CN114432721B - Polymer solution concentration method and application thereof - Google Patents
Polymer solution concentration method and application thereof Download PDFInfo
- Publication number
- CN114432721B CN114432721B CN202011211594.2A CN202011211594A CN114432721B CN 114432721 B CN114432721 B CN 114432721B CN 202011211594 A CN202011211594 A CN 202011211594A CN 114432721 B CN114432721 B CN 114432721B
- Authority
- CN
- China
- Prior art keywords
- butyl rubber
- hexane
- solution
- concentrating
- concentration
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D1/00—Evaporating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D1/00—Evaporating
- B01D1/30—Accessories for evaporators ; Constructional details thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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; the organic solvent gas is pressurized and then used as a heat source for the concentration process. According to the method for concentrating the polymer solution, disclosed by the invention, the organic solvent gas obtained from the top of the concentrating equipment is pressurized and then is used as a 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, hydrogenated derivatives thereof, solution polymerized butylbenzene and other polymers, and as the molecular weight of the polymers is large and the concentration is increased, the viscosity of the polymer solution is increased, and the excessively high viscosity greatly increases the energy consumption of mass transfer, and influences the operation effects of reaction, washing and the like. Therefore, the polymer needs to be controlled to a low concentration in the steps of preparing the reaction solution, washing the reaction solution, and the like. The problem of concentration of the polymer solution is present both before and after the reaction, due to the removal of impurities or the economic nature of the operation.
For example halogenated butyl rubber, is prepared by reacting butyl rubber with halogen in a solvent. Butyl rubber is an important synthetic rubber product because of excellent air tightness, weather resistance and the like, but the butyl rubber also has the defects of poor blending property with other rubbers and low vulcanization speed, and the halogenated butyl rubber overcomes the defects of the butyl rubber, so that the industrial application of the halogenated butyl rubber is expanded compared with that of the butyl rubber.
The production of butyl rubber products 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 10-20wt%, cationic polymerization is carried out at a low temperature of about minus 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, methyl chloride and unreacted monomers are separated from gas phase, and the separated butyl rubber colloidal particles and water mixture are subjected to water separation and drying dehydration to obtain the finished butyl rubber.
And dissolving the finished butyl rubber in C5-C6 alkane to obtain butyl rubber solution, then carrying out contact reaction with halogen to obtain halogenated butyl rubber solution, simultaneously obtaining byproduct hydrogen halide, carrying out alkali neutralization and water separation and condensation separation on the halogenated butyl rubber solution to obtain a mixture of halogenated butyl rubber colloidal particles and water, and carrying out dehydration and drying to obtain the finished halogenated butyl rubber.
It is apparent that the reaction systems of butyl rubber and halogenated butyl rubber are different, and different solvents are used, so that the problem of solvent replacement inevitably exists in the production process of continuously producing halogenated butyl rubber after synthesizing butyl rubber by using isobutene and isoprene as raw materials. The common method in industry is to directly contact hexane and butyl rubber slurry, dissolve butyl rubber particles in hexane to form a glue solution mixture, then separate chloromethane and unreacted monomers-isobutene and isoprene, and then obtain butyl rubber hexane solution for reaction with halogen to prepare halogenated butyl rubber. Since butyl rubber is slowly dissolved at low temperature and the viscosity of the solution formed after dissolution is high, the concentration of the gum solution after solvent conversion has to be maintained at 5 to 8wt% in order to remove the remaining unreacted monomers in the solution, and the gum solution concentration is an indispensable step for reaction economy.
The polymer prepared by the solution method is mostly separated from solvent and unreacted monomers by a water separation condensation method, the polymer solution is contacted with hot water and/or steam, the polymer in the polymer solution is gradually concentrated along with evaporation of a large amount of solvent to form solid particles, and the solvent is separated as gas phase and polymer along with steam. The water-out coagulation device of the polymer solution concentrates 80% of the loss amount of the solvent and 50% of the energy consumption, is equipment with the largest energy consumption and material consumption in the polymer production process, and is one of the important fields of energy conservation and consumption reduction in the polymer production process of the solution method.
The water vapor in the water separation and condensation process mainly comprises the following functions: (1) Sensible heat required for heating the glue solution and the condensed hot water to the condensation temperature is provided; (2) providing latent heat of vaporization of the hydrocarbon solvent in the gum solution; (3) carrying out the gas phase hydrocarbon in the coagulation kettle. Based on this, the increased polymer concentration reduces the amount of solvent entering the water-out coagulation step, which can effectively reduce the energy consumption.
Meanwhile, how to reduce the energy consumption in the concentration process of the glue solution is also 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; the organic solvent gas is pressurized and then used as a heat source for the concentration process.
