CN107051238B - Tetrahydrofurfuryl-containing CO2Permselective separation membranes - Google Patents
Tetrahydrofurfuryl-containing CO2Permselective separation membranes Download PDFInfo
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- CN107051238B CN107051238B CN201710345584.XA CN201710345584A CN107051238B CN 107051238 B CN107051238 B CN 107051238B CN 201710345584 A CN201710345584 A CN 201710345584A CN 107051238 B CN107051238 B CN 107051238B
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- tetrahydrofurfuryl
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- carbon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
- B01D71/82—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74 characterised by the presence of specified groups, e.g. introduced by chemical after-treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
Abstract
The invention relates to a gas separation membrane technology, in particular to CO containing tetrahydrofurfuryl2Separating the membrane. The separation membrane is formed by free radical polymerization among carbon-carbon double bonds, contains tetrahydrofurfuryl, and can improve CO of the separation membrane by improving the dissolution selectivity2Separation performance on CO2/CH4、CO2/N2Have good separation performance. The preparation method comprises the following steps: mixing a monomer containing tetrahydrofurfuryl and a cross-linking agent, adding an initiator, coating the mixed solution on a support, and carrying out free radical polymerization to obtain the separation membrane.
Description
Technical Field
The invention relates to a polymer separation membrane technology, in particular to a method for preparing CO containing tetrahydrofurfuryl2A permselective separation membrane.
Background
CO2The separation of (a) is a very promising separation process. CO 22The separation techniques mainly include adsorption, physical absorption, chemical absorption, cryogenic distillation, membrane separation, and combinations thereof. The membrane separation method has the advantages of simple device, easy operation, small occupied area, low energy consumption, low cost, small pollution and the like.
The current research and use of the method is more applied to CO2Most of the separated materials are glassy polymer materials, and most of the traditional glassy polymer membrane materials rely on the sieving capacity of a polymer chain segment for separation, so that the gas separation performance of the polymer can be improved by changing the structure to improve the sieving capacity of the polymer. However, since the gas permeation performance and the separation performance are usually contradictory due to the restriction of the "Robeson upper limit", it is difficult to obtain both high gas permeation performance and high separation performance. On the other hand, due to CO2When the condensed gas easily causes the plasticization of the glassy polymer membrane material, the glassy polymer chain segments are swelled, the chain segment spacing is increased, and the sieving performance (namely diffusion selectivity) of the glassy polymer membrane is weakened, so that the separation performance of the traditional glassy polymer membrane is reduced, so that the separation performance of the gas is sometimes difficult to improve only by improving the sieving capacity (improving the diffusion selectivity) of the polymerization, and particularly, the gas contains a large amount of CO2And the like. Therefore, attention has been focused on a method for improving the separation performance of a polymer membrane by improving the dissolution selectivity. The patent develops a tetrahydrofurfuryl-containing CO by introducing tetrahydrofurfuryl (tetrahydrofurfuryl) to improve the dissolution selectivity2A permselective separation membrane.
Disclosure of Invention
The invention aims to prepare the CO containing the tetrahydrofurfuryl2A permselective separation membrane.
In order to achieve the purpose, the invention adopts the technical scheme that: monomers containing tetrahydrofurfuryl and carbon-carbon double bonds are selected to carry out free radical polymerization with a cross-linking agent under the action of an initiator, and the separation membrane is obtained through cross-linking.
In particular, the CO having a tetrahydrofurfuryl group according to the invention2A permselective separation membrane prepared by the steps of:
uniformly mixing a certain amount of monomers containing carbon-carbon double bonds and tetrahydrofurfuryl, a certain amount of cross-linking agents, a certain amount of initiators and solvents, and coating the mixed solution on a support body after defoaming: and carrying out free radical polymerization under heating or ultraviolet irradiation, and obtaining the separation membrane after the reaction is finished.
The monomer containing the carbon-carbon double bond and the tetrahydrofurfuryl comprises acrylic acid tetrahydrofurfuryl ester, tetrahydrofurfuryl methacrylate and 2-vinyl-2-methyl-5- (1-methylvinyl) tetrahydrofuran, and the mass content of the monomer is 0.1-99.9%.
Crosslinking agents used in the preparation include polyethylene glycol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, polydipentaerythritol pentaacrylate, polydipentaerythritol hexaacrylate, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate and propoxylated trimethylolpropane triacrylate, hexanediol diacrylate, tripropylene glycol diacrylate, tris- (2-hydroxyethyl) isocyanurate triacrylate, neopentyl glycol diethoxy diacrylate, ditrimethylolpropane tetraacrylate, propoxylated glycerol triacrylate, neopentyl glycol diacrylate, 1-6 hexanediol diacrylate, propoxylated neopentyl glycol diacrylate, tris- (2-hydroxyethyl) isocyanurate triacrylate, ethoxylated pentaerythritol tetraacrylate, polyethylene glycol tetraacrylate, Ethoxylated bisphenol A diacrylate, triethylene glycol diacrylate, tripropylene glycol diacrylate, diethylene glycol diacrylate phthalate, 1, 4-butanediol diacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate.
The initiator used in the preparation process is a free radical initiator; the free radical initiator is 1-hydroxycyclohexyl phenyl ketone, dibenzoyl peroxide, lauroyl peroxide or azobisisobutyronitrile; the dosage of the free radical initiator is 100-10000 ppm.
The invention has the following advantages: the monomer contains tetrahydrofurfuryl, and the separation performance of the membrane is improved by improving the dissolution selectivity.
