CN116036885A - Mixed matrix membrane for carbon dioxide/nitrogen separation and preparation method and application thereof - Google Patents

Mixed matrix membrane for carbon dioxide/nitrogen separation and preparation method and application thereof Download PDF

Info

Publication number
CN116036885A
CN116036885A CN202310108607.0A CN202310108607A CN116036885A CN 116036885 A CN116036885 A CN 116036885A CN 202310108607 A CN202310108607 A CN 202310108607A CN 116036885 A CN116036885 A CN 116036885A
Authority
CN
China
Prior art keywords
mixed matrix
matrix membrane
carbon dioxide
membrane
metal
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.)
Pending
Application number
CN202310108607.0A
Other languages
Chinese (zh)
Inventor
谢亚勃
黄光灿
徐一然
彭昊欣
田英杰
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Beijing University of Technology
Original Assignee
Beijing University of Technology
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Beijing University of Technology filed Critical Beijing University of Technology
Priority to CN202310108607.0A priority Critical patent/CN116036885A/en
Publication of CN116036885A publication Critical patent/CN116036885A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • 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
    • B01D69/14—Dynamic membranes
    • B01D69/141—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
    • 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
    • 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
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/72—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of the groups B01D71/46 - B01D71/70 and B01D71/701 - B01D71/702
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Dispersion Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

The invention discloses a mixed matrix membrane for carbon dioxide/nitrogen separation, and a preparation method and application thereof, and belongs to the field of membrane preparation technology and gas separation. Dispersing metal-organic framework MIL-101 into an organic solvent, stirring, carrying out ultrasonic treatment to obtain a suspension, adding high molecular polymer PIM-1, stirring, carrying out ultrasonic treatment to obtain a mixed matrix membrane building solution, preparing a membrane, and drying to obtain a mixed matrix membrane for carbon dioxide/nitrogen separation. The mixed matrix membrane for carbon dioxide/nitrogen separation disclosed by the invention has the advantages of low cost of raw materials, simple synthesis method, realization of complete mixing with a polymer matrix, and overcoming of easy aggregation of fillers in the mixed matrix membrane and easy aggregation with the polymerThe problem of poor compatibility of the matrix can realize CO 2 /N 2 The high-efficiency separation of the catalyst has high use value and wide industrial application prospect.

