CN114432721A - Method for concentrating polymer solution and application thereof - Google Patents
Method for concentrating polymer solution and application thereof Download PDFInfo
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- CN114432721A CN114432721A CN202011211594.2A CN202011211594A CN114432721A CN 114432721 A CN114432721 A CN 114432721A CN 202011211594 A CN202011211594 A CN 202011211594A CN 114432721 A CN114432721 A CN 114432721A
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Abstract
The invention discloses a method for concentrating a polymer solution and application thereof. The method comprises the following steps: concentrating the organic solution containing the polymer to obtain organic solvent gas and the concentrated organic solution containing the polymer; and the organic solvent gas is used as a heat source for the concentration process after being pressurized. According to the method for concentrating the polymer solution, the organic solvent gas obtained from the top of the concentrating equipment is pressurized and then is used as the heat source of the tower kettle of the concentrating equipment, so that the energy consumption in the concentrating process can be effectively reduced, the energy is saved, and the production cost of the polymer is further reduced.
Description
Technical Field
The invention belongs to the field of polymer preparation, and particularly relates to a concentration method of a polymer solution and application thereof.
Background
The solution method is mostly adopted in industry to produce halogenated butyl rubber, ethylene propylene rubber, styrene block copolymer and hydrogenated derivatives thereof, solution polymerized butylbenzene and other polymers, and because the molecular weight of the polymers is large, the viscosity of the polymer solution is increased along with the increase of the concentration, and the excessively high viscosity can greatly increase the energy consumption of mass transfer and influence the operation effects of reaction, washing and the like. Therefore, the polymer needs to be controlled to have a low concentration in the steps of preparation of the reaction solution, washing treatment of the reaction solution, and the like. There is a problem of concentration of the polymer solution both before and after the reaction from the viewpoint of removal of impurities or economical efficiency of operation.
For example, halogenated butyl rubber, is prepared by reacting butyl rubber with a halogen in a solvent. Butyl rubber is an important synthetic rubber product due to excellent air tightness, weather resistance and other properties, but butyl rubber also has the defects of poor miscibility with other rubbers and slow vulcanization speed, and halogenated butyl rubber overcomes the defects of butyl rubber, so that the industrial application of halogenated butyl rubber is expanded compared with butyl rubber.
The production of the butyl rubber product adopts a slurry method low-temperature cationic polymerization process: isobutene and a small amount of isoprene are used as reaction monomers, aluminum trichloride is used as a catalyst, methyl chloride is used as a diluent, the concentration of the reaction monomers is 10-20 wt%, a cationic polymerization reaction is carried out at a low temperature of-100 ℃, a polymerization product is suspended in the methyl chloride to form slurry, the formed slurry enters a degassing kettle from an overflow pipe at the top of the polymerization kettle, the methyl chloride and unreacted monomers are separated out in a gas phase, and a mixture of separated butyl rubber particles and water is subjected to water separation, drying and dehydration to obtain a finished butyl rubber product.
Dissolving the finished product butyl rubber in C5-C6 alkane to obtain a butyl rubber solution, carrying out contact reaction with halogen to obtain a halogenated butyl rubber solution, simultaneously producing hydrogen halide as a byproduct, carrying out alkali neutralization and water precipitation on the halogenated butyl rubber solution to separate a solvent to obtain a mixture of halogenated butyl rubber particles and water, and dehydrating and drying to obtain the finished product halogenated butyl rubber.
It can be seen that, the butyl rubber and the halogenated butyl rubber have different reaction systems, and different solvents are used, so that the problem of solvent replacement inevitably exists in the production process of continuously producing the halogenated butyl rubber after the butyl rubber is synthesized by taking isobutene and isoprene as raw materials. The commercially usual process is to prepare halogenated butyl rubber by direct contact of hexane with a butyl rubber slurry, dissolution of the butyl rubber particles in hexane to form a gum mixture, separation of the methyl chloride and unreacted monomers isobutylene and isoprene, and reaction of the resulting hexane solution of butyl rubber with halogen. Since the butyl rubber is slowly dissolved at low temperature and the viscosity of the resulting solution after dissolution is high, the concentration of the dope after solvent conversion has to be maintained at 5 to 8 wt%, and the concentration of the dope becomes an indispensable step for removing the residual unreacted monomer in the solution and for the sake of reaction economy.
