Method for continuous solution copolymerization and device for its implementation

 

(57) Abstract:

The invention relates to the production of polymers, the synthetic rubber industry, namely the method of production of ethylene-propylene or ethylene propylene-diene copolymer and device for its implementation. The method comprises dissolving in a hydrocarbon solvent monomers, hydrogen and catalytic components of the complex flow of gas-liquid mixtures containing monomers, solvent and hydrogen, in the lower part of the first reactor, separate feeding solutions of the components of the catalytic complex in the reactor, the copolymerization under stirring the reaction mixture at elevated pressure and temperature, the supply of the solution of the copolymer in the second reactor for smoothing and stabilization and subsequent washing solution of the copolymer aqueous medium, representing water, steam, aqueous solution with a pH below neutral, from the products of the catalytic complex and allocation crumbs copolymer of its solution. The washing solution of the copolymer is carried out at the turbulent mixing of a solution of the copolymer and the water environment education in a tubular mixer flow speed is not less than 1,50,7 m/s Mixer cleaning products catalytic to the supply tube copolymer solution coincides with the axis of the tubular mixer, the axis of the feed pipe of the water environment is at an angle to the axis of the cone of the second section of the tubular mixer, and the end of the feed pipe of the water environment coincides with the axis of the tubular mixer and is located at a distance from the center of the confuser of the second section at least 1/6 of the length of the section. The proposed method and the device allow the mortar copolymerization of obtaining copolymers with low invariable residues of the catalytic complex. 2 S. p. f-crystals, 2 ill., table 1.

The invention relates to the field of polymers, industrial synthetic rubber, namely, the method of production of ethylene-propylene or ethylene propylene-diene copolymers.

The invention relates also to a device for carrying out the process of copolymerization of ethylene-propylene rubbers.

There is a method of continuous solution copolymerization and the reactor-mixer for its implementation (Patent RU N 2141873 IPC7B 01 J 19/18, C 08 F 2/06, op. 17.11.99).

The copolymerization is conducted in the preparation of gas-liquid mixture, and separate dissolved components of the catalytic complex in the solvent is carried out in a flow of not less than 32 m/s for gas-liquid mixture and at least 0.3 m/s copolymerization and to provide the necessary level of quality of the obtained copolymer.

The closest is essentially a method of producing a copolymer of ethylene and propylene double or triple in an environment of hydrocarbon solvent (Album technological schemes the main production of the synthetic rubber industry. P. A. Kirpichnikov, Century Century Berestnev, L. M. Popova. L., Chemistry - 1986, S. 154-162).

The copolymerization is carried out in two consecutive reactors equipped with stirrers srabnogo type and shirts for heat dissipation. Gas-liquid mixture is fed into the lower portion of the first reactor. The catalyst solution is fed through the lower fitting, and socialization - in-line charge. The copolymerization is carried out at a temperature of 402oC and a pressure of 1.4 MPa, time copolymerization of 0.5-1 hour. The solution of copolymer is removed from the top of the first reactor and served in the second reactor, where it is averaged and enter the stabilizer. Then, the solution of the copolymer serves in an intensive mixer with a stirrer, into which feed steam to remove the catalytic complex. After settling the water solution of the copolymer serves to krasnobrizhaya and on to further processing to obtain a briquette copolymer.

The described method does not allow to obtain a copolymer of ethylene and propylene necessary cutecolor in the product. In addition, the technology used requires significant energy consumption for the rotation of the agitator in the environment of high-viscosity solutions.

There is a method of continuous solution copolymerization of ethylene, propylene and 1,4-hexadiene and device for its implementation (U.S. Pat. Germany N 2413139, Z. 19.03.74, prior. USA from 19.03.73, N 342423, op. 11.09.80). The copolymerization of the monomers is carried out at a stirring in the presence of hydrogen and a coordination catalyst, the resulting preliminary mixture of the catalyst components with the solvent in the mixer with a rotating body and a continuous injection of a solution of catalyst in the reactor. A device for implementing the above method comprises a mixer for mixing and reactor. A cylindrical mixing chamber with the inlet channels, and inside it is rotating mixer capable when rotating to scrape the sides of the mixing chamber saducees the reaction products.

However, the disadvantage of this device is the inability to create equal conditions of copolymerization, because in such a reactor with a mixer difficult to obtain uniform distribution of the components in the reaction mass.

However, the disadvantage of this device is the lack of efficiency washing polymerizate of the catalyst and significant energy consumption on the rinse polymerizate.

The objective of the invention is to develop a method and device allowing to carry out continuous solution copolymerization of obtaining copolymers with low invariable residues of the catalytic complex.

