CN112237852A - Bionic material Bio-ZIF filled block polyether amide mixed matrix membrane and preparation method and application thereof - Google Patents

Bionic material Bio-ZIF filled block polyether amide mixed matrix membrane and preparation method and application thereof Download PDF

Info

Publication number
CN112237852A
CN112237852A CN202011102131.2A CN202011102131A CN112237852A CN 112237852 A CN112237852 A CN 112237852A CN 202011102131 A CN202011102131 A CN 202011102131A CN 112237852 A CN112237852 A CN 112237852A
Authority
CN
China
Prior art keywords
zif
bio
mixed matrix
matrix membrane
pebax
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
CN202011102131.2A
Other languages
Chinese (zh)
Inventor
李雪琴
黄路
丁思远
吕侠
魏忠
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.)
Shihezi University
Original Assignee
Shihezi University
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 Shihezi University filed Critical Shihezi University
Priority to CN202011102131.2A priority Critical patent/CN112237852A/en
Publication of CN112237852A publication Critical patent/CN112237852A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • 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
    • B01D71/56—Polyamides, e.g. polyester-amides
    • 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
    • B01D67/0006—Organic membrane manufacture by chemical reactions
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • C08G83/008—Supramolecular polymers
    • 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
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Manufacturing & Machinery (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

The invention provides a block polyether amide mixed matrix membrane filled with a bionic material Bio-ZIF, which is prepared from the Bio-ZIF and a block polyether amide Pebax; the thickness of the mixed matrix membrane is 100-130 mu m, and the invention also provides a preparation method and application thereof. The Pebax/Bio-ZIF mixed matrix membrane prepared by the method has the advantages of simple preparation process, controllable reaction, cheap and easily obtained raw materials and mild conditions, can ensure that the advantages of a metal organic framework and a high molecular matrix are complementary, and the introduced defect metal bionic site and amino group pair CO2Has synergistic promoting effect, and the prepared mixed matrix membrane has CO2Affinity and sievingCan intensify CO2Transport in the membrane.

Description

Bionic material Bio-ZIF filled block polyether amide mixed matrix membrane and preparation method and application thereof
Technical Field
The invention relates to a bionic material Bio-ZIF filled block polyether amide mixed matrix membrane and a preparation method and application thereof.
Background
The current society is increasingly dependent on fossil energy (coal, oil and natural gas), and due to the non-renewable nature of fossil energy, people face an energy crisis while enjoying life convenience. In order to alleviate the energy crisis caused by fossil energy, the biological methane gas enters the lives of people as clean renewable energy. The main component in the biogas is methane (CH)4) And carbon dioxide (CO)2) And CO2The existence of the methane gas can affect the heat value and transportation of the biological methane gas. Thus CO in biomethane gas2Ablation is the focus of current investigator research. At present, CO2Gas separation methods are mainly classified into pressure swing adsorption, cryogenic separation, membrane separation, and chemical absorption. CO in biomethane2In the separation technology, the membrane separation technology has the advantages of high efficiency, environmental protection, low energy consumption, simple operation, small occupied area and the like, so that the membrane separation technology has wider application prospect.
The gas separation membrane can be classified into an inorganic membrane, an organic membrane, and a mixed matrix membrane, depending on the membrane material. The inorganic membrane has the advantages of regular pore channel structure, high temperature and pressure resistance, acid and alkali corrosion resistance and the like, but the industrial application of the inorganic membrane is limited by the defects of high brittleness, high production difficulty, high price and the like. The organic film has the advantages of low price, easy processing, good film forming property and the like, but the organic polymer film is restricted by the trade-off effect and has the defect of incapability of combining high permeability and high selectivity. At present, therefore, the mixed matrix membrane is most widely used in membrane separation. The mixed matrix membrane is prepared by doping a filler into a high polymer material, integrates the advantages of a high polymer membrane and an inorganic membrane, can derive new advantages at the same time, has the advantages of improving the permeability and selectivity of gas, and can overcome the trade-off effect. The fillers commonly used at present are: zeolite, silica, graphene oxide, carbon nanotubes, various metal-organic frameworks, and covalent organic frameworks.