The polymer prepared by the solution method is mostly separated from the solvent and unreacted monomers by a water precipitation condensation method, the polymer solution is contacted with hot water and/or steam, the polymer in the polymer solution is gradually concentrated along with vaporization and evaporation of a large amount of solvent so as to form solid particles, and the solvent is separated from the polymer as a gas phase along with the steam. The polymer solution elutriation and condensation device concentrates 80% of the loss amount of the solvent and 50% of energy consumption, is the equipment with the largest energy consumption and material consumption in the polymer production process, and is one of the fields of energy conservation and consumption reduction key issues in the polymer production process by the solution method.
The function of the water vapor in the process of the water precipitation and condensation mainly comprises the following steps: (1) sensible heat required for heating the glue solution and the condensation hot water to the condensation temperature is provided; (2) providing latent heat of vaporization of hydrocarbon solvents in the glue solution; (3) carrying out the gaseous hydrocarbons in the condensation kettle. Based on the method, the concentration of the polymer is improved, the solvent amount entering a water precipitation and condensation process is reduced, and the energy consumption can be effectively reduced.
Meanwhile, how to reduce the energy consumption in the process of concentrating the glue solution also becomes an important means for reducing the production cost of the polymer.
Disclosure of Invention
The invention provides a method for concentrating a polymer solution, which comprises the following steps: concentrating the organic solution containing the polymer to obtain organic solvent gas and the concentrated organic solution containing the polymer; and pressurizing the organic solvent gas to be used as a heat source in a concentration process.
According to an embodiment of the present invention, the organic solvent in the organic solution is a C5 alkane and/or a C6 alkane, for example n-hexane.
According to an embodiment of the invention, the polymer is selected from butyl rubber, halogenated butyl rubber, ethylene-propylene rubber, styrenic block copolymerizers and hydrogenated derivatives thereof, hydrogenated nitrile rubber or solution polymerized styrene-butadiene.
Preferably, the polymer is a halogenated butyl rubber or butyl rubber.
According to an embodiment of the present invention, the means of concentration may be distillation. For example, the concentration is carried out in a distillation apparatus.
According to an embodiment of the invention the concentration of the polymer-containing organic solution after concentration is increased by 1-30 wt%, such as 2-20 wt%, preferably 3-15 wt% higher than the concentration of the polymer-containing organic solution before concentration.
According to an embodiment of the present invention, the pressurization is performed by using a pressurization device for pressurizing the organic solvent gas, for example, the pressurization device is a compressor. Preferably, the pressure ratio is from 1.1 to 6, for example from 1.5 to 4.
According to an embodiment of the present invention, the pressure of the pressurized organic solvent gas is 180-1000kPa, such as 200-500kPa, and further such as 220-260 kPa.
According to an embodiment of the present invention, the pressurization process is accompanied by a temperature increase of the organic solvent gas. For example, the temperature of the organic solvent gas after pressurization is increased by 20 to 60 deg.C, such as 20 to 45 deg.C, and as another example 25 to 40 deg.C, compared to the temperature of the organic solvent gas before pressurization.
According to the embodiment of the invention, the pressurized organic solvent gas is used as a heat source of the distillation equipment and exchanges heat with the tower bottom liquid of the distillation equipment to obtain the tower bottom liquid and the organic solvent condensate after the temperature is increased. Wherein, the tower bottom liquid after temperature increase returns to the tower bottom of the distillation equipment, and the organic solvent condensate is recovered.
The invention also provides a concentration method of the butyl rubber solution, which comprises the following steps: concentrating the n-hexane solution containing the butyl rubber to obtain n-hexane gas and the concentrated n-hexane solution containing the butyl rubber; and the n-hexane gas is used as a heat source for the concentration process after being pressurized.
Preferably, the n-hexane solution containing the butyl rubber can also contain a small amount of unreacted monomers, wherein the unreacted monomers comprise isobutene and/or isoprene.
Preferably, the n-hexane solution containing the butyl rubber can be prepared by the following processes: the butyl rubber slurry prepared by a methyl chloride slurry method is contacted with an n-hexane solvent, butyl rubber is dissolved in the n-hexane, and methyl chloride and most of unreacted isobutene and isoprene monomers are separated and removed to obtain an n-hexane solution of the butyl rubber.
The invention provides the application of the concentration method of the polymer solution in the preparation of polymers.
Wherein the polymer has the meaning as described above.
The concentration method is generally applicable to the following cases: where it is desired to reduce or eliminate the level of impurities in the polymer solution and/or simply increase the polymer concentration.
The "dope" and the "solution" as used herein mean the same.
The invention has the beneficial effects that:
according to the method for concentrating the polymer solution, the organic solvent gas obtained from the top of the concentrating equipment is pressurized and then is used as the heat source of the tower kettle of the concentrating equipment, so that the energy consumption in the concentrating process can be effectively reduced, the energy is saved, and the production cost of the polymer is further reduced.
Drawings
FIG. 1 is a schematic flow chart of a method for concentrating an n-hexane solution of butyl rubber in example 1;
reference numerals: E. the device comprises a reboiler, a K compressor, a T distillation tower, a V receiving tank, 1 dilute glue solution, 2 n-hexane gas phase, 3 pressurized n-hexane gas phase, 4 tower kettle solution, 5 heated tower kettle solution, 6 n-hexane condensate, 7 concentrated glue solution.
Detailed Description
The technical solution of the present invention will be further described in detail with reference to specific embodiments. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Unless otherwise specified, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.
Example 1
The method comprises the steps of contacting butyl rubber slurry liquid prepared by a methyl chloride slurry method with an n-hexane solvent, dissolving butyl rubber in the slurry liquid in the n-hexane, separating methyl chloride and most unreacted isobutene and isoprene monomers, feeding residual butyl rubber n-hexane dilute glue liquid 1 from the middle of a distillation tower T, feeding n-hexane gas phase 2 from the top of the distillation tower into a compressor K for pressurization to obtain pressurized n-hexane gas phase 3, feeding the pressurized n-hexane gas phase 3 into a reboiler E for heat exchange with a tower bottom solution 4 from the bottom of the distillation tower, cooling and liquefying the pressurized n-hexane gas phase 3 to obtain n-hexane condensate 6, feeding the n-hexane condensate 6 into a receiving tank V, feeding the tower bottom solution 4 after heat exchange to obtain a temperature-increased tower bottom solution 5, and returning to the lower part of a concentration tower T. And (4) discharging concentrated glue liquor 7 from the tower bottom of the distillation tower T.
Example 2
In the procedure of the concentration method shown in example 1, a butyl rubber slurry prepared by a methyl chloride slurry method was contacted with an n-hexane solvent to dissolve butyl rubber in the slurry in the n-hexane, after methyl chloride and most of unreacted monomers are separated, butyl rubber n-hexane solution with the concentration of 13 weight percent is obtained, the flow rate is 143900kg/h, wherein the content of normal hexane is 87 weight percent, the normal hexane enters a distillation tower from the middle lower part, the operating pressure of the distillation tower is 130kPa, 40000kg/h of normal hexane gas phase produced at the top of the tower is controlled, the temperature of the normal hexane gas phase at the top of the tower is 79 ℃, the normal hexane gas phase enters a compressor K, the pressure is increased to 240kPa, the temperature is increased to 105 ℃, the heated and pressurized normal hexane gas phase enters a reboiler E of the distillation tower T, exchanging heat with the tower bottom solution at the temperature of 81 ℃, heating the tower bottom solution to 84 ℃, returning the tower bottom solution to the lower part of the distillation tower, and maintaining the tower bottom temperature of the distillation tower by taking the n-hexane gas phase after heating and pressurizing as a heat source. And (4) pressurizing the n-hexane gas phase for liquefaction after heat exchange to obtain n-hexane condensate for recovery. The column bottom obtained 103900kg/h of a concentrated butyl rubber cement solution with a concentration of 18 wt%. The power of the compressor K is 320 kW.
Comparative example
The feeding amount and the tower operation parameters are the same as those of the embodiment 2, except that: a reboiler E at the tower bottom of the distillation tower adopts 0.8MPa water vapor as a heat source, and gas-phase hexane at the tower top is condensed and cooled by circulating water at the temperature of 30 ℃. The steam consumption was 6.7t/h and the amount of circulating water for cooling was 580 t/h.
