CN112870983B - Method for desorbing CO from organic solvent2The preparation method of the polyimide film - Google Patents
Method for desorbing CO from organic solvent2The preparation method of the polyimide film Download PDFInfo
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- CN112870983B CN112870983B CN202110046862.8A CN202110046862A CN112870983B CN 112870983 B CN112870983 B CN 112870983B CN 202110046862 A CN202110046862 A CN 202110046862A CN 112870983 B CN112870983 B CN 112870983B
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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
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- 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
- B01D53/14—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 absorption
- B01D53/1425—Regeneration of liquid absorbents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
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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
- B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
- B01D71/62—Polycondensates having nitrogen-containing heterocyclic rings in the main chain
- B01D71/64—Polyimides; Polyamide-imides; Polyester-imides; Polyamide acids or similar polyimide precursors
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/50—Carbon dioxide
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- 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
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2
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Abstract
The invention belongs to the field of membrane separation, and particularly relates to a method for separating CO from a gas containing CO2To separate CO from the organic solution of2The method for producing a desorption membrane of (1). Which comprises the following steps: dissolving polyimide raw material powder in an organic solvent, and adding an inorganic nano material to obtain a membrane casting solution; preparing a polyimide film on the support film by adopting rotary film coating equipment; placing the mixture into deionized water for coagulation bath at the temperature of 5-90 ℃ for 1-12 h; putting into an organic solvent containing a cross-linking agent; and (3) conveying the cross-linked polyimide film into a vacuum drying oven for drying. The film prepared by the method has the advantages of good solvent resistance, high film uniformity and CO2High separation factor and high flux.
Description
Technical Field
The invention belongs to the field of membrane separation, and particularly relates to a method for separating CO from a gas containing CO2To separate CO from the organic solution of2The method for producing a desorption membrane of (1).
Background
Solvent absorption method for capturing CO before combustion2The conventional organic absorbents include methanol (MeOH), polyethylene glycol dimethyl ether (NHD), Propylene Carbonate (PC), N-methyl pyrrolidone (NMP), etc., and dimethyl carbonate (DMC), diethyl carbonate (DEC), diethyl succinate (DES), etc., have been developed in recent years.
In view of the above, the present patent proposes to prepare solvent-resistant CO by using polyimide as the main film material2The service life of the desorption film is greatly prolonged. CO capture by absorption in general2Regeneration of the absorbent then needs to be accomplished by thermal desorption or inert gas desorption, but this way the desorption energy consumption is too high. The applicant team develops the mining through experimental researchThe original methods of heating desorption and inert gas desorption are replaced by membrane desorption, so that the desorption energy consumption is greatly reduced. However, the desorption membrane which is developed in the early stage and takes the PDMS as the main membrane material has poor solvent resistance in long-term use, and the membrane material is frequently replaced, so that the membrane desorption cost is increased.
The polyimide film is widely used for gas separation, such as separation and recovery of carbon dioxide, including separation of carbon dioxide and methane in biogas, removal of carbon dioxide in natural gas, recovery of carbon dioxide in oil field oil extraction and other fields. Polyimide membranes can also be used to prepare pervaporation membranes for the separation of volatile components.
Disclosure of Invention
Technical problem to be solved by the invention
The invention aims to provide a method for further improving the separation of CO from an organic solvent by a polyimide membrane2Is excellent in mechanical properties, solvent resistance and separation performance (permeation flux and separation factor).
Means for solving the technical problem
In view of the above problems, the present invention proposes a method for desorbing CO from an organic solvent2The polyimide film of (1) is prepared.
According to one embodiment of the present invention, there is provided a process for desorbing CO from an organic solvent2The preparation method of the polyimide film comprises the following steps:
(1) dissolving polyimide raw material powder shown in the following formula in an organic solvent, adding an inorganic nano material, stirring for 1-12h at 10-80 ℃, standing for 5-24h, and performing centrifugal deaeration at the rotation speed of 500-2000r/min to obtain a casting solution;
(n＝50～200)
(2) preparing a polyimide film on the support film by adopting rotary film coating equipment;
(3) putting the polyimide film prepared in the step (2) into deionized water for coagulation bath at the temperature of 5-90 ℃, and controlling the time to be 1-12 h;
(4) putting the polyimide film subjected to the coagulating bath in the step (3) into an organic solvent containing a cross-linking agent, controlling the temperature at 10-50 ℃ and the time at 1-12 h;
(5) and (4) conveying the polyimide film crosslinked in the step (4) into a vacuum drying oven for drying, and drying in the vacuum drying oven for 5-24h at the temperature of 10-80 ℃.