Carbonic Anhydrase (CA) as a catalytic CO2One of the fastest hydration enzymes, catalyzing CO2And water are quickly converted into carbonic acid H2CO3And decompose into bicarbonate radical (HCO) according to the predominant species concentration3 -) And protons. However, CA catalyzes CO2The hydration reaction rate has incomparable advantages and simultaneously has the defect of harsh catalytic reaction conditions: it is not resistant to acid, alkali and high temperature. CA is a metalloenzyme, a metal ion pair CO that binds only within the active site cavity2Catalytically, the active center usually comprises m (ii) ions of tetrahedral geometry, with three amino acid residues as ligands in addition to the water/hydroxide ions coordinating the metal.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a bionic material Bio-ZIF filled block polyether amide mixed matrix membrane, which is used for separating CO2/CH4Mixed gas (20/80, v/v) with high permeability and high separation factor.
The invention utilizes a Zn metal site of a bionic zeolite imidazolate framework (Bio-ZIF) to link three imidazole groups with a water molecule, which is similar to a tetrahedral molecular structure of an active site of CA (shown in figure 1), and catalyzes CO on the metal bionic site of the framework2Hydration reaction of (2), and amino group with CO2The reversible water and the reaction of (A) are cooperated in a mixed matrix membrane using polyoxyethylene-polyamide block copolymer (Pebax) as a matrix to construct efficient CO in the membrane2A transfer path to promote the perm-selective properties of the mixed matrix membrane and to overcome the trade-off effect.
In FIG. 1, panel A shows the chemical structure of the CA active site, and panel B shows the chemical structure of the Bionical active site of Bio-ZIF.
The invention provides a block polyether amide mixed matrix membrane filled with a bionic material Bio-ZIF, which is prepared from the Bio-ZIF and a block polyether amide Pebax; the thickness of the mixed matrix membrane is 100-130 μm.
Preferably, in the mixed matrix membrane, the mass percent of the Bio-ZIF is 4-16%, and the mass percent of the block polyether amide Pebax is 84-96%.
Preferably, the mass ratio of Bio-ZIF to block polyetheramide Pebax in the mixed matrix membrane is 4:96, 8:92, 12:88 or 16: 84.
Preferably, the preparation method of the Bio-ZIF comprises the following steps: 2-methylimidazole and Zn (NO)3)2Mixing and reacting to obtain ZIF-8; and then, ZIF-8 and 3-amino-1, 2, 4-triazole are reacted to prepare Bio-ZIF.
The invention provides a preparation method of a block polyether amide mixed matrix membrane filled with the bionic material Bio-ZIF, wherein the mixed matrix membrane is prepared by doping Bio-ZIF serving as a filling agent into a block polyether amide Pebax matrix.
Preferably, the preparation method of the Bio-ZIF comprises the following steps: 2-methylimidazole and Zn (NO)3)2Mixing and reacting to obtain ZIF-8; and then, ZIF-8 and 3-amino-1, 2, 4-triazole are reacted to prepare Bio-ZIF.
Preferably, the preparation method of the Bio-ZIF comprises the following steps: 2-methylimidazole and Zn (NO)3)2Respectively dissolving and mixing, carrying out ultrasonic reaction, standing, centrifuging, collecting precipitate and washing to obtain ZIF-8; drying ZIF-8, dispersing in methanol to obtain ZIF-8 suspension, adding 3-amino-1, 2, 4-triazole into the ZIF-8 suspension, stirring in water bath for reaction, centrifuging, collecting precipitate, washing, and drying to obtain Bio-ZIF.
Preferably, the 2-methylimidazole or Zn (NO) is used3)2And 3-amino-1, 2, 4-triazole in a molar ratio of: 4: 1: 1.49.
preferably, the specific method for doping the block polyether amide Pebax matrix by using Bio-ZIF as a filler comprises the following steps: and physically blending the Bio-ZIF and the block polyether amide Pebax, stirring at room temperature to obtain a casting solution, casting and drying the casting solution to obtain the block polyether amide mixed matrix membrane filled with the bionic material Bio-ZIF.
The invention also provides the Bio-ZIF filler of the bionic materialSeparation of CO from filled block polyether amide mixed matrix film2/CH4The application in mixed gas.
The bionic material Bio-ZIF filled block polyether amide mixed matrix membrane is used for separating CO2/CH4Mixed gas of CO2Flux 406-525 barrel (1 barrel 10)-10cm3cm/cm2scmHg)，CO2/CH4The selectivity is 30-40.