According to an embodiment of the 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 copolymers and hydrogenated derivatives thereof, hydrogenated nitrile rubber or solution polymerized styrene-butadiene.
Preferably, the polymer is halogenated butyl rubber or butyl rubber.
According to an embodiment of the invention, the means of concentration may be distillation. For example, the concentration is performed 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.%, for example by 2-20 wt.%, preferably by 3-15 wt.%, compared to the concentration of the polymer-containing organic solution before concentration.
According to an embodiment of the invention, the pressurizing is pressurizing the organic solvent gas using a pressurizing device, e.g. the pressurizing device is a compressor. Preferably, the pressure ratio is 1.1-6, for example 1.5-4.
According to an embodiment of the invention, the pressurized organic solvent gas has a pressure of 180-1000kPa, e.g. 200-500kPa, and, as another example, 220-260kPa.
According to an embodiment of the invention, the pressurization process is accompanied by a concomitant increase in the temperature of the organic solvent gas. For example, the temperature of the organic solvent gas after pressurization is increased by 20-60 ℃, for example 20-45 ℃, and for example 25-40 ℃ compared with the temperature 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 tower bottom liquid of the distillation equipment to obtain Wen Houda kettle liquid and organic solvent condensate. Wherein, the tower bottom liquid after the temperature is increased returns to the tower bottom of the distillation equipment, and the organic solvent condensate is recovered.
The invention also provides a method for concentrating 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; the n-hexane gas is pressurized and then used as a heat source for the concentration process.
Preferably, the n-hexane solution containing butyl rubber may further contain a small amount of unreacted monomers including isobutylene and/or isoprene.
Preferably, the n-hexane solution containing butyl rubber can be prepared by the following process: the butyl rubber slurry prepared by the methyl chloride slurry method is contacted with a normal hexane solvent, the butyl rubber is dissolved in normal hexane, and methyl chloride and most of unreacted isobutene and isoprene monomers are separated and removed, so that a normal hexane solution of the butyl rubber is obtained.
The invention provides an application of the concentration method of the polymer solution in preparing 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 remove the impurity levels in the polymer solution and/or simply increase the polymer concentration.
The "dope" and the "solution" as used herein mean the same meaning.
The invention has the beneficial effects that:
according to the method for concentrating the polymer solution, disclosed by the invention, the organic solvent gas obtained from the top of the concentrating equipment is pressurized and then is used as a 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 a butyl rubber n-hexane solution in example 1;
reference numerals: E. reboiler, K, compressor, T, distillation tower, V, receiving tank, 1, thin gum solution, 2, n-hexane gas phase, 3, pressurized n-hexane gas phase, 4, tower kettle solution, 5, wen Houda kettle solution, 6, n-hexane condensate, 7, concentrated gum solution.
Detailed Description
The technical scheme of the invention will be further described in detail below with reference to specific embodiments. It is to be understood that the following examples are illustrative only and are not to be construed as limiting the scope of the invention. All techniques implemented based on the above description of the invention are intended to be included within the scope of the invention.
Unless otherwise indicated, the starting materials and reagents used in the following examples were either commercially available or may be prepared by known methods.
Example 1
Butyl rubber slurry prepared by a methyl chloride slurry method is contacted with a normal hexane solvent, butyl rubber in the slurry is dissolved in normal hexane, after methyl chloride and most of unreacted isobutene and isoprene monomers are separated, residual butyl rubber normal hexane thin rubber liquid 1 enters from the middle part of a distillation tower T, normal hexane gas phase 2 which is discharged from the top of the tower enters a compressor K for pressurization to obtain pressurized normal hexane gas phase 3, the pressurized normal hexane gas phase 3 enters a reboiler E for heat exchange with a tower bottom solution 4 from the bottom of the distillation tower, the pressurized normal hexane gas phase 3 is cooled and liquefied to obtain normal hexane condensate 6, the normal hexane condensate 6 enters a receiving tank V, and the tower bottom solution 4 is subjected to heat exchange to obtain heated tower bottom solution 5 and returns to the lower part of the concentration tower T. And the concentrated glue solution 7 after the concentration is discharged from the T tower kettle of the distillation tower.