One embodiment is that the polyimide raw material powder is one or a mixture of several of the following materials, and the particle size is 0.05-5 mm.
In one embodiment, the organic solvent of the casting solution is one or more of Acetonitrile (ACN), N-Dimethylformamide (DMF), N-methylformylmorpholine (NMP), and Dimethylacetamide (DMAC).
In one embodiment, the inorganic nanomaterial is silicon dioxide (SIO)2) Titanium dioxide (TiO)2) And metatitanic acid (TiO (OH)2) One or a mixture of several of them.
One embodiment is that, the material of the support membrane is one or a mixture of more of poly dimethyl sulfoxide, cellulose acetate, cellulose, polyacrylonitrile, polytetrafluoroethylene, polyvinylidene fluoride and polyethylene terephthalate; the aperture of the basement membrane is 20-80 μm, and the thickness is 10-100 μm.
One embodiment is that, the cross-linking agent is one or a mixture of Ethylenediamine (EDA), Propylenediamine (PDA) and Butylenediamine (BDA).
One embodiment is that, the organic solvent of the cross-linking agent is one or a mixture of methanol (MeOH), Acetone (ACT), and isopropyl alcohol (IPA).
One embodiment is one in which the polyimide film prepared in step (2) is carried out in a nitrogen atmosphere at a nitrogen temperature of 10-80 ℃ and a rotation speed of 500-2000 rmp/min.
According to a second aspect of the present invention, there is provided a separation membrane prepared by the above method in the separation of dimethyl carbonateCO in organic solvents (DMC), diethyl carbonate (DEC), diethyl succinate (DES), dimethyl 2, 5-dioxaadipate (DMC-C2)2The use of (1).
The invention has the advantages of
Separation of CO from organic solvents according to the invention2The polyimide film is excellent in mechanical properties, solvent resistance and separation properties (permeation flux and separation factor).
Further features of the present invention will become apparent from the following description of exemplary embodiments.
Drawings
FIG. 1 is a schematic diagram of the structure of a polyimide frit for preparing a film
FIG. 2 shows a process for desorbing CO from an organic solvent according to the present invention2A schematic diagram of the method for producing a polyimide film of (1).
1 nitrogen heat exchanger 2 nitrogen inlet 3 nitrogen sealing cover 4 nitrogen outlet 5 casting film liquid inlet 6 rotary disk 7 rotary disk 8 control table
Detailed Description
One embodiment of the present disclosure will be specifically described below, but the present disclosure is not limited thereto.
The invention provides a method for desorbing CO from an organic solvent2The method for preparing a polyimide film (hereinafter abbreviated as PI film) comprises the following steps: (1) polyimide raw material powder (PI powder) shown in figure 1 is dissolved in an organic solvent, inorganic nano materials are added at the same time, the mixture is stirred for 1 to 12 hours at the temperature of between 10 and 80 ℃, the mixture is kept stand for 5 to 24 hours, and after centrifugal deaeration is carried out at the rotating speed of 500-2000r/min, casting solution is obtained. (2) A PI film was prepared in a part number 3-nitrogen enclosure in fig. 2 using a spin coating apparatus as shown in fig. 2. The support membrane is pre-paved on a part number 6-rotating disk in figure 2 (the uniform and compact PI membrane is prepared on the support membrane, the temperature of nitrogen can be controlled at 10-80 ℃ through a part number 1-nitrogen heat exchanger in figure 2, the thickness and the uniformity of the PI membrane can be controlled at 500-2000rmp/min through the quality of the added casting solution and the frequency of a part number 6-rotating disk in figure 2. the rotating disk is connected with a part number 8 control console through a part number 7-rotating shaft in figure 2,the rotational speed is regulated by the console. (3) And (3) putting the PI film prepared in the step (2) into deionized water for coagulation bath at the temperature of 5-90 ℃, and controlling the time to be 1-12 h. (4) And (4) putting the PI film in the coagulating bath in the step (3) into an organic solvent of a cross-linking agent, controlling the temperature at 10-50 ℃ and the time at 1-12 h. (5) And (4) conveying the crosslinked PI film obtained in the step (4) into a vacuum drying oven for drying, and drying in the vacuum drying oven for 5-24h at the temperature of 10-80 ℃.