Compared with the prior art, the invention has the beneficial effects that: the Pebax/Bio-ZIF mixed matrix membrane prepared by the method has the advantages of simple preparation process, controllable reaction, cheap and easily obtained raw materials and mild conditions, can ensure that the advantages of a metal organic framework and a high molecular matrix are complementary, and the introduced defect metal bionic site and amino group pair CO2Has synergistic promoting effect, and the prepared mixed matrix membrane has CO2Affinity and sieving effects, and can enhance CO2Transport in the membrane to CO2/CH4The mixture's permselectivity has exceeded the 2008 Robeson upper limit.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
in FIG. 1, panel A shows the chemical structure of the CA active site, and panel B shows the chemical structure of the Bionical active site of Bio-ZIF.
FIG. 2 is a chemical structural diagram of Bio-ZIF.
FIG. 3 is a sectional view of a scanning electron microscope of the Pebax/Bio-ZIF-4 mixed matrix membrane prepared in example 1.
FIG. 4 is a cross-sectional view of a scanning electron microscope of the Pebax/ZBio-ZIF-8 mixed matrix membrane prepared in example 2.
FIG. 5 is a sectional view of a Pebax/Bio-ZIF-12 mixed matrix membrane prepared in example 3 under a scanning electron microscope.
FIG. 6 is a sectional view of a Pebax/Bio-ZIF-16 mixed matrix membrane prepared in example 4 under a scanning electron microscope.
Fig. 7 is a cross-sectional view of the Pebax film obtained in comparative example 1 under a scanning electron microscope.
FIG. 8 is a sectional view of a scanning electron microscope of the Pebax/ZIF-8-12 film obtained in comparative example 2.
Detailed Description
The following examples are given to facilitate a better understanding of the invention, but do not limit the invention. The experimental procedures in the following examples are conventional unless otherwise specified. The test materials used in the following examples are commercially available unless otherwise specified.
The preparation method of the Pebax/Bio-ZIF mixed matrix membrane comprises the following steps:
step 1, preparation of Bio-ZIF:
1mmol of Zn (NO) at room temperature3)2·6H2O was dissolved in xmL methanol (designated solution A) and 4mmol 2-methylimidazole was dissolved in xmL methanol (designated solution B). Then, the two solutions were separately sonicated for 15 minutes, and then the solution B was slowly added to the solution A under sonication, which was sonicated at room temperature for 4 hours, followed by standing at room temperature for 24 hours. The precipitate was collected by centrifugation and washed three times with methanol to give ZIF-8. Finally, the precipitate was dried at 60 ℃ overnight to obtain ZIF-8 nanofiller.
TABLE 1ZIF-8 nanofiller particle size vs. methanol solution volume relationship
Figure BDA0002725736220000041
The prepared ZIF-8 nanofiller (200mg) was uniformly dispersed in 100mL of methanol by sonication for 30 minutes to obtain a uniform suspension of ZIF-8. Then, 3-amino 1,2, 4-triazole (Atz) (585mg) was added to the suspension of ZIF-8, and stirred for 8h in a water bath at 50 ℃. The precipitate was collected by centrifugation and washed with methanol. Finally, the precipitate was dried at 70 ℃ for 3 days under vacuum, thereby obtaining a Bio-ZIF nanofiller (see fig. 2) having no change in particle size compared to ZIF-8.
FIG. 2 is a chemical structural diagram of Bio-ZIF.
Step 2, preparation of Pebax solution:
0.537g of block polyetheramide was weighed out
Figure BDA0002725736220000051
1657 the granules are dissolved in 10ml ethanol and water mixed solution (ethanol and water at 70%/30% by mass), and heated in 80 deg.C water bath under stirring for 2h to completely dissolve Pebax to obtain 6 wt% Pebax matrix solution.
Step 3, preparation of a mixed matrix membrane:
physically blending the Bio-ZIF prepared in the step 1 and the 6 wt% Pebax solution prepared in the step 2, wherein the mass ratio of the Pebax to the Bio-ZIF is 0.96:0.04, 0.92:0.08, 0.88:0.12 and 0.84:0.16, stirring for 3-6 h at room temperature to obtain a casting solution, and pouring the casting solution on a clean culture dish for casting; drying for 36-60 h at room temperature (25 ℃), and then carrying out vacuum drying in a vacuum drying oven at 25-50 ℃ to remove residual solvent on the surface of the mixed matrix membrane to obtain the Pebax/Bio-ZIF mixed matrix membrane with the membrane thickness of 100-130 mu m.
The prepared Pebax/Bio-ZIF mixed matrix membrane is used for separating CO2/CH4Mixed gas of CO2Flux 406-525 barrel (1 barrel 10)-10cm3cm/cm2scmHg)，CO2/CH4The selectivity is 30-40.