Example 2
As shown in the concentration method flow in example 1, butyl rubber slurry prepared by a methyl chloride slurry method is contacted with an n-hexane solvent, butyl rubber in the slurry is dissolved in n-hexane, methyl chloride and most of unreacted monomers are separated to obtain a butyl rubber n-hexane solution with the concentration of 13wt%, the flow rate is 143900kg/h, wherein the n-hexane content is 87wt%, the butyl rubber n-hexane solution enters a distillation column from the middle lower part, the operation pressure of the distillation column is 130kPa, the n-hexane gas phase produced by the top of the column is controlled to 40000kg/h, the temperature of the n-hexane gas phase at the top of the column is 79 ℃, the n-hexane gas phase enters a compressor K and is pressurized to 240kPa, the temperature is raised to 105 ℃, the n-hexane gas phase after the temperature and the pressure are heated and pressurized enters a reboiler E of a distillation column T, heat exchange is carried out with a column bottom solution at 81 ℃, the column bottom solution is heated to 84 ℃ and then returned to the lower part of the distillation column, and the column bottom temperature of the distillation column is maintained. And (5) pressurizing the gas phase of the n-hexane for liquefying after heat exchange to obtain n-hexane condensate for recycling. The column bottom is prepared into 103900kg/h of concentrated butyl rubber glue solution with the concentration of 18 wt%. The power of the compressor K was 320kW.
Comparative example
The feed and column operating parameters were the same as in example 2, except that: the reboiler E of the tower bottom of the distillation tower adopts 0.8MPa water vapor as a heat source, and the gas-phase hexane at the top of the distillation tower is condensed and cooled by 30 ℃ circulating water. The water vapor consumption was 6.7t/h, and the cooling water circulation amount was 580t/h.
In the embodiment 2, the gas phase at the top of the tower after pressurization is used as a heat source of a reboiler at the bottom of the tower, so that the water vapor consumption is saved, the use of circulating water is reduced, the assumption is made that the electricity charge is according to 0.65 yuan/ton, the water vapor treatment charge is calculated according to 0.45 yuan/ton, and the energy consumption in the embodiment 2 is that: 320×0.65=208 yuan/h; the energy consumption in the comparative example was: 6.7X180+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, improvement, etc. 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 butyl rubber solution, the method comprising the steps of:
contacting butyl rubber slurry prepared by a methyl chloride slurry method with a normal hexane solvent, dissolving butyl rubber in normal hexane, and separating and removing methyl chloride and most of unreacted isobutene and isoprene monomers to obtain a normal hexane solution containing butyl rubber;
concentrating the n-hexane solution containing the butyl rubber in distillation equipment to obtain n-hexane gas and the concentrated n-hexane solution containing the butyl rubber; the n-hexane gas is used as a heat source of distillation equipment after being pressurized, and exchanges heat with tower bottom liquid of the distillation equipment to obtain Wen Houda kettle liquid and organic solvent condensate; the pressure of the pressurized normal hexane gas is 180-1000kPa.
2. The method of claim 1, wherein the concentration of the butyl rubber-containing n-hexane solution after the concentration is increased by 1 to 30wt% compared to the concentration of the butyl rubber-containing n-hexane solution before the concentration.
3. The method of claim 1, wherein the pressurizing is pressurizing the n-hexane gas using a pressurizing device.
4. A method of concentrating according to claim 3 wherein the supercharging device is a compressor.
5. A method of concentrating according to claim 3 wherein the pressure ratio of the boost is 1.1-6.
6. The method of claim 1 to 5, wherein the pressure of the pressurized n-hexane gas is 200 to 500kPa.
7. The method of claim 1 to 5, wherein the pressurization is accompanied by a rise in the temperature of the n-hexane gas.
8. The method of claim 7, wherein the temperature of the n-hexane gas is increased by 20-60 ℃ after pressurization compared to before pressurization.