Detailed Description
The gas permeability of the separation membrane is characterized by the permeation rate:
permeation rate J of gas A in a polymer membraneA(cm3(STP)·cm-2·s-1·cmHg-1) Calculated according to the following formula:
JA＝273V/A/p/(273+T) (1)
wherein subscript a represents gas a; v is the gas volume flow (cm)3S); a is the effective area (cm) of the sample film2) (ii) a T is the test temperature (. degree. C.); p is the pressure difference (cmHg) between the upper and lower sides of the membrane-1)。
Ideal separation coefficient alpha of gas A/B in polymer filmA/BCalculated according to the following formula: alpha is alphaA/B＝JA/JB(2)。
Example 1
Taking a certain amount of tetrahydrofuran acrylate, a certain amount of poly dipentaerythritol hexaacrylate and 1000ppm of initiator 1-hydroxycyclohexyl phenyl ketone, uniformly mixing, defoaming, placing on a quartz glass plate, exposing the quartz glass plate to ultraviolet light for a certain time, and crosslinking to obtain a solid film. The separation membrane performance is shown in table 1.
TABLE 1
| Monomer mass/crosslinker mass | CO2Permeation Rate (10)-6cm3(STP)·cm-2·s-1·cmHg-1) | CO2/N2Coefficient of separation |
| 999∶1 | 120 | 35 |
| 100∶1 | 95 | 36 |
| 50∶1 | 90 | 34 |
| 10∶1 | 76 | 36 |
| 1∶1 | 120 | 25 |
| 1∶2 | 180 | 33 |
| 1∶50 | 40 | 44 |
| 1∶999 | 20 | 32 |
Example 2
Taking a certain amount of tetrahydrofuran methacrylate, a certain amount of cross-linking agent (the mass ratio of the monomer to the cross-linking agent is 10: 1) and 100ppm of initiator dibenzoyl peroxide, uniformly mixing, defoaming, placing on a polyacrylonitrile ultrafiltration membrane, exposing the polyacrylonitrile ultrafiltration membrane to ultraviolet light for a certain time, and crosslinking to obtain the solid membrane. The separation membrane performance is shown in table 2.
TABLE 2
Example 3
Taking a certain amount of 2-vinyl-2-methyl-5- (1-methylvinyl) tetrahydrofuran, uniformly mixing with equal mass of polydipentaerythritol pentaacrylate and 10000ppm of initiator azobisisobutyronitrile, defoaming, placing on a glass plate, heating at 45 ℃ for 10 hours, and crosslinking to obtain a solid film. Separation membrane CO2Permeation rate: 29X 10-6cm3(STP)·cm-2·s-1·cmHg-1，CO2/CH4The separation factor is 20.
Example 4
Taking a certain amount of tetrahydrofuran acrylate, pentaerythritol tetraacrylic acid with equal mass and 500ppm initiator lauroyl peroxide, mixing uniformly, defoaming, placing on a glass plate, heating at 70 ℃ for 10 hours, and crosslinking to obtain a solid film. Separation membrane CO2Permeation rate: 97X 10-6cm3(STP)·cm-2·s-1·cmHg-1，CO2/H2The separation factor 36.
As can be seen from the above examples, tetrahydrofurfuryl containing polymers have higher CO2Separation performance. The above examples do not indicate a limited scope of application of the patent. Any person skilled in the art of membrane preparation can very easily apply the teachings of the patent to any other possible system.
Claims (1)
1. CO (carbon monoxide)2The preferential permeation separation membrane is characterized in that the membrane contains tetrahydrofurfuryl, the separation performance of the membrane can be greatly improved, and the preparation steps are as follows: uniformly mixing a certain amount of monomers containing carbon-carbon double bonds and tetrahydrofurfuryl, a certain amount of cross-linking agents, a certain amount of initiators and solvents, and coating the mixed solution on a support body after defoaming: under the heating or ultraviolet irradiation, free radical polymerization is carried out, and a separation membrane is obtained after the reaction is finished; the cross-linking agent is hexanediol diacrylate;
the monomer containing the carbon-carbon double bond and the tetrahydrofurfuryl is tetrahydrofuran methacrylate, and the mass ratio of the monomer to the cross-linking agent is 10: 1;
the initiator is free radical initiator dibenzoyl peroxide;
the amount of the radical initiator used was 100 ppm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710345584.XA CN107051238B (en) | 2017-05-12 | 2017-05-12 | Tetrahydrofurfuryl-containing CO2Permselective separation membranes |
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|---|---|---|---|
| CN201710345584.XA CN107051238B (en) | 2017-05-12 | 2017-05-12 | Tetrahydrofurfuryl-containing CO2Permselective separation membranes |
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| CN107051238A CN107051238A (en) | 2017-08-18 |
| CN107051238B true CN107051238B (en) | 2020-10-27 |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103566781A (en) * | 2013-11-19 | 2014-02-12 | 天津工业大学 | Polyoxyethylene CO2 precedence permeation separation membrane with stellate reticular structure |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103566781A (en) * | 2013-11-19 | 2014-02-12 | 天津工业大学 | Polyoxyethylene CO2 precedence permeation separation membrane with stellate reticular structure |
Non-Patent Citations (1)
| Title |
|---|
| 聚氧化乙烯气体分离膜的发展;赵红永等;《膜科学与技术》;20110630;第31卷(第3期);第18-24页 * |
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