Example 1
Preparing a Pebax/Bio-ZIF mixed matrix membrane, wherein the thickness of the mixed matrix membrane is 117 mu m, the Pebax is taken as a membrane matrix of the mixed matrix membrane, and the Bio-ZIF is added into the membrane matrix, the mass ratio of the Pebax to the Bio-ZIF is 0.96:0.04, and the preparation method of the mixed matrix membrane is as follows:
step 1, preparation of Bio-ZIF:
1mmol of Zn (NO) at room temperature3)2·6H2O was dissolved in 10mL of methanol (designated as solution A), and 4mmol 2-methylimidazole was dissolved in 10mL of methanol (designated as solution B). Then, both solutions were sonicated for 15 minutes, and then solution B was slowly added to solution A under sonication, which was sonicated at room temperature for 4 hours, followed by standing at room temperature for 24 hours. The precipitate was collected by centrifugation and washed three times with methanol to give ZIF-8. Finally, the precipitate was dried at 60 ℃ overnight and ZIF-8 nanofiller was obtained. Prepared ZIF-8(200mg) was uniformly dispersed in 100mL of methanol by sonication for 30 minutes to obtain a uniform suspension of ZIF-8. Then, Atz (585mg) was added to the suspension of ZIF-8, and stirred for 8h in a water bath at 50 ℃. The precipitate was collected by centrifugation and washed with methanol. Finally, the precipitate was dried at 70 ℃ for 3 days under vacuum, thereby obtaining a Bio-ZIF nanofiller.
Step 2, weighing 0.537g of Pebax, dissolving the Pebax into 10ml of ethanol-water mixed solution with the mass fraction ratio of 7:3, heating and stirring the mixture in a water bath at the temperature of 80 ℃ for 2 hours to completely dissolve Pebax particles, and preparing a Pebax matrix solution with the mass fraction of 6 wt% for later use.
Step 3, physically blending the Bio-ZIF (0.0208g) prepared in the step 1 with 0.4992g of 6 wt% Pebax matrix solution prepared in the step 2, stirring for 4 hours at room temperature to obtain membrane casting solution, and pouring the membrane casting solution on a clean culture dish for casting; drying at room temperature (25 ℃) for 48 hours, and then drying in a vacuum drying oven at 40 ℃ in vacuum to remove residual solvent on the surface of the mixed matrix membrane to obtain a Pebax/Bio-ZIF mixed matrix membrane, wherein the thickness of the mixed matrix membrane is 117 mu m, and the weight percentage of the Bio-ZIF in the Pebax/Bio-ZIF mixed matrix membrane is 4 percent, so that the Pebax/Bio-ZIF-4 mixed matrix membrane is named.
FIG. 3 is a sectional view of a Pebax/Bio-ZIF-4 mixed matrix membrane prepared in example 1 under a scanning electron microscope.
The Pebax/Bio-ZIF-4 mixed matrix membrane was used for CO at 25 ℃ under 2bar conditions220% by volume of CO2/CH4Mixed gas separation test of CO2Flux of 406barrer, CO2/CH4The selectivity was 30.
Example 2
A Pebax/Bio-ZIF-8 mixed matrix membrane was prepared, which differs from the Pebax/Bio-ZIF-4 mixed matrix membrane of example 1 in that: the resulting Pebax/Bio-ZIF-4 mixed matrix membrane, having a thickness of 120 μm and a mass ratio of Pebax to Bio-ZIF of 0.92:0.08, was prepared in a manner different from that of example 1 only in that: step 3, changing the weighing of 0.0208gBio-ZIF into the weighing of 0.0434 gBio-ZIF; finally, a mixed matrix film having a thickness of 120 μm was obtained.
FIG. 4 is a sectional view of a scanning electron microscope of the Pebax/Bio-ZIF-8 mixed matrix membrane prepared in example 2.
The Pebax/Bio-ZIF-8 mixed matrix membrane obtained in example 2 was used for CO at 25 ℃ under 2bar220% by volume of CO2/CH4Separation test of mixture gas, CO thereof2Flux 451barrer, CO2/CH4The selectivity was 39.