In the embodiment 2, the gas phase at the top of the pressurized tower is used as the heat source of the reboiler of the tower kettle, so that the water vapor consumption is saved, the use of circulating water is reduced, and assuming that the electric charge is 0.65 yuan/degree, the water vapor is 180 yuan/ton, the circulating water treatment cost is calculated according to 0.45 yuan/ton, and the energy consumption in the embodiment 2 is the power consumption: 320 × 0.65 ═ 208 yuan/h; the energy consumption in the comparative example was: 6.7 × 180+580 × 0.45 ═ 1467 yuan/h. Example 2 saves 1259 yuan/h of energy costs.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. A method for concentrating a polymer solution, comprising the steps of: concentrating the organic solution containing the polymer to obtain organic solvent gas and the concentrated organic solution containing the polymer; and the organic solvent gas is used as a heat source for the concentration process after being pressurized.
2. The concentration method according to claim 1, wherein the organic solvent in the organic solution is a C5 alkane and/or a C6 alkane, preferably n-hexane.
3. A concentration process according to claim 1 or 2, characterized in that the polymer is selected from butyl rubber, halogenated butyl rubber, ethylene-propylene rubber, styrenic block copolymerizers and hydrogenated derivatives thereof, hydrogenated nitrile rubber or solution polymerized styrene-butadiene.
Preferably, the polymer is a halogenated butyl rubber or butyl rubber.
4. A concentration method according to any of claims 1-3, characterized in that the way of concentration is distillation. Preferably, the concentration is carried out in a distillation apparatus.
Preferably, the concentration of the polymer-containing organic solution after concentration is increased by 1 to 30 wt% compared to the concentration of the polymer-containing organic solution before concentration.
5. A concentration method according to any one of claims 1-4, wherein the pressurization is carried out by using a pressurization device to pressurize the organic solvent gas, such as a compressor. Preferably, the pressure ratio is 1.1-6.
6. The concentration method according to any one of claims 1 to 5, wherein the pressure of the pressurized organic solvent gas is 180-1000kPa, preferably 200-500 kPa.
Preferably, the pressurization process is accompanied by a temperature increase of the organic solvent gas. Preferably, the temperature of the organic solvent gas after pressurization is increased by 20 to 60 ℃ as compared to that before pressurization.
Preferably, the pressurized organic solvent gas is used as a heat source of the distillation equipment, and exchanges heat with the tower bottom liquid of the distillation equipment to obtain the tower bottom liquid and the organic solvent condensate after the temperature is increased.
7. The concentration process according to any one of claims 1 to 6, wherein the polymer solution is a butyl rubber solution, and the concentration process of the butyl rubber solution comprises the following steps: concentrating the n-hexane solution containing the butyl rubber to obtain n-hexane gas and the concentrated n-hexane solution containing the butyl rubber; and the n-hexane gas is used as a heat source for the concentration process after being pressurized.
8. The concentration method according to claim 7, wherein the n-hexane solution containing the butyl rubber further contains a small amount of unreacted monomers, and the unreacted monomers comprise isobutene and/or isoprene.
Preferably, the n-hexane solution containing the butyl rubber is prepared by the following steps: the butyl rubber slurry prepared by a methyl chloride slurry method is contacted with an n-hexane solvent, butyl rubber is dissolved in the n-hexane, and methyl chloride and most of unreacted isobutene and isoprene monomers are separated and removed to obtain an n-hexane solution of the butyl rubber.
9. Use of a method of concentrating a polymer solution according to any one of claims 1 to 8 in the preparation of a polymer, preferably in the preparation of a polymer by a solution process.
Preferably, the polymer has the meaning as defined in claim 3.
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| GB850429A (en) * | 1958-01-24 | 1960-10-05 | Exxon Research Engineering Co | Processing halogenated butyl rubber |
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| CN111793154A (en) * | 2020-06-30 | 2020-10-20 | 北京诺维新材科技有限公司 | Preparation method and preparation device of rubber |
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| GB850429A (en) * | 1958-01-24 | 1960-10-05 | Exxon Research Engineering Co | Processing halogenated butyl rubber |
| CN102770461A (en) * | 2010-01-20 | 2012-11-07 | 朗盛国际股份公司 | Common solvent process for producing high molecular weight brominated rubber |
| CN102702409A (en) * | 2012-06-07 | 2012-10-03 | 北京石油化工学院 | Technology for directly producing halogenated butyl rubber using butyl glue prepared by solution method |
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