The problem is solved using the method of continuous solution copolymerization, comprising dissolving in a hydrocarbon solvent monomers, hydrogen and catalytic components of the complex flow of gas-liquid mixtures containing monomers, rasho complex in the reactor, the copolymerization under stirring the reaction mixture at elevated pressure and temperature, the supply of the solution of the copolymer in the second reactor for smoothing and stabilization and subsequent washing solution of the copolymer aqueous medium, representing water, steam, aqueous solution with a pH below neutral, from the products of the catalytic complex, highlighting crumbs copolymer of its solution. The washing solution of the copolymer is carried out at the turbulent mixing of a solution of the copolymer and the water environment education in a tubular mixer flow with the speed of at least 1.5 0.7 m/s, while the axis of the feed pipe of the water environment is to the axis of the tubular mixer at an angle , and the inner surface of the tubular mixer is a sequential combination of narrowing and widening the diameter of the nozzles.

The inventive method is carried out in a device for the continuous solution copolymerization containing preparation system, the gas-liquid mixture and the catalytic components of the complex, two reactors copolymerization, mixer cleaning products of the catalytic complex and crosscoordination. The housing of the mixer tube, composed of sections confuser and cone rigidly connected to the second mixer, the axis of the feed pipe of the water environment is at an angle to the axis of the cone of the second section of the tubular mixer, and the socket end coincides with the axis of the tubular mixer at a distance from the center of the confuser at least 1/6 of the length of the section.

Distinctive features of the proposed method continuous solution copolymerization is that the washing solution of the copolymer is carried out at the turbulent mixing of a solution of the copolymer and the water environment education in a tubular mixer flow with the speed of at least 1.5 0.7 m/s, while the axis of the feed pipe of the water environment is to the axis of the tubular mixer at an angle , and the inner surface of the tubular mixer is a sequential combination of narrowing and widening the diameter of the nozzles.

Distinctive features of the proposed device for the continuous solution copolymerization is that the housing of the mixer tube, composed of sections confuser and cone rigidly interconnected into a single structure, with the axis of tube feeding copolymer solution coincides with the axis of the tubular mixer, the axis of the feed pipe of the water environment is at an angle to the axis of the cone of the second section, and the end of tube feeding Vodnany section.

The process of cleaning products deactivated catalytic complex of the copolymer solution is an aqueous medium, representing water, steam or an aqueous solution of various compounds having a pH below neutral.

The process consists in dissolving in the aqueous environment of the products of the catalytic complex. The degree and time of washing is largely determined by the conditions of distribution of the aquatic environment in the volume of the polymer solution and the intensity of mixing. Given that the process of continuous copolymerization, and the resulting copolymer in an organic solvent and water have different surface tension, density, nature and viscosity, the creation of a continuous flow organology emulsion with rapidly changing interfacial surface at the border of the aqueous medium solution of the copolymer is only possible if developed turbulent motion.

Developed turbulent motion of the flow for the configuration of the inner surface of the tubular mixer, which is a sequential combination of narrowing and widening the diameter of the nozzles without ponding. When this stream is subjected to alternately compress and expand, contributing to education is about the whole volume of the moving stream.

Under the action of turbulent eddies in the solution of the copolymer aqueous solution quickly dispersed into fine particles and is uniformly distributed throughout the volume of flow of a solution of the copolymer.

On the formed interfacial boundary of the emulsion is in the process of dissolution products of catalytic complex in the aquatic environment. Swirl flow is called continuous intensive movement of the lamellae, which provides continuous updates to the interface. This leads to the intensification of the process of washing. Iterative (6 or more times) turbulization of the flow provides the most complete cleaning products of the catalytic complex of the copolymer solution.

The use of the inventive device provides a high degree of mixing of a solution of the copolymer aqueous medium to form a thin emulsion continuously updated interfacial surface.

The choice of geometry of the tubular mixer, diameters of the cone and confuser, the angles of the narrowing and widening truncated cones confuser, the position of connectors input copolymer solution and water, all this ensures the achievement of a developed turbulent motion in the ass the thief copolymer, the reliability of the equipment and saves energy consumed for rotation of the mixing elements.

In the patent and scientific literature there is no information about the aggregate marked distinctive features with the above purpose, a method of continuous solution copolymerization, and device for its implementation.

In addition, the implementation of the method of continuous solution copolymerization, in which the washing solution of the copolymer are in the turbulent regime, is only possible in the inventive device.

In Fig. 1 shows a diagram of a continuous mortar of copolymerizate. Cooking system gas-liquid mixture contains the comb 1 and the tubular turbulent mixer 2. The first polymerization reactor 3 is equipped with a stirrer, a heat-exchange jacket (not labeled), a hose gas-liquid mixture 4, the hose of a solution of catalyst 6 and socializaton 5 and fitting exhaust solution of copolymer 7.

The second copolymerization reactor 8 is connected to the first reactor 3 by a pipe 9. The reactor 8 equipped with a stirrer and heat transfer face (not labeled), a hose dissolve the shaped products 13 for recirculation.

The solution of copolymer pipeline pump 14 is fed in a tubular mixer 15 through the pipe 16 serves aqueous medium and then to crosscoordination 17 and degassing chamber 18.

In Fig. 2 shows a tubular mixer, which is a pipe of variable cross-section, consisting of sections. The section consists of a diffuser 19 and confuser 20. The confuser is made of narrowing and widening truncated cones connected together, with the angle . Sections rigidly interconnected. Tubular mixer is attached by the flange 21 to the supply pipe copolymer solution 22, with their axes coincide. In the diffuser of the second section introduced the nozzle 16, the axis of which forms with the axis of the tubular mixer angle . The end of the feed pipe of the water environment 16 coincides with the axis of the tubular mixer and is located from the center of the confuser at least 1/6 of the length of the section.

Continuous solution copolymerization works as follows. The cooled components of the gas-liquid mixture (monomer, solvent and hydrogen) in certain proportions under pressure is fed to the comb 1 and the tubular turbulent mixer 2. Gas-liquid mixture through the nozzle 4 of the first reactor 3 is fed in the Torah 3 using a mixing device is homogenized, forming a reaction mass, and begins the process of copolymerization. The resulting copolymer through the nozzle 7, the pipe 9 and nozzle 10 gets to the second polymerization reactor 8. In the reactor 8 are removed from the copolymer solution through the nozzle 13 unreacted gaseous monomers, and the introduction of the stabilizer is made through the fitting 11. Average and stable solution of the copolymer through the nozzle 12 by the pump 14 is fed to the cleaning products of the catalytic complex in a tubular mixer (Fig. 2). In the first section of the cone-confused-type solution of the copolymer turbulizers, it turbulent eddies and supplied water after passing through the confuser second section quickly finely dispersed by the volume of the main stream with the formation of aqueous-organic emulsion. The washed copolymer emulsion is served in crosscoordination 17, which under the influence of water vapor is released copolymer from solution in the form of crumbs. Aqueous dispersion in the crystallizer 18 is divided into separate streams of water, solvent and crumbs copolymer. Crumb copolymer then enters the drying and briquetting.

The claimed method of continuous mortar, copolymerizate the CLASS="ptx2">

Example 1

In the first polymerization reactor with a volume of 16.6 m3and the mixer rotation speed of 35 rpm below enter cooled to a temperature of minus 10oC gas-liquid mixture in an amount of 2480 kg/h containing the following components:

Propylene liquid (GOST 25043-87) - 0,15

Ethylene (GOST 25070-87) - 0,10

The purified hydrogen (GOST 3022-80) - 0,05

The Dicyclopentadiene (TU 14-6-35-86) - 0.104 G

The recirculation gas (ethylene, propylene, hydrogen, Dicyclopentadiene) - 0,66

The components of the gas-liquid mixture proportioning is fed to the distributor and from there to a 4-sectioned tubular turbulent mixer. Filing solutions catalyst VOCl3(THE 48-4-533-90) in the amount of 1.5 0.1 kg/h and socializaton Al(C2H5)2Cl (TU 38.1011228-90) to 150.2 kg/h nerase separately through the side fittings. The total flow of nefras 5000 kg/hour, a Pressure in the first reactor 0.55 MPa, the temperature of the reaction mixture inside the reactor is maintained within the range of 35-45oC. Unloading solution ternary copolymer of ethylene and propylene (Sept) carry out through the nozzle in the cover of the first reactor. The solution of copolymer gravity through the conduit through the nozzle input is fed to the second polymerization reactor. The pressure inside the reaction the unreacted gaseous monomers and hydrogen diverted for recycling. Through the side fitting of the second reactor is injected stabilizer is 2,2-Methylenebis(6-tert-butyl-4-METHYLPHENOL) - Agidol-2 (TU 38.101.617-80) in the amount of 0.4-0.6 kg/h Averaged and stable solution of the copolymer pump AH 20/150-400 is served in a tubular mixer. It has a diameter of 150 mm, and confuser - 75 mm, the Angle of the truncated cones confuser 60o. The length of the tubular section of the mixer 400 mm, number of sections - 8.

In the case of the second diffuser section made the hole and through it entered and sealed tube feeding aqueous medium with a diameter of 50 mm, the axis of the nozzle and diffuser form an angle of 45o. The end of the feed pipe of the water environment and outdoor coincides with the axis of the tubular mixer and is at a distance of 70 mm from the center of the cone. Weight solution of the copolymer 7500 kg/h, water environment 7500 kg/h when driving aqueous organic emulsion in a tubular mixer is implemented, the flow rate of 0.93 (at least 1,50,7) m/s, which provides the conditions of a developed turbulent motion and effective washing of the solution of the copolymer products of the catalytic complex. In krasnobratii aqueous-organic emulsion is treated with steam under a pressure of 0.8-1.0 MPa. Formed in the crystallizer strikethrough. The results of the experiments are shown in the table, the experience 1.

Example 2

The conditions of the experiment as described in example 1, but the copolymerization process in the first reactor is carried out at a pressure of 0.35 MPa. Under these conditions, the output solution of the copolymer smaller and 6300 kg/H. Hence the quantity of the water environment in the washing solution of the copolymer is less. Speed total flow rate of 0.7 m/s the Results are shown in the table, the experience 2.

Example 3

The conditions of the experiment as described in example 1, the position of the end of tube feeding aquatic environment relative to the center of the cone of the second section of the tubular mixer is 45 mm, the results of the experiments are shown in the table, experience 3.

Example 4 (comparison)

The conditions of the experiment as shown in example 1. But instead of tubular mixer at the stage of washing with water solution of copolymer is used mixer GARTH AVE-A4-6 speed mixer 720 rpm motor power 20 kW. The results of the experiments are shown in the table, the experience 4.

Example 5

In the device described in example 1, shall receive isoprene elastomer (SKI-3).

A liquid mixture containing

Isoprene (TU 38.103659-88) - 0,20

From the in which hydrogen is introduced in an amount of 1% of the volume of the liquid mixture. The catalytic complex, a mixture of titanium tetrachloride (TU 1715-455-05785388-99) and triisobutylaluminum (TU 38.103154-79) in the amount of 350 kg/h in a solution of toluene (GOST 14710-78), through the side pipe is served in the volume of the reactor. The polymerization is carried out at a pressure of 0.5 MPa and a temperature of the reaction mass 38-42oC.

In the second reactor, the polymerization is carried out at a pressure of 0.35 MPa and the temperature of the reaction mixture 54-58oC. Stabilization of the solution of isoprene elastomer in the reactor does not operate.

The solution of the elastomer in the number 41200 kg/h mixed with 2500 m3water in a tubular mixer at a flow rate of more than 3.6 m/s, which provides the conditions of a developed turbulent motion and effective washing of the solution products of catalytic complex salts of titanium). Further, the processing solution of the elastomer is carried out on the technology.

The results of the experiments show that the wash water solution of a copolymer of SKEPT experience 1 provides the greatest removal of vanadium from the copolymer. Changing conditions of flow below 0.8 m/s lowers washing vanadium.

The quality of the copolymer is reflected in noncompliance with the provisions of the socket end from the center of the cone of the WTO is RA (although it is within tolerance) and additionally electricity is consumed by the rotation of the agitator.

The reduction of the titanium content in the isoprene elastomer (experiment 5) is also achieved by the conditions of the wash water solution of the elastomer under conditions of turbulent flow.

1. Method for continuous solution copolymerization, comprising dissolving in a hydrocarbon solvent monomers, hydrogen and catalytic components of the complex flow of gas-liquid mixtures containing monomers, solvent and hydrogen, in the lower part of the first reactor, separate feeding solutions of the components of the catalytic complex in the reactor, the copolymerization under stirring the reaction mixture at elevated pressure and temperature, the supply of the solution of the copolymer in the second reactor for smoothing and stabilization and subsequent washing solution of the copolymer aqueous medium, representing water, steam, aqueous solution with a pH below neutral, from the products of the catalytic complex and allocation crumbs copolymer of its solution, characterized in that the washing solution of the copolymer is carried out at the turbulent mixing of a solution of the copolymer and the water environment education in a tubular mixer flow speed is not less than 1,50,7 m/s, while the axis of the feed pipe of the water environment is to the axis of the tubular specialagent and expansion of the diameter of the nozzles.

2. Device for the continuous solution copolymerization containing preparation system, the gas-liquid mixture and the catalytic components of the complex, two reactors copolymerization, mixer cleaning products of the catalytic complex and crosscoordination, characterized in that the housing of the mixer tube, composed of sections of confusion and diffusers, rigidly interconnected into a single structure, with the axis of tube feeding copolymer solution coincides with the axis of the tubular mixer, the axis of the feed pipe of the water environment is at an angle to the axis of the cone of the second section of the tubular mixer, and the end of the feed pipe of the water environment coincides with the axis of the tubular mixer and is located at a distance from the center of the confuser of the second section at least 1/6 of the length of the section.

 

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