Description

Mixed matrix membrane for carbon dioxide/nitrogen separation and preparation method and application thereof
Technical Field
The invention belongs to the field of membrane preparation technology and gas separation, and particularly relates to a mixed matrix membrane for carbon dioxide/nitrogen separation, and a preparation method and application thereof.
Background
With the development of new fossil fuel power plants and the growth of energy intensive industries, further increases in carbon dioxide emissions have been unavoidable. Therefore, carbon Capture and Storage (CCS) has become a major component of many national and global emission abatement scenarios.
Compared with the traditional gas separation process, the membrane separation technology has many advantages of gas separation, such as simple operation, small occupied area, low cost and strong processability, and the permeation selectivity of the gas separation membrane is an important standard for evaluating the comprehensive performance of the gas separation membrane. However, there is a trade-off in this technique that selectivity decreases as permeability increases, which is referred to by researchers as the Robeson (Robeson) upper limit. Since mixed matrix membranes (mixed matrix membranes, MMMs) are capable of combining the advantages of polymer matrices and fillers, they represent a cost-effective measure of breaking the upper Robeson limit. Thus, in the last twenty years, mixed matrix membranes were used for CO 2 Isolation has led to extensive research.
The mixed matrix membrane is a novel organic-inorganic hybrid membrane which takes a high molecular polymer matrix as a continuous phase and inorganic materials as a disperse phase, and can have the advantages of two components, on one hand, the unique advantages of the inorganic filler in the aspect of gas adsorption separation are exerted, and on the other hand, the good processability of the polymer materials is also reserved. The incorporation of nanoscale fillers into high molecular polymer matrices is an effective method of increasing their permeability and selectivity.
To date, many nanoscale fillers have been added to PIM-1 or other polymer matrices to produce mixed matrix films, and the fillers are generally divided into two types: non-porous fillers and porous fillers. Common porous fillers include fumed silica, carbon nanotubes, graphene, and the like. However, such fillers are generally not very compatible with polymers, and have the following drawbacks: the filler is easy to agglomerate, the film forming uniformity is poor, the morphology is irregular, the surface roughness is high, and the like, and the selectivity of the mixed matrix film is lower and lower along with the increase of the load. In contrast, the organic framework of the novel porous filler MOFs can effectively improve compatibility with the polymer matrix.
The metal-organic framework Materials (MOFs) are porous hybrid materials formed by connecting organic ligands with metal ions, so that the MOFs have the common characteristics and unique structures of organic high polymer materials and inorganic materials, and have potential application values in the fields of adsorption separation, gas storage, sensing, catalysis and the like due to the characteristics of high porosity, large specific surface area, adjustable pore size and properties and the like. More importantly, the MOFs material has the greatest characteristics that: the high specific surface area and porous structure of MOFs are extremely advantageous for rapid permeation of gas molecules, and MOFs can also be designed and modified according to gas separation requirements, which makes MOFs one of the most promising gas separation membrane materials at present.
The chemical characteristics of the material can be changed by designing, regulating and modifying MOFs and pore canals thereof, the characteristic of easy functionalization is shown, and the respective advantages of MOFs and macromolecules are combined, so that the characteristics of the polymer chain can be reserved, such as compatibility and processability of various chemical groups, and the like, and the porosity and certain functions of the MOFs can be obtained. In addition, the MOFs have flexible components and structures and strong designability, and can conveniently introduce groups or structures with specific functions into materials according to the structures and properties of selected polymers so as to realize strong binding force on different types of polymers to meet different environmental requirements (such as separation, catalysis, conduction, biological medicine and the like). MOFs materials are generally more compatible with polymer matrices because the organic linkers in MOFs have stronger interactions with the polymer chains (similar compatibility), and therefore MOFs have been proposed as novel adsorbents for industrial gas separations and also identified as promising high performance Mixed Matrix Membrane (MMMs) filler components.
Disclosure of Invention
The invention aims to solve the problem of CO in the flue gas of a power plant 2 /N 2 Is to solve the separation problem of (1)The aim of emission reduction is to provide a mixed matrix membrane for carbon dioxide/nitrogen separation, and a preparation method and application thereof, so that the performance of the mixed matrix membrane for separating carbon dioxide/nitrogen is improved.
In order to achieve the above object, the present invention provides the following solutions:
according to one of the technical schemes of the invention, a mixed matrix membrane for carbon dioxide/nitrogen separation is provided, wherein a disperse phase of the mixed matrix membrane is a metal-organic framework MIL-101, and a continuous phase of the mixed matrix membrane is a high polymer PIM-1.
Further, the metal-organic framework MIL-101 is filled in an amount of 5-40wt% in the mixed matrix film.
Still further, the metal-organic framework MIL-101 was filled in an amount of 15wt% in the mixed matrix film.
Further, the preparation method of the metal-organic framework MIL-101 comprises the following steps: mixing chromium nitrate, terephthalic acid, concentrated nitric acid and water, heating, cooling, centrifuging, washing and vacuum drying to obtain the metal-organic framework MIL-101.
Still further, the feed liquid ratio of chromium nitrate, terephthalic acid, concentrated nitric acid and water is 800mg:328mg:0.135mL:10mL; the heating temperature is 220 ℃, and the heating time is 8 hours; vacuum oven drying (120deg.C, 1200 Pa) for 5h.
Further, the high polymer PIM-1 is a linear self-microporous polymer which is widely researched at present and is prepared by polycondensation reaction of a monomer TTSBI with a twisted spiral structure and a monomer TFTPN. PIM-1 has a large specific surface area (760-850 m) 2 And controllable microporous structure, the synthesis method is relatively simple, has good processibility, and shows application potential in the fields of gas storage, separation and purification.
The PIM-1 preparation method comprises the following steps: TTSBI (5, 5', 6' -tetrahydroxy-3, 3', 3' -tetramethyl-1, 1' -helical biindane), TFTPN (tetrafluoro terephthalonitrile) and potassium carbonate are added into a solvent, stirred under the nitrogen atmosphere, and reaction products are separated out after methanol is added, washed and dried in vacuum, thus obtaining the high polymer PIM-1.
Still further, the feed liquid ratio of TTSBI, TFTPN, potassium carbonate and solvent is: 6.404g:4.002g:6.91g:40mL; the solvent is a mixed solution of N-methylpyrrolidone (NMP) and toluene (N-methylpyrrolidone: toluene=3:1, volume ratio); the stirring time was 0.5h, the drying temperature was 70℃and the drying time was 48h.
The second technical scheme of the invention is that the preparation method of the mixed matrix membrane for separating carbon dioxide/nitrogen comprises the following steps: dispersing metal-organic frame MIL-101 into an organic solvent, stirring and carrying out ultrasonic treatment to obtain metal-organic frame suspension; adding the high polymer PIM-1 into the metal-organic frame suspension, stirring, performing ultrasonic treatment to obtain a mixed matrix membrane building solution, preparing a membrane, drying to obtain the mixed matrix membrane for carbon dioxide/nitrogen separation, and placing the obtained mixed matrix membrane into a vacuum oven to be dried for 8-12h at 120 ℃.
Further, the organic solvent is chloroform.
Further, the ratio of the metal-organic framework MIL-101 to the high polymer PIM-1 to the organic solvent is as follows: (2-60) mg: (40-150) mg: (4-15) mL.
Further, the drying temperature is 26.5 ℃, the drying humidity is 65%, and the drying time is 24-48 h.
Further, the drying time was 48 hours.
The third technical scheme of the invention is the application of the mixed matrix membrane for carbon dioxide/nitrogen separation in carbon dioxide/nitrogen separation.
The invention discloses the following technical effects:
the invention takes MIL-101 which has high porosity, chemical stability and thermal stability, cheap preparation raw materials and simple synthesis process as a disperse phase, takes PIM-1 which has high free volume and high gas permeability and is a microporous high polymer as a continuous phase, and prepares the metal-organic frame mixed matrix membrane by strictly controlling the volatilization temperature and humidity of membrane building liquid, thus obtaining the carbon dioxide/nitrogen component with high permeability and high selectivityAn isolated mixed matrix membrane for separating CO in an industrial setting 2 And N 2 . The preparation method of the mixed matrix membrane is simple, easy to implement, easy to produce in batches and easy to produce CO 2 /N 2 The separation performance is high, the doping amount of the metal-organic framework MIL-101 is low, and the industrial application is easy.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions of the prior art, the drawings that are needed in the embodiments will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a scanning electron microscope topography of a metal-organic framework MIL-101 prepared in example 1;
FIG. 2 is N at 77K of the metal-organic framework MIL-101 prepared in example 1 2 Sucking the attached drawings;
FIG. 3 is an X-ray powder diffraction pattern of the metal-organic framework MIL-101 prepared in example 1 and a mixed matrix membrane for carbon dioxide/nitrogen separation;
FIG. 4 is a physical diagram of a mixed matrix membrane for carbon dioxide/nitrogen separation prepared in example 1;
FIG. 5 is a scanning electron microscope topography of the mixed matrix membrane for carbon dioxide/nitrogen separation prepared in example 1;
FIG. 6 is 2019 CO 2/ N 2 Upper bound of Robeson, where the ordinate P CO2 /P N2 Is CO 2 /N 2 Selectivity, abscissa P CO2 (Barrer) is CO 2 Permeability coefficient.
Detailed Description
Various exemplary embodiments of the invention will now be described in detail, which should not be considered as limiting the invention, but rather as more detailed descriptions of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the invention described herein without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from consideration of the specification of the present invention. The specification and examples are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are intended to be inclusive and mean an inclusion, but not limited to.
The normal temperature in the examples of the present invention means 25.+ -. 2 ℃.
Embodiments of the present invention provide a mixed matrix membrane for carbon dioxide/nitrogen separation, wherein the dispersed phase of the mixed matrix membrane is metal-organic framework MILs-101, and the continuous phase of the mixed matrix membrane is high molecular polymer PIM-1.
Further, the metal-organic framework MIL-101 is filled in an amount of 5-40wt% in the mixed matrix film.
In some embodiments of the invention, the metal-organic framework MIL-101 is present in the mixed matrix membrane in an amount of 15wt%.
The embodiment of the invention also provides a preparation method of the mixed matrix membrane for carbon dioxide/nitrogen separation, which comprises the following steps: dispersing metal-organic frame MIL-101 into an organic solvent, stirring and carrying out ultrasonic treatment to obtain metal-organic frame suspension; adding the high polymer PIM-1 into the metal-organic framework suspension, stirring, performing ultrasonic treatment to obtain a mixed matrix membrane building solution, preparing a membrane, and drying to obtain the mixed matrix membrane for carbon dioxide/nitrogen separation.
Further, the organic solvent is chloroform; the feed liquid ratio of the metal-organic framework MIL-101 to the high polymer PIM-1 to the organic solvent is as follows: (2-60) mg: (40-150) mg: (4-15) mL; the drying temperature is 26.5 ℃, the drying humidity is 65%, and the drying time is 24-48 h.
In some embodiments of the invention, the drying time is 48 hours.
The embodiment of the invention also provides application of the mixed matrix membrane for carbon dioxide/nitrogen separation in carbon dioxide/nitrogen separation.
Example 1
A method for preparing a mixed matrix membrane for carbon dioxide/nitrogen separation, comprising the steps of:
(1) Synthesis of Polymer (PIM-1)
a. Purifying TTSBI; weighing TTSBI, placing into a flat-bottom beaker, adding anhydrous methanol, stirring at constant speed until the solid is completely dissolved, placing the beaker on a heating plate, continuously heating to boil the solution, and filtering the solution with a funnel while the solution is hot; then placing the obtained solution in a beaker, continuously heating and evaporating the solvent, immediately stopping heating until a small amount of white crystals are separated out from the bottom of the solution, slowly cooling to room temperature, separating out a large amount of white precipitates from the bottom of the beaker, filtering by a funnel, and collecting the product; and placing the obtained white or light brown solid into a vacuum drying oven to obtain the TTSBI.
b. Purifying TFTPN; weighing TFTPN, placing at the bottom of a vacuum sublimator, mounting the sublimator in a fume hood with an oil bath pan and double calandria, opening a vacuum pump to vacuumize the sublimator for 15min, opening the oil bath pan, and slowly heating until a layer of colorless crystal product is gradually separated out at the bottom of a condensate pipe; then slowly reducing the vacuum degree in the system to the standard atmospheric pressure, removing the condenser, carefully scraping off the crystallized product and collecting the crystallized product, repeating the operation until no obvious residue exists in the vacuum sublimator, and collecting colorless crystals, namely the TFTPN.
c. Synthesis of PIM-1: purified TTSBI (6.404 g), TFTPN (4.002 g), K 2 CO 3 (6.91 g) and a solvent (40 mL) were added to a three-necked flask to obtain a mixture, the solvent was a mixed solution of NMP/toluene (30/10), the mixture was stirred under a nitrogen atmosphere, the reaction was carried out for 0.5h, the reaction product was poured into methanol, then the yellow solid was washed three times with deionized water, and the yellow solid was dried under vacuum at 70℃for 48h.
(2) Synthesis of metal-organic frameworks MIL-101
Weighing Cr (NO) 3 ) 3 ·9H 2 O800 mg and terephthalic acid 328mg were mixed with 0.135mL of concentrated nitric acid and 10mL of deionized water, and the mixture was transferred to a Teflon lined hot liquid autoclave. The autoclave was placed in an oven, heated to 220 ℃, heated for 8h, cooled to room temperature within 6 h. Separating the product in the autoclave with a centrifuge, washing with hot DMF three times, each time with hot methanol and ethanol (DMF, methanol and ethanol each having a temperature of 160deg.C), and drying the finally separated solid in a vacuum oven (120deg.C, 1200 Pa) for 5h to obtain metal-organic framework MIL-101, wherein FIG. 1 is a scanning electron microscope topography of the metal-organic framework MIL-101, and FIG. 2 is N of the metal-organic framework MIL-101 at 77K 2 The drawing is sucked.
(3) Synthesis of mixed matrix membrane building solution
Adding 17.65mg of the metal-organic frame (MIL-101) prepared in the step (2) into 6mL of chloroform, magnetically stirring for 3h, and performing ultrasonic treatment until the metal-organic frame (MIL-101) is completely dispersed in the chloroform; adding 100mg of the high molecular polymer (PIM-1) prepared in the step (1) into the metal-organic framework suspension, magnetically stirring for 6 hours until the high molecular polymer (PIM-1) is completely dissolved, performing ultrasonic treatment for 0.5 hour, and removing bubbles to obtain the mixed matrix membrane building solution.
(4) Preparation of mixed matrix membranes for carbon dioxide/nitrogen separation
Pouring the mixed matrix membrane construction solution prepared in the step (3) into a 46X 18mm membrane-making planar glass surface dish, putting the dish into a constant temperature and humidity box with the temperature of 26.5 ℃ and the relative humidity of 65%, and volatilizing the solvent for 48 hours to obtain the green mixed matrix membrane for separating carbon dioxide from nitrogen.
FIG. 3 is an X-ray powder diffraction pattern of the metal-organic framework MIL-101 and the mixed matrix membrane for carbon dioxide/nitrogen separation obtained in this example, and it can be seen from FIG. 3 that the metal-organic framework MIL-101 is already present in the mixed matrix membrane.
FIG. 4 is a physical diagram of a mixed matrix membrane for carbon dioxide/nitrogen separation prepared in example 1.
Fig. 5 is a scanning electron microscope morphology diagram of the mixed matrix membrane for carbon dioxide/nitrogen separation prepared in example 1, and as can be seen from fig. 5, the metal-organic framework MILs-101 has good dispersibility in the high molecular polymer (PIM-1) and no agglomeration.
(5) Performance test of mixed matrix membranes for carbon dioxide/nitrogen separation:
the single component gas test shows that the gas separation membrane prepared in the embodiment has CO under the test condition of 25 ℃ and 0.2MPa 2 The permeability coefficient can reach 14879barrer, N 2 Is 612barrer; CO 2 /N 2 Selectivity is 24.3, CO exceeds 2019 2 /N 2 The upper Robeson limit of (2) is shown in detail in FIG. 6.
Examples 2 to 6
The difference from example 1 is that the metal-organic frameworks (MIL-101) were filled in different amounts in the synthesis of the mixed matrix dope in step (3), as shown in Table 1.
TABLE 1
Figure BDA0004075917610000091
The single component gas tests show that the gases prepared in examples 2-6Separation membrane, CO under test conditions of 25 ℃ and 0.2MPa 2 And N 2 Is (are) CO 2 /N 2 The selectivity is shown in Table 2, and the CO is over 2019 2 /N 2 Upper Robeson limit of (c).
TABLE 2
Figure BDA0004075917610000092
Figure BDA0004075917610000101
Comparative example 1
The difference from example 1 is that no metal-organic framework MILs-101 was added in step (3), and the specific operation was:
adding 100mg of the high molecular polymer (PIM-1) prepared in the step (1) into 6mL of chloroform, magnetically stirring for 6h to completely dissolve, and then performing ultrasonic treatment for 0.5h to remove bubbles; obtaining the pure polymer membrane building liquid. Pouring the obtained pure polymer film building solution into a 46X 18mm film-forming glass surface dish, and putting the film-forming glass surface dish into a constant temperature and humidity box with the temperature of 26.5 ℃ and the relative humidity of 65%; after 48h of solvent evaporation, a pure high molecular polymer (PIM-1) film was obtained.
Single-component gas tests show that the pure polymer gas separation membrane prepared in the comparative example 1 has CO under the test condition of 25 ℃ and 0.2MPa 2 The permeability coefficient can reach 70000 barrer, CO 2 /N 2 Selectivity of 22, lower than 2019 CO 2/ N 2 Upper Robeson limit of (c).
As can be seen by comparing comparative example 1 with example 1, after the metal-organic framework MIL-101 was introduced, CO 2 Permeability and CO 2 /N 2 The selectivity is greatly improved.
The above embodiments are only illustrative of the preferred embodiments of the present invention and are not intended to limit the scope of the present invention, and various modifications and improvements made by those skilled in the art to the technical solutions of the present invention should fall within the protection scope defined by the claims of the present invention without departing from the design spirit of the present invention.

Claims (9)

1. A mixed matrix membrane for carbon dioxide/nitrogen separation, characterized in that the dispersed phase of the mixed matrix membrane is a metal-organic framework MILs-101, and the continuous phase of the mixed matrix membrane is a high molecular polymer PIM-1.
2. The mixed matrix membrane for carbon dioxide/nitrogen separation of claim 1, wherein the metal-organic framework MIL-101 is present in the mixed matrix membrane in an amount of 5-40wt%.
3. The mixed matrix membrane for carbon dioxide/nitrogen separation of claim 2, wherein the metal-organic framework MIL-101 is present in the mixed matrix membrane in an amount of 15wt%.
4. A method for preparing a mixed matrix membrane for carbon dioxide/nitrogen separation according to any one of claims 1 to 3, comprising the steps of:
dispersing metal-organic frame MIL-101 into an organic solvent, stirring and carrying out ultrasonic treatment to obtain metal-organic frame suspension; adding the high polymer PIM-1 into the metal-organic framework suspension, stirring, performing ultrasonic treatment to obtain a mixed matrix membrane building solution, preparing a membrane, and drying to obtain the mixed matrix membrane for carbon dioxide/nitrogen separation.
5. The method according to claim 4, wherein the organic solvent is chloroform.
6. The method according to claim 4, wherein the ratio of the metal-organic frameworks MILs-101 to the high molecular polymer PIM-1 to the organic solvent is: (2-60) mg: (40-150) mg: (4-15) mL.
7. The process according to claim 4, wherein the drying temperature is 26.5 ℃, the drying humidity is 65% and the drying time is 24 to 48 hours.
8. The method of claim 7, wherein the drying time is 48 hours.
9. Use of a mixed matrix membrane for carbon dioxide/nitrogen separation according to any one of claims 1 to 3 in carbon dioxide/nitrogen separation.
CN202310108607.0A 2023-02-14 2023-02-14 Mixed matrix membrane for carbon dioxide/nitrogen separation and preparation method and application thereof Pending CN116036885A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202310108607.0A CN116036885A (en) 2023-02-14 2023-02-14 Mixed matrix membrane for carbon dioxide/nitrogen separation and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202310108607.0A CN116036885A (en) 2023-02-14 2023-02-14 Mixed matrix membrane for carbon dioxide/nitrogen separation and preparation method and application thereof

Publications (1)

Publication Number Publication Date
CN116036885A true CN116036885A (en) 2023-05-02

Family

ID=86119970

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202310108607.0A Pending CN116036885A (en) 2023-02-14 2023-02-14 Mixed matrix membrane for carbon dioxide/nitrogen separation and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN116036885A (en)

Similar Documents

Publication Publication Date Title
Ahmad et al. Enhanced gas separation performance of 6FDA-DAM based mixed matrix membranes by incorporating MOF UiO-66 and its derivatives
US7658784B2 (en) Composite material, in particular composite membrane, and process for the production of the same
Zhang et al. Enhanced flux of polydimethylsiloxane membrane for ethanol permselective pervaporation via incorporation of MIL-53 particles
Yahia et al. Effect of incorporating different ZIF-8 crystal sizes in the polymer of intrinsic microporosity, PIM-1, for CO2/CH4 separation
CN113209841B (en) Mixed matrix membrane of aminated ZIF-8 and polyvinyl alcohol, and preparation method and application thereof
Mao et al. Zeolitic imidazolate frameworks in mixed matrix membranes for boosting phenol/water separation: Crystal evolution and preferential orientation
CN112029106B (en) Preparation method and application of modified HKUST-1 sulfur-resistant adsorbent for adsorbing n-hexane
CN113713636A (en) Mixed matrix membrane based on PIM-1 and preparation method thereof
CN113817116A (en) Preparation of covalent organic framework material and application of covalent organic framework material in rare earth separation
CN112675720A (en) Preparation method and application of mixed matrix membrane filled with bimetallic strip material
Jiang et al. Solvent-processable 0D covalent organic framework quantum dot engineered composite membranes for biogas upgrading
Chang et al. Influence of casting solvents on sedimentation and performance in metal–organic framework mixed-matrix membranes
Hu et al. The influence of intermediate layer and graphene oxide modification on the CO2 capture efficiency of Pebax-GO/PDMS/PSf mixed matrix composite membranes
Guan et al. Boosting the pervaporation performance of PDMS membrane for 1-butanol by MAF-6
CN112957928B (en) Microporous polymer composite membrane and preparation method thereof
CN108744991B (en) Preparation method and application of organic-inorganic mixed matrix membrane doped with zeolite imidazole ester framework porous carbon nano material
CN112316741B (en) Mixed matrix membrane of beaded MOF filled silicone rubber
CN110270231B (en) MOF (Metal organic framework) derivative gas separation membrane as well as preparation method and application thereof
CN116036885A (en) Mixed matrix membrane for carbon dioxide/nitrogen separation and preparation method and application thereof
CN112156660A (en) Metal organic framework M-gate mixed matrix membrane and preparation and application thereof
KR102062865B1 (en) A gas separator and a method for manufacturing the same
CN114939350A (en) Preparation of metal-organic cage complex mixed matrix membrane for gas separation
CN110787657B (en) Preparation method of Pebax/MIL-101 mixed matrix membrane
CN113856494A (en) Preparation and application of metal organic framework filled mixed matrix membrane with photoresponse
CN114939349B (en) Preparation of metal-organic cavity complex mixed matrix membrane for gas separation

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