Example 3
A Pebax/Bio-ZIF-12 mixed matrix membrane was prepared, which differs from the Pebax/Bio-ZIF-4 mixed matrix membrane of example 1 in that: the thickness of the resulting Pebax/Bio-ZIF-4 mixed matrix membrane was 125 μm, wherein the mass ratio of Pebax to Bio-ZIF was 0.88:0.12, and the preparation of the mixed matrix membrane was different from the preparation method of example 1 only in that: step 3, changing the weighing of 0.0208gBio-ZIF into the weighing of 0.0680 gBio-ZIF; finally, a mixed matrix film having a thickness of 125 μm was obtained.
FIG. 5 is a sectional view of a Pebax/Bio-ZIF-12 mixed matrix membrane prepared in example 3 under a scanning electron microscope.
The Pebax/Bio-ZIF-12 mixed matrix membrane obtained in example 3 was used for CO at 25 ℃ under 2bar220% by volume of CO2/CH4Separation test of mixture gas, CO thereof2Flux of 525barrer, CO2/CH4The selectivity was 40.
Example 4
A Pebax/Bio-ZIF-16 mixed matrix membrane was prepared, which differs from the Pebax/Bio-ZIF-4 mixed matrix membrane of example 1 in that: the thickness of the resulting Pebax/Bio-ZIF-4 mixed matrix membrane was 125 μm, wherein the mass ratio of Pebax to Bio-ZIF was 0.84:0.16, and the preparation of the mixed matrix membrane was different from the preparation method of example 1 only in that: step 3, changing the weighing of 0.0208gBio-ZIF into the weighing of 0.0951 gBio-ZIF; finally, a mixed matrix film having a thickness of 125 μm was obtained.
FIG. 6 is a sectional view of a Pebax/Bio-ZIF-16 mixed matrix membrane prepared in example 4 under a scanning electron microscope.
At 25 deg.C and 2barNext, the Pebax/Bio-ZIF-16 mixed matrix membrane prepared in example 4 was used for CO220% by volume of CO2/CH4Separation test of mixture gas, CO thereof2Flux 452barrer, CO2/CH4The selectivity was 35.
Example 5
The preparation method of the Pebax/Bio-ZIF mixed matrix membrane comprises the following steps:
step 1, preparation of Bio-ZIF:
1mmol of Zn (NO) at room temperature3)2·6H2O was dissolved in 7.5mL of methanol (designated as solution A), and 4mmol 2-methylimidazole was dissolved in 7.5mL of methanol (designated as solution B). Then, both solutions were sonicated for 15 minutes, and then solution B was slowly added to solution A under sonication, which was sonicated at room temperature for 4 hours, followed by standing at room temperature for 24 hours. The precipitate was collected by centrifugation and washed three times with methanol to give ZIF-8. Finally, the precipitate was dried at 60 ℃ overnight and ZIF-8 nanofiller was obtained. Prepared ZIF-8(200mg) was uniformly dispersed in 100mL of methanol by sonication for 30 minutes to obtain a uniform suspension of ZIF-8. Then, Atz (585mg) was added to the suspension of ZIF-8, and stirred for 8h in a water bath at 50 ℃. The precipitate was collected by centrifugation and washed with methanol. Finally, the precipitate was dried at 70 ℃ for 3 days under vacuum, thereby obtaining a Bio-ZIF nanofiller.
Step 2, weighing 0.537g of Pebax, dissolving the Pebax into 10ml of ethanol-water mixed solution with the mass fraction ratio of 7:3, heating and stirring the mixture in a water bath at the temperature of 80 ℃ for 2 hours to completely dissolve Pebax particles, and preparing a Pebax matrix solution with the mass fraction of 6 wt% for later use.
Step 3, physically blending the Bio-ZIF (0.0208g) prepared in the step 1 with 0.4992g of 6 wt% Pebax matrix solution prepared in the step 2, stirring for 3 hours at room temperature to obtain membrane casting solution, and pouring the membrane casting solution on a clean culture dish for casting; drying for 60h at room temperature (25 ℃), and then removing residual solvent on the surface of the mixed matrix membrane by vacuum drying in a vacuum drying oven at 25 ℃ to obtain the Pebax/Bio-ZIF mixed matrix membrane.
