a mixer, and a cover fixed over the reactor body, characterized in that it comprises a feed block, a reaction block, a combined absorption and condensation unit, and a discharge unit for the removal of the finished product structurally formed in the installation, wherein: a) the supply unit comprises a heated helical conveyor equipped with a tubular metal housing with a shaft located therein, driven by an electric motor and reduction gear, on which a spiral is installed, and the middle part of the metal body of the heated helical conveyor is equipped with electric heaters and temperature sensors to achieve the melting of the main outlet polymer,The free outlet of the thermal helical conveyor is located above an intermediate vessel for pouring the melt from the thermal helical conveyor. The intermediate vessel is equipped with a cover, in which a degasser and an explosion-proof valve are installed, while in the middle part of the intermediate vessel there are valves installed for supplying other reagents, and the lower part of the intermediate vessel is fixed to a screw feeder with a single-pass monolithic conveying coil integrated therein; b) the reaction unit also includes a heating coil built into the reactor body and an outlet pipe fixed at the top, the purpose of which is to permanently connect a diffuser, and in the cover that is fixed to the top of the reactor body there are inlet openings located laterally and opposite each other,to which is permanently attached a pipe for feeding the reaction mixture from the screw feeder and an inlet pipe with a fixed check valve for introducing condensate from the outlet of the double-shell heat exchanger into the inside of the reactor body, while at the top of the cover there is a pipe installed to fix an electric motor and reduction gear that drive the mixer located at the bottom of the reactor body and is connected to the reduction gear by means of a metal rod; c) the combined absorption-diffusion and absorption-condensation unit includes an outlet pipe fixed to the top of the reactor body with a diffuser attached to the same, with an integrated check valve fixed to one end of the pipe,whose other end is fixed to a grinding plate installed and extending into the inner part of the outer housing of the double-shelled heat exchanger, the outer housing also comprising a hollow conical tubular body connected to the top of the grinding plate constructed within the outer housing, and at the outlet of the double-shelled heat exchanger one end of the pipe is fixed to an inlet pipe with a check valve installed therein, which is fixed to the side inlet in the cover; d) the unit for discharging the finished product includes an outlet pipe fixed at one end to the bottom of the reactor body, and at the other end to an outlet screw conveyor terminating with an outlet screw head.

2. The polymerization installation with an integrated combined absorption-diffusion and absorption-condensation unit according to claim 1, characterized in that the connections fixed thereto are preferably made as flange connections.

3. The integrated combined absorption-diffusion and absorption-condensation unit in a polymerization installation according to claim 1, which MA / a / ZUZZ / UUOl 1 z comprises a heat exchanger and a Venturi tube as a structural element, characterized in that it also comprises an outlet pipe fixed to the top of the reactor body to which a diffuser is permanently attached, with an integrated check valve, fixed to one end of the pipe having initially a horizontal arrangement that varies in length commensurate with the vertical length of the double-shelled heat exchanger, and the pipe at its other end being fixed to the rectification plate permanently attached to and constructed in the outer housing of the double-shelled heat exchanger,whereby in the outer housing of the double-shell heat exchanger there is also a hollow conical tubular body connected to the top of the rectification plate and at the outlet of the double-shell heat exchanger one end of the pipe is fixed to an inlet pipe with a check valve installed therein, which is fixed to the side inlet in the cover fixed to the top of the reactor body; 4. The use of the polymerization installation according to claim 1 for the preparation of poly(ethylene-vinyl acetate) copolymers from a primary or secondary starting polymer by addition polymerization. MA / a / ZUZZ / UUOl 1 z 5. The use of the polymerization facility according to claim 1 for the preparation of butadiene styrene from a primary or secondary starting polymer by addition, emulsion or radical polymerization.

6. The use of the polymerization facility according to claim 1 for the preparation of latex products from a primary or secondary starting polymer by addition, emulsion or radical polymerization.

7. The use of the polymerization facility according to claim 1 for the preparation of methyl methacrylate and its copolymers from a primary or secondary starting polymer by emulsion or suspension polymerization.

8. The use of the polymerization facility according to claim 1 for the preparation of styrene acrylonitrile copolymers from a primary or secondary starting polymer by emulsion or suspension polymerization.

9. The use of the polymerization facility according to claim 1 for the preparation of styrene carboxylate copolymers for concrete modifications by emulsion or suspension polymerization.

10. The use of a MA / a / ZUZZ / UUOl 1 z polymerization installation in accordance with claim 1 for the preparation of low-density polyethylene (LDPE) or high-density polyethylene (HDPE) from a primary or secondary starting polymer by radical polymerization.

Images