The PI powder is one or a mixture of several of the following, and the particle size is 0.05-5 mm.
The organic solvent of the casting solution is one or a mixture of more of Acetonitrile (ACN), N-Dimethylformamide (DMF), N-methylmorpholine N (NMP) and Dimethylacetamide (DMAC).
The added inorganic nano material is silicon dioxide (SIO)2) Titanium dioxide (TiO)2) And metatitanic acid (TiO (OH)2) One or a mixture of several of them.
The supporting membrane material is characterized in that the base membrane is made of one or a mixture of more of poly dimethyl sulfoxide, poly acetate fiber, poly cellulose, polyacrylonitrile, polytetrafluoroethylene, polyvinylidene fluoride or polyethylene glycol terephthalate; the aperture of the basement membrane is 20-80 μm, and the thickness is 10-100 μm.
The cross-linking agent is one or a mixture of more of Ethylenediamine (EDA), Propylenediamine (PDA) and Butylenediamine (BDA).
The crosslinking agent is one or a mixture of more of organic solvents of methanol (MeOH), Acetone (ACT) and Isopropanol (IPA).
The separation membrane is used for separating CO from organic solvent in dimethyl carbonate (DMC), diethyl carbonate (DEC), diethyl succinate (DES) and dimethyl 2, 5-dioxaadipate (DMC-C2)2。
The rotary coating equipment shown in figure 2 is adopted for film preparation, so that the uniformity of film preparation is improved; supporting with base membrane such as poly dimethyl sulfoxide, cellulose acetate, cellulose, polyacrylonitrile, polytetrafluoroethylene, polyvinylidene fluoride or polyethylene glycol terephthalate, coagulating with deionized water, and coagulating with waterDiamine (EDA), Propane Diamine (PDA), Butanediamine (BDA) and the like, and improves the mechanical property of the polyimide film. By adding silicon dioxide (SIO) into polyimide2) Titanium dioxide (TiO)2) And metatitanic acid (TiO (OH)2) And the method of inorganic nano material can raise permeation flux of polyimide film.
Examples
The present invention is described in more detail by way of examples, but the present invention is not limited to the following examples.
Example 1
Weighing 6g of PI powder, adding nanoscale SIO21.2g of the casting solution is dissolved by 34g of DMF, stirred for 5h at 25 ℃, kept stand for 12h and subjected to centrifugal deaeration at the rotation speed of 1200r/min to obtain the casting solution. In a spin coating apparatus as shown in fig. 2, a surface of a cellulose-based film was coated. The polyimide film is prepared under the conditions of controlling the temperature to be 25 ℃ and the rotating speed to be 500 rpm/min. Placing the mixture into deionized water for coagulation bath at 25 ℃ for 1 h. Then the falling film is soaked in EDA-IPA solvent for 5h, and the temperature is controlled at 25 ℃. And finally, conveying the prepared PI film into a vacuum drying oven for drying, and drying in the vacuum drying oven for 12 hours at the temperature of 80 ℃.
And (3) putting the prepared PI film into DMC to soak for 24h, taking out and weighing, wherein the swelling rate is about 1.7%. Testing the membranes to desorb CO from DMC2Has a penetration flux of 0.758 kg/(m)2h) DMC did not penetrate.
Example 2
Weighing 6g of PI powder, adding nano TiO21.2g of the casting solution is dissolved by 34g of DMF, stirred for 5h at 25 ℃, kept stand for 12h and subjected to centrifugal deaeration at the rotation speed of 1200r/min to obtain the casting solution. In a spin coating apparatus as shown in FIG. 2, a surface of a cellulose-based film is coated. The polyimide film is prepared under the conditions of controlling the temperature to be 25 ℃ and the rotating speed to be 500 rpm/min. Placing the mixture into deionized water for coagulation bath at 25 ℃ for 1 h. Then the falling film is soaked in EDA-IPA solvent for 5h, and the temperature is controlled at 25 ℃. And finally, conveying the prepared PI film into a vacuum drying oven for drying, and drying in the vacuum drying oven for 12 hours at the temperature of 80 ℃.
Putting the prepared PI film into DMC to soak for 24h, taking out and weighing, and obtaining the swelling ratioAbout 2%. Testing the membranes to desorb CO from DMC2Has a permeation flux of 0.805 kg/(m)2h) DMC did not penetrate.
Example 3
Weighing 6g of PI powder, adding nano TiO (OH)21.2g of the casting solution is dissolved by 34g of DMF, stirred for 5h at 25 ℃, kept stand for 12h and subjected to centrifugal deaeration at the rotation speed of 1200r/min to obtain the casting solution. In a spin coating apparatus as shown in FIG. 2, a surface of a cellulose-based film is coated. The polyimide film is prepared under the conditions of controlling the temperature to be 25 ℃ and the rotating speed to be 500 rpm/min. Placing the mixture into deionized water for coagulation bath at 25 ℃ for 1 h. Then the falling film is soaked in EDA-IPA solvent for 5h, and the temperature is controlled at 25 ℃. And finally, conveying the prepared PI film into a vacuum drying oven for drying, and drying in the vacuum drying oven for 12 hours at the temperature of 80 ℃.
And (3) putting the prepared PI film into DMC to soak for 24h, taking out and weighing, wherein the swelling rate is about 1.6%. Testing the membranes to desorb CO from DMC2Has a permeation flux of 0.742 kg/(m)2h) DMC did not penetrate.
Industrial applicability
The film prepared by the method has the advantages of good solvent resistance, high film uniformity and CO2High separation factor and high flux, and has good industrial applicability.
The present invention is not limited to the above embodiments, and any modifications or alterations that can be easily conceived by those skilled in the art within the technical scope of the present invention are intended to be covered by the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (6)
1. Method for desorbing CO from organic solvent2The method for preparing the polyimide film is characterized by comprising the following steps:
(1) dissolving polyimide raw material powder of a structural unit shown as the following formula in an organic solvent, adding an inorganic nano material, stirring for 1-12h at 10-80 ℃, standing for 5-24h, and performing centrifugal deaeration at the rotation speed of 500-2000r/min to obtain a casting solution;
(n＝50～200)
(2) preparing a polyimide film on a support film by adopting rotary film coating equipment, wherein the polyimide film is carried out in a nitrogen atmosphere, the nitrogen temperature is 10-80 ℃, and the rotating speed is 500-2000 r/min;
(3) putting the polyimide film prepared in the step (2) into deionized water for coagulation bath at the temperature of 5-90 ℃, and controlling the time to be 1-12 h;
(4) putting the polyimide film subjected to the coagulating bath in the step (3) into an organic solvent containing a cross-linking agent, controlling the temperature at 10-50 ℃ and the time at 1-12h, wherein the cross-linking agent is one or a mixture of more of Ethylenediamine (EDA), Propylenediamine (PDA) and Butylenediamine (BDA), and the organic solvent of the cross-linking agent is one or a mixture of more of methanol (MeOH), Acetone (ACT) and Isopropanol (IPA);
(5) and (4) conveying the polyimide film crosslinked in the step (4) into a vacuum drying oven for drying, and drying in the vacuum drying oven for 5-24h at the temperature of 10-80 ℃.
2. The method according to claim 1, wherein the particle size of the polyimide raw material powder is 0.05 to 5 mm.
3. The preparation method according to claim 1, wherein the organic solvent of the casting solution is one or more of acetonitrile ACN, N-dimethylformamide DMF, N-methylformyl morpholine NMP and dimethylacetamide DMAC.
4. The method of claim 1, wherein the inorganic nanomaterial is silica SIO2Titanium oxide TiO2And metatitanic acid TiO (OH)2One or a mixture of several of them.
5. The preparation method according to claim 1, wherein the material of the support membrane is one or a mixture of more of poly dimethyl sulfoxide, cellulose acetate, cellulose, polyacrylonitrile, polytetrafluoroethylene, polyvinylidene fluoride and polyethylene terephthalate; the aperture of the basement membrane is 20-80 μm, and the thickness is 10-100 μm.
6. Separation membrane prepared by the process according to any one of claims 1 to 5 for separating CO from an organic solvent selected from the group consisting of dimethyl carbonate DMC, diethyl carbonate DEC, diethyl succinate DES, dimethyl 2, 5-dioxaadipate DMC-C22The use of (1).
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