9. Use of a method for concentrating a polymer solution according to any one of claims 1 to 8 for the preparation of butyl rubber.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011211594.2A CN114432721B (en) | 2020-11-03 | 2020-11-03 | Polymer solution concentration method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011211594.2A CN114432721B (en) | 2020-11-03 | 2020-11-03 | Polymer solution concentration method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114432721A CN114432721A (en) | 2022-05-06 |
| CN114432721B true CN114432721B (en) | 2023-09-15 |
Family
ID=81361010
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011211594.2A Active CN114432721B (en) | 2020-11-03 | 2020-11-03 | Polymer solution concentration method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114432721B (en) |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB850429A (en) * | 1958-01-24 | 1960-10-05 | Exxon Research Engineering Co | Processing halogenated butyl 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 |
| 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 |
| CN104592544A (en) * | 2015-01-27 | 2015-05-06 | 湖南百利工程科技股份有限公司 | Process for refining solvent in synthetic rubber production process |
| CN104761659A (en) * | 2014-01-03 | 2015-07-08 | 中国石油化工股份有限公司 | Method for preparing butyl rubber solution for halogenation, and apparatus thereof |
| CN105693460A (en) * | 2016-03-14 | 2016-06-22 | 江苏乐科节能科技股份有限公司 | Heat-pump distillation technology for recycling dichloromethane solvent |
| CN111234059A (en) * | 2020-03-17 | 2020-06-05 | 北京诺维新材科技有限公司 | Method for treating polymer solution |
| CN111228842A (en) * | 2020-03-17 | 2020-06-05 | 北京诺维新材科技有限公司 | Separation method |
| CN111234058A (en) * | 2020-03-17 | 2020-06-05 | 北京诺维新材科技有限公司 | Method for treating polymer solution |
| CN111302922A (en) * | 2020-03-27 | 2020-06-19 | 北京诺维新材科技有限公司 | Rectification separation method and rectification system |
| 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 |
| CN111808222A (en) * | 2020-06-30 | 2020-10-23 | 北京诺维新材科技有限公司 | Preparation method of halogenated butyl rubber |
-
2020
- 2020-11-03 CN CN202011211594.2A patent/CN114432721B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN104761659A (en) * | 2014-01-03 | 2015-07-08 | 中国石油化工股份有限公司 | Method for preparing butyl rubber solution for halogenation, and apparatus thereof |
| CN104592544A (en) * | 2015-01-27 | 2015-05-06 | 湖南百利工程科技股份有限公司 | Process for refining solvent in synthetic rubber production process |
| CN105693460A (en) * | 2016-03-14 | 2016-06-22 | 江苏乐科节能科技股份有限公司 | Heat-pump distillation technology for recycling dichloromethane solvent |
| CN111234059A (en) * | 2020-03-17 | 2020-06-05 | 北京诺维新材科技有限公司 | Method for treating polymer solution |
| CN111228842A (en) * | 2020-03-17 | 2020-06-05 | 北京诺维新材科技有限公司 | Separation method |
| CN111234058A (en) * | 2020-03-17 | 2020-06-05 | 北京诺维新材科技有限公司 | Method for treating polymer solution |
| CN111302922A (en) * | 2020-03-27 | 2020-06-19 | 北京诺维新材科技有限公司 | Rectification separation method and rectification system |
| 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 |
| CN111808222A (en) * | 2020-06-30 | 2020-10-23 | 北京诺维新材科技有限公司 | Preparation method of halogenated butyl rubber |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114432721A (en) | 2022-05-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2019090883A1 (en) | Method for preparing polypropylene or propylene-ethylene copolymer | |
| WO2019090884A1 (en) | Polymerization process of impact polypropylene | |
| CN111234058A (en) | Method for treating polymer solution | |
| CN101346401A (en) | Recovering ethylene and vinyl acetate from the residual gas stream of vinyl ester-ethylene copolymer preparation | |
| CN111234059A (en) | Method for treating polymer solution | |
| CN114432721B (en) | Polymer solution concentration method and application thereof | |
| CN106188400B (en) | A kind of preparation process of polystyrene multi-component copolymer high molecular material | |
| CN111808222A (en) | Preparation method of halogenated butyl rubber | |
| WO2019090882A1 (en) | Method for homopolymerization and random copolymerization of propylene | |
| CN114316090A (en) | Low-solvent-residue polymer and preparation method thereof | |
| CN106397089B (en) | Method and system for recovering and purifying hexane solvent in ethylene propylene rubber production | |
| KR101043464B1 (en) | Method and apparatus for production of polyvinyl alcohol with high degree of saponification | |
| BR112020023655B1 (en) | Process for preparing a multimodal ethylene copolymer in suspension in a cascade of reactors and apparatus for polymerizing olefinic monomers in suspension in a cascade of reactors | |
| CN111793154A (en) | Preparation method and preparation device of rubber | |
| CN102503762A (en) | Production method for vinyl toluene | |
| CN111886259B (en) | Solvent purification process | |
| CN109957056B (en) | Preparation method of halogenated monoolefin-conjugated diene copolymer | |
| CN114149519B (en) | Polymer coagulation method | |
| CN102443103A (en) | Preparation method of low-chroma high-softening-point dicyclopentadiene petroleum resin | |
| CN114437254B (en) | Preparation method and application of butyl rubber solution | |
| CN110921630A (en) | Method for preparing hydrogen chloride by resolving hydrochloric acid | |
| US3740381A (en) | Purification of olefinic polymers obtained in liquid phase | |
| CN212758597U (en) | Polymer solution separation device by water precipitation coagulation method | |
| CN112694639B (en) | Method and device for purifying polymerization liquid in EVOH production process | |
| CN112125987B (en) | Method for coagulating styrene thermoplastic elastomer solution |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |