CN111644073A - CO (carbon monoxide)2/N2Preparation method and application of separation membrane material - Google Patents

CO (carbon monoxide)2/N2Preparation method and application of separation membrane material Download PDF

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CN111644073A
CN111644073A CN202010545428.XA CN202010545428A CN111644073A CN 111644073 A CN111644073 A CN 111644073A CN 202010545428 A CN202010545428 A CN 202010545428A CN 111644073 A CN111644073 A CN 111644073A
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vinyl
separation
separation membrane
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史利娟
易群
吴玉程
邱明月
高丽丽
单媛媛
齐凯
王晓波
张鼎
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Taiyuan University of Technology
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
    • B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/10—Single element gases other than halogens
    • B01D2257/102—Nitrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/504—Carbon dioxide
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2

Abstract

The invention discloses CO2/N2The preparation method comprises the steps of taking water and oil phases as media, enabling the pH range to be 6-14, taking the functionalized polyionic liquid and any one of dialdehyde, diamine and metal salt as raw materials, enabling the molar ratio to be 1:0.5-2, enabling the concentration of the functionalized polyionic liquid to be 10-100mM, enabling the reaction temperature to be 25-60 ℃ and the reaction time to be 4-24 hours, dissolving any one of the dialdehyde, diamine and metal salt in chloroform or water, enabling the functionalized polyionic liquid to be dissolved in water or chloroform, mixing the water and the chloroform, and standing for 4-24 hours to form the ionic liquid based polymer self-supporting film. The obtained self-supporting film can effectively separate CO2/N2The method has simple preparation process, no pollution, and CO2/N2Separation effectGood and has high industrial application potential.

Description

CO (carbon monoxide)2/N2Preparation method and application of separation membrane material
Technical Field
The invention relates to CO2/N2A preparation method and application of a separation membrane material, belonging to the field of porous organic membrane separation and adsorption.
Background
With industrial CO2The increasing discharge amount causes a series of environmental problems such as greenhouse effect and the like. Fossil fuel combustion is currently the most predominant CO2A source of emissions. However, CO in conventional flue gas of fuel gas, fuel oil and coal2Low concentration (8-15 vol.%), and separating and purifying CO from the gas mixture containing nitrogen as main component under low pressure2The gas has the technical bottlenecks of high difficulty, high energy consumption, high cost (the power generation cost is increased by 50 percent, and the energy utilization efficiency is reduced by 8-12 percent) and the like. Thus, designing CO2High-efficiency adsorption/separation material and technology for realizing CO2The key technical problem of source enrichment.
The membrane separation technology realizes gas separation through the difference of permeation rates of substance molecules in mixed gas in a separation membrane, has multiple functions of separation, concentration, purification, refining and the like, and is widely applied to the fields of industrial production, gas purification and separation, waste gas treatment, environmental protection and the like due to the advantages of high efficiency, energy conservation, environmental protection and the like. The current membrane preparation method usually needs covalent polymerization or an inorganic carrier, the synthesis process is complicated, and the preparation cost is high. Compared with covalent polymerization, a specific ordered structure is constructed through non-covalent action (hydrogen bonds, metal coordination, pi-pi bonds and the like), and the preparation method has the advantages of adjustable structure, simplicity in preparation, multiple functions and the like.
The ionic liquid has unique physical chemistryThe property, non-volatility, low vapor pressure, strong dissolving capacity and the like. As a green solvent, the ionic liquid is used for CO2Has excellent dissolving capacity and is widely applied to CO2The fields of capture and conversion.
Disclosure of Invention
The invention aims to provide CO2/N2Preparation method and application of separation membrane material, and the method has simple preparation process, is green and pollution-free, and is applied to CO2/N2Good separation effect and high industrial application potential.
The invention adopts an interface assembly method to prepare the ionic liquid-based polymer film on the water-oil interface, the method is simple to operate, a compact porous film can be prepared without a support body, and CO can be realized2/N2The separation is efficient.
The invention provides CO2/N2The preparation method of the separation membrane material comprises the following steps:
taking a water phase and an oil phase as media, setting the pH range to be 6-14, taking a functionalized polyionic liquid and any one of dialdehyde, diamine and metal salt as raw materials, setting the molar ratio to be 1:0.5-2, setting the functionalized polyionic liquid to be 10-100mM, setting the assembly temperature to be 25-60 ℃, setting the assembly time to be 4-24h, dissolving any one of the dialdehyde, the diamine and the metal salt in chloroform or water, dissolving the functionalized polyionic liquid in water or chloroform, mixing the water and the chloroform, and standing for 4-24h to form the ionic liquid-based self-supporting film.
The functionalized polyion liquid in the method is obtained by dissolving a functionalized ionic liquid monomer in water, adding an initiator Azobisisobutyronitrile (AIBN), and reacting for 8-24 hours at 60-80 ℃.
The functionalized ionic liquid monomer in the method is any one of 1-vinyl-3-ethylamino imidazole chloride salt, 1-vinyl-3-ethylamino imidazole bromide salt, 1-vinyl-3- (2- (4-phenoxy) benzaldehyde) imidazole chloride salt, 1-vinyl-3- (2- (4-phenoxy) benzaldehyde) imidazole bromide salt, 1-vinyl-3-ethylamino imidazole tetrafluoroborate or 1-vinyl-3-carboxyl imidazole tetrafluoroborate.
The preparation process of each functionalized ionic liquid monomer is as follows:
1-vinyl-3-ethylamino imidazole bromide salt: 1.8-5.6 g (20-50 mmol) of 1-vinylimidazole and 4.1-10.2 g (20-50 mmol) of 2-bromoethylamine hydrobromide are respectively weighed, added into 15-30 ml of anhydrous acetonitrile, introduced with nitrogen for protection, and subjected to reflux reaction for 8 hours. Filtering to obtain a solid, washing the solid with absolute ethyl alcohol, and drying the solid for 12 hours in vacuum to obtain 1-vinyl-3-ethylamino imidazole bromine salt which is named as [ Amim ] Br;
1-vinyl-3-ethylamino imidazole chloride salt: respectively weighing 1.8-5.6 g (20-50 mmol) of 1-vinyl imidazole and 2.3-5.8 g (20-50 mmol) of 2-chloroethylamine hydrochloride, adding into 15-30 ml of anhydrous acetonitrile, introducing nitrogen for protection, and carrying out reflux reaction for 8 hours. Filtering to obtain a solid, washing the solid with absolute ethyl alcohol, and drying the solid for 12 hours in vacuum to obtain 1-vinyl-3-acetamido imidazole chloride salt which is named as [ Amim ] Cl;
1-vinyl-3- (2- (4-phenoxy) benzaldehyde) imidazole bromide salt: respectively weighing 1.88-5.645 g (20-50 mmol) of 1-vinylimidazole and 4.58-11.45 g (20-50 mmol) of 3-bromo-4-oxobenzaldehyde, adding into 15-30 ml of anhydrous acetonitrile, introducing nitrogen for protection, and carrying out reflux reaction for 24 hours. Filtering to obtain a solid, washing with anhydrous ether, and vacuum drying for 12h to obtain 1-vinyl-3- (2- (4-phenoxy) benzaldehyde) imidazole bromide, which is named as [ Bmim ] Br;
1-vinyl-3- (2- (4-phenoxy) benzaldehyde) imidazole chloride salt: respectively weighing 1.8-5.6 g (20-50 mmol) of 1-vinyl imidazole and 3.7-9.2 g (20-50 mmol) of 3-chloro-4-oxo benzaldehyde, adding into 15-30 ml of anhydrous acetonitrile, introducing nitrogen for protection, and carrying out reflux reaction for 24 hours. Filtering to obtain a solid, washing with anhydrous ether, and vacuum drying for 12h to obtain 1-vinyl-3- (2- (4-phenoxy) benzaldehyde) imidazole chloride salt which is named as [ Bmim ] Cl;
1-vinyl-3-ethylamino imidazole tetrafluoroborate: dissolving 0.2-0.5 g of 1-vinyl-3-acetamido imidazole bromide in acetone, and adding equimolar LiBF4Stirring for 72h, removing the precipitate to obtain 1-vinyl-3-ethylamino imidazole tetrafluoroborate which is named as [ Amim]BF4；
1-vinyl-3-carboxyimidazole tetrafluoroborate: 1.88-5.645 g (20-50 mmol) of 1-vinylimidazole and 3-bromopropionic acid are weighed respectively3.06-7.65 g (20-50 mmol), adding into 15-30 ml of anhydrous acetonitrile, introducing nitrogen for protection, and carrying out reflux reaction for 24 hours. Filtering to obtain a solid, washing with anhydrous ether, and vacuum drying for 12h to obtain 1-vinyl-3-carboxyl imidazole bromide; dissolving 0.2-0.5 g of 1-vinyl-3-carboxyl imidazole bromide in acetone, and adding equimolar LiBF4Stirring for 72h, removing precipitate to obtain 1-vinyl-3-carboxyl imidazole tetrafluoroborate, which is named as [ Cnim [ ]]BF4。
The dialdehyde in the method is any one of succinaldehyde, glutaraldehyde, hexanedial, 1, 4-benzenedicarboxaldehyde and 4, 4' -biphenyldicarboxaldehyde.
The diamine in the method is any one of o-phenylenediamine, m-phenylenediamine, 1, 4-phenylenediamine, 2, 4-diaminotoluene, cis-1, 4-diaminocyclohexane and melamine.
The metal salt in the method is any one of zinc nitrate hexahydrate, chromium nitrate nonahydrate and copper nitrate hexahydrate.
The invention provides CO prepared by the method2/N2Separating membrane material in CO2/N2Application in the separation: fixing the separation membrane in a membrane pool, turning on a vacuum pump to make the separation membrane in a vacuum state, and introducing CO into the raw material side2Or N2Controlling the test temperature to be 25-75 ℃, and calculating to obtain CO by monitoring the downstream gas pressure of the membrane2Or N2Permeability and CO2/N2Selectivity of separation.
The invention has the beneficial effects that:
(1) the ionic liquid-based polymer film prepared by the invention is simple in preparation process, green and environment-friendly;
(2) the membrane material prepared by the invention is used for CO2/N2Upon separation, CO2/N2Has excellent separation performance and solves the problem of CO2/N2High separation energy consumption and the like, and has higher industrial application potential.
Drawings
FIG. 1 is a schematic diagram of a gas permeation separation performance testing device.
In the figure: 1. raw gas cylinder (N)2、CO2) (ii) a 2. A pressure maintaining valve; 3. raw material side pressure sensor: 4. a membrane tank; 5. a permeate side pressure sensor; 6. a first ball valve; 7. a buffer tank; 8. a second ball valve; 9. a vacuum pump.
Detailed Description
The present invention is further illustrated by, but is not limited to, the following examples.
Example 1
1-vinyl-3-ethylamino imidazole bromide salt: 1.8g (20mmol) of 1-vinyl imidazole and 4.1g (20mmol) of 2-bromoethylamine hydrobromide are respectively weighed and added into 15ml of anhydrous acetonitrile, nitrogen is introduced for protection, and the reflux reaction is carried out for 8 hours. Filtering to obtain a solid, washing the solid with absolute ethyl alcohol, and drying the solid for 12 hours in vacuum to obtain the 1-vinyl-3-ethylamino imidazole bromine salt which is named as [ Amim ] Br.
Weighing [ Amim ] Br 2g (6.7mmol) and dissolving in 15ml water, adding 0.01g AIBN, introducing nitrogen for protection, heating to 75 ℃ under stirring and reacting for 8 hours. Cooling to room temperature, removing the solvent by rotary evaporation, and drying in vacuum at 60 ℃ to obtain the functionalized polyamino ionic liquid named as [ PAmim ] Br.
0.15g of [ PAmim ] Br (0.5mmol, 100mM) was weighed out in 5ml of water, the pH of the aqueous solution was adjusted to = 6, 0.02g (0.25mmol) of succinaldehyde was weighed out in 5ml of chloroform, and the two phases were mixed in a round quartz flask with a diameter of 5 cm. Putting the quartz bottle into a thermostat, setting the temperature at 30 ℃, assembling for 4 hours to obtain an assembled film, and carrying out vacuum drying at 50 ℃ for 12 hours, wherein the label is PAP-1.
Example 2
In the same manner as in example 1, the pH of the solution was adjusted to 9, and the other conditions were not changed, and the obtained product was designated as PAP-2.
Example 3
As in example 1, the [ PAmim ] Br and succinaldehyde concentrations were adjusted to 200 mM, and the other conditions were not changed, and the resulting product was labeled as PAP-3.
Example 4
As in example 1, the amount of succinaldehyde was adjusted to 0.043g (0.5 mmol) under otherwise unchanged conditions, and the product obtained was designated PAP-4.
Example 5
In the same manner as in example 1, the diameter of the quartz bottle was changed to 8cm, and the other conditions were not changed, and the obtained product was designated as PAP-5.
Example 6
As in example 1, the incubator temperature was adjusted to 50 ℃ and other conditions were not changed, and the resulting product was designated as PAP-6.
Example 7
The assembly time was adjusted to 10h, other conditions were unchanged, and the product obtained was labeled as PAP-7, as in example 1.
Example 8
1-vinyl-3- (2- (4-phenoxy) benzaldehyde) imidazole bromide salt: 1.88g (20mmol) of 1-vinylimidazole and 4.58g (20mmol) of 3-bromo-4-oxobenzaldehyde are weighed respectively, added into 15ml of anhydrous acetonitrile, and subjected to reflux reaction for 24 hours under the protection of nitrogen. Filtering to obtain a solid, washing with anhydrous ether, and vacuum drying for 12h to obtain 1-vinyl-3- (2- (4-phenoxy) benzaldehyde) imidazole bromide, which is named as [ Bmim ] Br.
Weighing [ Bmim ] Br 2.16g (6.7mmol) and dissolving in 15ml water, adding 0.01g AIBN, introducing nitrogen for protection, heating to 75 ℃ under stirring and reacting for 8 hours. Cooling to room temperature, removing the solvent by rotary evaporation, and drying in vacuum at 60 ℃ to obtain the functionalized polyamino ionic liquid named as [ PBmim ] Br.
0.16g of [ PBmim ] Br (0.5mmol, 100mM) was weighed out and dissolved in 5ml of water, the pH of the aqueous solution was adjusted to = 6, 0.027g (0.25mmol) of m-phenylenediamine was weighed out and dissolved in 5ml of chloroform, and the two phases were mixed in a circular quartz flask having a diameter of 5 cm. And (3) putting the quartz bottle into a thermostat, setting the temperature to be 30 ℃, assembling for 4 hours to obtain an assembled film, and carrying out vacuum drying for 12 hours at the temperature of 50 ℃, wherein the label is PBP-1.
Example 9
1-vinyl-3-carboxyimidazole tetrafluoroborate: 1.88g (20mmol) of 1-vinylimidazole and 3.06g (20mmol) of 3-bromopropionic acid are respectively weighed, added into 15ml of anhydrous acetonitrile, and refluxed for 24 hours under the protection of nitrogen. Filtering to obtain a solid, washing with anhydrous ether, and vacuum drying for 12h to obtain 1-vinyl-3-carboxyl imidazole bromide; dissolving 0.2g of 1-vinyl-3-carboxyl imidazole bromide salt in acetone, and adding equimolar LiBF4Stirring for 72h, removing precipitate to obtain 1-vinyl-3-carboxyl imidazole tetrafluoroborate, which is named as [ Cmi [ ]m]BF4。
Weighing [ Cnim]BF41.70g (6.7mmol) of the compound is dissolved in 15ml of ethanol, 0.01g of AIBN is added, nitrogen is introduced for protection, and the mixture is heated to 75 ℃ under stirring for reaction for 8 hours. Cooling to room temperature, removing the solvent by rotary evaporation, and drying in vacuum at 60 ℃ to obtain the functionalized polyamino ionic liquid named as [ PCmim ]]BF4。
Weighing [ PCmim ]]BF40.127g (0.5mmol, 100mM) was dissolved in 5ml of chloroform, the aqueous solution pH = 6 was adjusted, 0.037g (0.125 mmol) of zinc nitrate hexahydrate was weighed out dissolved in 5ml of water, and the two phases were mixed in a circular quartz flask having a diameter of 5 cm. And (3) putting the quartz bottle into a thermostat, setting the temperature to be 30 ℃, assembling for 4 hours to obtain an assembled film, and performing vacuum drying at the temperature of 50 ℃ for 12 hours, wherein the mark is PCP-1.
The ionic liquid-based polymer film was studied for CO2/N2The separation performance of (3).
Application example 1:
CO separation on gas permeation separation performance device2/N2The separation performance was tested and the apparatus is shown in FIG. 1. Before the test is started, the separation membrane is placed in a membrane pool, a vacuum pump is started, the separation membrane is in a vacuum state, and gas adsorbed in the air by the membrane is removed. During testing, the testing temperature is controlled to be 25 ℃, the testing pressure is 1bar, the vacuum pump is closed, and the separation membrane PNH is obtained by recording the change of the pressure of the permeation side and combining the membrane area and the membrane thickness of the separation membrane2CO of P-12/N2Separation selectivity of 30.6, CO2Permeability of 120 barrer, N2The permeability was 4 barrer.
Application example 2:
in the same manner as in application example 1, the separation membrane selected was PAP-2, and other conditions were not changed, and CO was calculated2/N2Separation selectivity of 20.8, CO2Permeability of 100 barrer, N2The permeability was 4.3 barrer.
Application example 3:
in the same manner as in application example 1, the separation membrane selected was PAP-3, and other conditions were not changed, and CO was calculated2/N2Separation selectivity of 25.2, CO2Permeability of 110 barrer, N2The permeability was 4.1 barrer.
Application example 4:
in the same manner as in application example 1, the separation membrane selected was PAP-4, and other conditions were not changed, and CO was calculated2/N2Separation selectivity of 38.4, CO2Permeability of 145 barrer, N2The permeability was 4.1 barrer.
Application example 5:
in the same manner as in application example 1, the separation membrane selected was PAP-5, and other conditions were not changed, and CO was calculated2/N2Separation selectivity of 42, CO2Permeability of 150 barrer, N2The permeability was 3.75 barrer.
Application example 6:
in the same manner as in application example 1, the separation membrane selected was PAP-6, and other conditions were not changed, and CO was calculated2/N2Separation selectivity of 25.7, CO2Permeability of 105 barrer, N2The permeability was 3.77 barrer.
Application example 7:
in the same manner as in application example 1, the separation membrane selected was PAP-7, and other conditions were not changed, and CO was calculated2/N2Separation selectivity of 36.6, CO2Permeability of 140 barrer, N2The permeability was 4.2 barrer.
Application example 8:
in the same manner as in application example 1, the separation membrane selected was PBP-1, and the other conditions were not changed, and CO was calculated2/N2Separation selectivity of 15.8, CO2Permeability of 90 barrer, N2The permeability was 5 barrer.
Application example 9:
in the same manner as in application example 1, the separation membrane selected was PCP-1, and other conditions were not changed, and CO was calculated2/N2Separation selectivity of 30.3, CO2Permeability of 115 barrer, N2The permeability was 4 barrer.
TABLE 1 separation Performance of different separation membranes
Figure RE-981289DEST_PATH_IMAGE002
Further research the simulation temperature on the prepared membrane CO2/N2Effect of separation Performance
Application example 10:
in the same way as in application example 1, the test temperature is changed to 35 ℃, other conditions are unchanged, and CO is obtained by calculation2/N2Separation selectivity of 38.8, CO2Permeability of 146 barrer, N2The permeability was 4.05 barrer.
Application example 11:
in the same way as in application example 1, the test temperature is changed to 50 ℃, other conditions are unchanged, and CO is obtained by calculation2/N2Separation ratio of 40.5, CO2Permeability of 133 barrer, N2The permeability was 3.5 barrer.
TABLE 2 PNH2Separation Performance of P-1 at different temperatures
Figure RE-632850DEST_PATH_IMAGE004
Further study of inlet pressure on the membrane CO produced2/N2Effect of separation Performance
Application example 12:
in the same application example 1, the test pressure is changed to be 2 bar, other conditions are unchanged, and CO is obtained through calculation2/N2Separation selectivity of 37.2, CO2Permeability of 135 barrer, N2The permeability was 3.97 barrer.
Application example 13:
in the same application example 1, the test pressure is changed to 5 bar, other conditions are unchanged, and CO is obtained through calculation2/N2Separation selectivity of 35.6, CO2Permeability of 132 barrer, N2The permeability was 4 barrer.
TABLE 3 PNH2Separation Performance of P-1 at different pressures
Figure RE-147008DEST_PATH_IMAGE006
It can be seen that the invention produces for CO2/N2The separated ionic liquid-based polymer self-supporting film does not need a support body in the preparation process and has excellent CO2/N2Separation Performance, CO2/N2The separation selectivity of the catalyst can reach 42 at most; meanwhile, the polymer film can realize CO at normal temperature and normal pressure2/N2The high-efficiency separation is realized.
Several of the highly effective CO separations prepared in the above examples2/N2Separation membrane realizes the separation of CO2/N2Effective separation into CO under different operating conditions2/N2Provides a new approach.
Finally, the above embodiments are only for the technical solution of the present invention, and the skilled person in the art can make changes to the technical solution of the present invention according to the understanding, but all such changes should fall within the protection scope of the claims of the present invention.

Claims (8)

1. CO (carbon monoxide)2/N2The preparation method of the separation membrane material is characterized by comprising the following steps:
taking a water phase and an oil phase as media, controlling the pH range to be 6-14, taking a functionalized polyionic liquid and any one of dialdehyde, diamine or metal salt as raw materials, controlling the molar ratio of the functionalized polyionic liquid to the latter to be 1:0.5-2, controlling the concentration of the functionalized polyionic liquid to be 10-100mM, controlling the assembly temperature to be 25-60 ℃ and the assembly time to be 4-24h, dissolving any one of the dialdehyde, the diamine or the metal salt in chloroform or water, dissolving the functionalized polyionic liquid in water or chloroform, mixing the water and the chloroform, and standing for 4-24h to form the ionic liquid based polymer self-supporting film.
2. CO according to claim 12/N2The preparation method of the separation membrane material is characterized by comprising the following steps: the functionalized polyion liquid is obtained by dissolving a functionalized ionic liquid monomer in water, adding an initiator azobisisobutyronitrile, and reacting at 60-80 ℃ for 8-24 hours.
3. According to claim 2Said CO2/N2The preparation method of the separation membrane material is characterized by comprising the following steps: the functionalized ionic liquid monomer is any one of 1-vinyl-3-ethylamino imidazole chloride salt, 1-vinyl-3-ethylamino imidazole bromide salt, 1-vinyl-3- (2- (4-phenoxy) benzaldehyde) imidazole chloride salt, 1-vinyl-3- (2- (4-phenoxy) benzaldehyde) imidazole bromide salt, 1-vinyl-3-ethylamino imidazole tetrafluoroborate or 1-vinyl-3-carboxyl imidazole tetrafluoroborate.
4. CO according to claim 12/N2The preparation method of the separation membrane material is characterized by comprising the following steps: the dialdehyde is any one of succinaldehyde, glutaraldehyde, adipaldehyde, 1, 4-benzenedicarboxaldehyde and 4, 4' -biphenyldicarboxaldehyde.
5. CO according to claim 12/N2The preparation method of the separation membrane material is characterized by comprising the following steps: the diamine is any one of o-phenylenediamine, m-phenylenediamine, 1, 4-phenylenediamine, 2, 4-diaminotoluene, cis-1, 4-diaminocyclohexane and melamine.
6. CO according to claim 12/N2The preparation method of the separation membrane material is characterized by comprising the following steps: the metal salt is any one of zinc nitrate hexahydrate, chromium nitrate nonahydrate and copper nitrate hexahydrate.
7. CO prepared by the preparation method of any one of claims 1 to 62/N2Separating membrane material in CO2/N2Use in separation.
8. Use according to claim 7, characterized in that: fixing the separation membrane in a membrane pool, turning on a vacuum pump to make the separation membrane in a vacuum state, and introducing CO into the raw material side2Or N2Controlling the test temperature to be 25-75 ℃, and calculating to obtain CO by monitoring the downstream gas pressure of the membrane2Or N2Permeability and CO2/N2Selectivity of separation.
CN202010545428.XA 2020-06-16 2020-06-16 CO (carbon monoxide)2/N2Preparation method and application of separation membrane material Withdrawn CN111644073A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115010718A (en) * 2022-07-27 2022-09-06 北京石油化工学院 Method for preparing isosorbide by dehydrating sorbitol under catalysis of polymeric ionic liquid
CN115253702A (en) * 2022-08-11 2022-11-01 武汉工程大学 Double-sided characteristic flexible self-supporting membrane material and preparation method and application thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115010718A (en) * 2022-07-27 2022-09-06 北京石油化工学院 Method for preparing isosorbide by dehydrating sorbitol under catalysis of polymeric ionic liquid
CN115253702A (en) * 2022-08-11 2022-11-01 武汉工程大学 Double-sided characteristic flexible self-supporting membrane material and preparation method and application thereof

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Application publication date: 20200911