Example 6
The preparation method of the Pebax/Bio-ZIF mixed matrix membrane comprises the following steps:
step 1, preparation of Bio-ZIF:
1mmol of Zn (NO) at room temperature3)2·6H2O was dissolved in 20mL of methanol (designated as solution A), and 4mmol 2-methylimidazole was dissolved in 20mL of methanol (designated as solution B). Then, both solutions were sonicated for 15 minutes, and then solution B was slowly added to solution A under sonication, which was sonicated at room temperature for 4 hours, followed by standing at room temperature for 24 hours. The precipitate was collected by centrifugation and washed three times with methanol to give ZIF-8. Finally, the precipitate was dried at 60 ℃ overnight and ZIF-8 nanofiller was obtained. Prepared ZIF-8(200mg) was uniformly dispersed in 100mL of methanol by sonication for 30 minutes to obtain a uniform suspension of ZIF-8. Then, Atz (585mg) was added to the suspension of ZIF-8, and stirred for 8h in a water bath at 50 ℃. The precipitate was collected by centrifugation and washed with methanol. Finally, the precipitate was dried at 70 ℃ for 3 days under vacuum, thereby obtaining a Bio-ZIF nanofiller.
Step 2, weighing 0.537g of Pebax, dissolving the Pebax into 10ml of ethanol-water mixed solution with the mass fraction ratio of 7:3, heating and stirring the mixture in a water bath at the temperature of 80 ℃ for 2 hours to completely dissolve Pebax particles, and preparing a Pebax matrix solution with the mass fraction of 6 wt% for later use.
Step 3, physically blending the Bio-ZIF (0.0434g) prepared in the step 1 with 0.4992g of 6 wt% Pebax matrix solution prepared in the step 2, stirring for 6 hours at room temperature to obtain membrane casting solution, and pouring the membrane casting solution on a clean culture dish for casting; drying at room temperature (25 ℃) for 36h, and then removing residual solvent on the surface of the mixed matrix membrane through vacuum drying in a vacuum drying oven at 50 ℃ to obtain the Pebax/Bio-ZIF mixed matrix membrane.
Comparative example 1
Preparing a Pebax film with the film thickness of 116 mu m; the preparation method comprises the following steps: 0.537g of Pebax particles is weighed and dissolved in a 70% ethanol/30% water mixed solution by mass fraction, after stirring for 2h at 80 ℃, the obtained casting solution is poured on a clean super flat dish for casting, dried for 48h at room temperature (25 ℃), and then put in a vacuum oven at 40 ℃ for 24h to remove the residual solvent, so as to obtain a Pebax film with the thickness of 117 μm.
FIG. 7 is a cross-sectional view of a pure Pebax film prepared in the comparative example under a scanning electron microscope.
The Pebax membrane prepared in the comparative example was used for CO at 25 ℃ and 2bar220% by volume of CO2/CH4Separation test of mixture gas, CO thereof2Flux of 270barrer, CO2/CH4The selectivity was 25.
Comparative example 2
Pebax/ZIF-8-12 membranes were prepared, in contrast to example 3 Pebax/Bio-ZIF-12: the film thickness was 124. mu.m. The preparation of this mixed matrix membrane differs from the preparation of example 3 only in that: step 3, changing the weighing of 0.0680g Bio-ZIF into the weighing of 0.0680g ZIF-8; finally, a mixed matrix film having a thickness of 124 μm was obtained.
FIG. 8 is a sectional view of a scanning electron microscope of the Pebax/ZIF-8-12 mixed matrix membrane prepared in comparative example 2.
The Pebax/ZIF-8-12 mixed matrix membrane prepared in the comparative example 2 is used for CO at 25 ℃ and 2bar220% by volume of CO2/CH4Separation test of mixture gas, CO thereof2Flux was 382barrer, CO2/CH4The selectivity was 30.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A bionic material Bio-ZIF filled block polyether amide mixed matrix membrane is characterized in that: the mixed matrix membrane is prepared from Bio-ZIF and block polyether amide Pebax; the thickness of the mixed matrix membrane is 100-130 μm.
2. The Bio-ZIF filled block polyetheramide mixed matrix membrane as claimed in claim 1, wherein: in the mixed matrix membrane, the mass percent of the Bio-ZIF is 4% -16%, and the mass percent of the block polyether amide Pebax is 84% -96%.
3. The Bio-ZIF filled block polyetheramide mixed matrix membrane as claimed in claim 2, wherein: in the mixed matrix membrane, the mass ratio of Bio-ZIF to the block polyetheramide Pebax is 4:96, 8:92, 12:88 or 16: 84.
4. A biomimetic material Bio-ZIF filled block polyetheramide mixed matrix membrane according to any of claims 1-3, characterized in that: the preparation method of the Bio-ZIF comprises the following steps: 2-methylimidazole and Zn (NO)3)2Mixing and reacting to obtain ZIF-8; and then, ZIF-8 and 3-amino-1, 2, 4-triazole are reacted to prepare Bio-ZIF.
5. The method for preparing the Bio-ZIF filled block polyetheramide mixed matrix membrane as a biomimetic material according to any of claims 1 to 4, characterized in that: the mixed matrix membrane is prepared by doping Bio-ZIF serving as a filler into a block polyether amide Pebax matrix.
6. The method of claim 5, wherein: the preparation method of the Bio-ZIF comprises the following steps: 2-methylimidazole and Zn (NO)3)2Mixing and reacting to obtain ZIF-8; and then, ZIF-8 and 3-amino-1, 2, 4-triazole are reacted to prepare Bio-ZIF.
7. The method of claim 6, wherein: the preparation method of the Bio-ZIF comprises the following steps: 2-methylimidazole and Zn (NO)3)2Respectively dissolving, mixing, performing ultrasonic reaction, standing, centrifuging, collecting precipitate, washing,obtaining ZIF-8; drying ZIF-8, dispersing in methanol to obtain ZIF-8 suspension, adding 3-amino-1, 2, 4-triazole into the ZIF-8 suspension, stirring in water bath for reaction, centrifuging, collecting precipitate, washing, and drying to obtain Bio-ZIF.
8. The production method according to claim 6 or 7, characterized in that: the 2-methylimidazole Zn (NO)3)2And 3-amino-1, 2, 4-triazole in a molar ratio of: 4: 1: 1.49.
9. the production method according to any one of claims 5 to 8, characterized in that: the specific method for doping the Bio-ZIF serving as a filler into the block polyether amide Pebax matrix comprises the following steps: and physically blending the Bio-ZIF and the block polyether amide Pebax, stirring at room temperature to obtain a casting solution, casting and drying the casting solution to obtain the block polyether amide mixed matrix membrane filled with the bionic material Bio-ZIF.
10. Use of the biomimetic material Bio-ZIF filled block polyetheramide mixed matrix membrane according to any of claims 1-4 for CO separation2/CH4The application in mixed gas.
CN202011102131.2A 2020-10-15 2020-10-15 Bionic material Bio-ZIF filled block polyether amide mixed matrix membrane and preparation method and application thereof Pending CN112237852A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202011102131.2A CN112237852A (en) 2020-10-15 2020-10-15 Bionic material Bio-ZIF filled block polyether amide mixed matrix membrane and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202011102131.2A CN112237852A (en) 2020-10-15 2020-10-15 Bionic material Bio-ZIF filled block polyether amide mixed matrix membrane and preparation method and application thereof

Publications (1)

Publication Number Publication Date
CN112237852A true CN112237852A (en) 2021-01-19

Family

ID=74169216

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202011102131.2A Pending CN112237852A (en) 2020-10-15 2020-10-15 Bionic material Bio-ZIF filled block polyether amide mixed matrix membrane and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN112237852A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112915821A (en) * 2021-02-02 2021-06-08 石河子大学 Preparation method of amphiphilic polymer blending modified rubbery polymer blending membrane
CN112934011A (en) * 2021-03-04 2021-06-11 江西师范大学 For CO2Separated membrane material and preparation method thereof
CN116099390A (en) * 2022-11-14 2023-05-12 石河子大学 Mixed dimension material PNT@NiCo-LDH and preparation method and application thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105582823A (en) * 2015-12-23 2016-05-18 南京工业大学 ZIF-8/polyether-b-polyamide mixed matrix membrane and preparation and application thereof
US20180304193A1 (en) * 2017-04-21 2018-10-25 King Fahd University Of Petroleum And Minerals Mixed matrix membrane, a method of making thereof, and a method for gas separation
CN109316978A (en) * 2018-10-25 2019-02-12 上海科技大学 A kind of MOFs material and its preparation method and application
CN109865439A (en) * 2019-01-22 2019-06-11 石河子大学 A kind of mixed substrate membrane containing nano-grade molecular sieve and preparation method and application of the filling of ZIF-8/ graphite phase carbon nitride
CN111333583A (en) * 2018-12-18 2020-06-26 国家纳米科学中心 Chiral ligand, chiral zeolite imidazole framework material, and preparation method and application thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105582823A (en) * 2015-12-23 2016-05-18 南京工业大学 ZIF-8/polyether-b-polyamide mixed matrix membrane and preparation and application thereof
US20180304193A1 (en) * 2017-04-21 2018-10-25 King Fahd University Of Petroleum And Minerals Mixed matrix membrane, a method of making thereof, and a method for gas separation
CN109316978A (en) * 2018-10-25 2019-02-12 上海科技大学 A kind of MOFs material and its preparation method and application
CN111333583A (en) * 2018-12-18 2020-06-26 国家纳米科学中心 Chiral ligand, chiral zeolite imidazole framework material, and preparation method and application thereof
CN109865439A (en) * 2019-01-22 2019-06-11 石河子大学 A kind of mixed substrate membrane containing nano-grade molecular sieve and preparation method and application of the filling of ZIF-8/ graphite phase carbon nitride

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
KIE YONG CHO等: "Synthesis of amine-functionalized ZIF-8 with 3-amino-1,2,4-triazole by postsynthetic modification for efficient CO2-selective adsorbents and beyond", 《JOURNAL OF MATERIALS CHEMISTRY A》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112915821A (en) * 2021-02-02 2021-06-08 石河子大学 Preparation method of amphiphilic polymer blending modified rubbery polymer blending membrane
CN112934011A (en) * 2021-03-04 2021-06-11 江西师范大学 For CO2Separated membrane material and preparation method thereof
CN116099390A (en) * 2022-11-14 2023-05-12 石河子大学 Mixed dimension material PNT@NiCo-LDH and preparation method and application thereof

Similar Documents

Publication Publication Date Title
CN112237852A (en) Bionic material Bio-ZIF filled block polyether amide mixed matrix membrane and preparation method and application thereof
Li et al. Sequential co-immobilization of enzymes in metal-organic frameworks for efficient biocatalytic conversion of adsorbed CO2 to formate
Zhang et al. Adjust the arrangement of imidazole on the metal-organic framework to obtain hybrid proton exchange membrane with long-term stable high proton conductivity
Xin et al. Zr‐MOF‐enabled controllable ion sieving and proton conductivity in flow battery membrane
Sun et al. Konjac glucomannan/cellulose nanofibers composite aerogel supported HKUST-1 for CO2 adsorption
Si et al. A high-efficiency diffusion process in carbonized ZIF-8 incorporated mixed matrix membrane for n-butanol recovery
Si et al. Carbonized ZIF-8 incorporated mixed matrix membrane for stable ABE recovery from fermentation broth
Zhou et al. Selenium-functionalized metal-organic frameworks as enzyme mimics
Lv et al. Mixed matrix membranes comprising dual-facilitated bio-inspired filler for enhancing CO2 separation
CN110732308B (en) Preparation method of MOFs-based solid acid ammonia gas adsorbent
CN111205469B (en) Ultramicropore zirconium-based metal organic framework material and preparation method and application thereof
CN109663512A (en) The mixed substrate membrane containing nano-grade molecular sieve and preparation method and application of ionic liquid@hollow polyhedron filling
Zhang et al. Biomimetic material functionalized mixed matrix membranes for enhanced carbon dioxide capture
CN112675720B (en) Preparation method and application of mixed matrix membrane filled with bimetallic strip material
Wu et al. Bionic mineralization growth of UIO-66 with bovine serum for facile synthesis of Zr-MOF with adjustable mesopores and its application in enzyme immobilization
Zheng et al. Dual-function biomimetic carrier based facilitated transport mixed matrix membranes with high stability for efficient CO2/N2 separation
Wu et al. Immobilization of carbonic anhydrase for facilitated CO2 capture and separation
Xu et al. Immobilization of cellulase proteins on zeolitic imidazolate framework (ZIF-8)/polyvinylidene fluoride hybrid membranes
Ding et al. Novel and versatile PEI modified ZIF-8 hollow nanotubes to construct CO2 facilitated transport pathway in MMMs
WO2023221564A1 (en) Hydrophobic mof-based porous liquid carbon capture absorbent and preparation method therefor
CN111617645A (en) Preparation method of low-resistance high-selectivity mixed matrix membrane based on hollow MOFs (metal-organic frameworks) material
CN105837842B (en) Method for preparing cation membrane for diffusion dialysis by using mesoporous silica
CN113828170A (en) Mixed matrix membrane and preparation method and application thereof
CN114849665B (en) Amino metal organic framework adsorbent capable of adsorbing carbon dioxide in air and preparation and application thereof
Li et al. Ultrathin Ni-Co nanosheets with disparate-CO2-affinity nanodomains in membranes to improve 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
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20210119