CN113209841A - Mixed matrix membrane of aminated ZIF-8 and polyvinyl alcohol and preparation method and application thereof - Google Patents

Mixed matrix membrane of aminated ZIF-8 and polyvinyl alcohol and preparation method and application thereof Download PDF

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CN113209841A
CN113209841A CN202110529199.7A CN202110529199A CN113209841A CN 113209841 A CN113209841 A CN 113209841A CN 202110529199 A CN202110529199 A CN 202110529199A CN 113209841 A CN113209841 A CN 113209841A
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zif
polyvinyl alcohol
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CN113209841B (en
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熊芸
邓妮艳
张静
张权
刘生鹏
孙国锋
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Wuhan Institute of Technology
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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
    • B01D71/38—Polyalkenylalcohols; Polyalkenylesters; Polyalkenylethers; Polyalkenylaldehydes; Polyalkenylketones; Polyalkenylacetals; Polyalkenylketals
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
    • C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/12—Specific ratios of components used

Abstract

The invention belongs to the technical field of membrane separation, and particularly relates to a mixed matrix membrane of aminated ZIF-8 and polyvinyl alcohol, and a preparation method and application thereof. The method comprises the following steps: 1) preparing ZIF-8; 2) preparing aminated ZIF-8; 3) preparing a polyvinyl alcohol solution; 4) and preparing a mixed matrix membrane of the aminated ZIF-8 and the polyvinyl alcohol. The invention aims to solve the problems that ZIF-8 agglomeration is caused due to poor compatibility and hydrophobicity between ZIF-8 and a polymer, a mixed matrix membrane has defects, the separation performance of the mixed matrix membrane is limited and the like, and provides a method for modifying ZIF-8 by utilizing a shell-ligand exchange reaction and introducing amino so as to remarkably improve the Trade Off effect between flux and selectivity.

Description

Mixed matrix membrane of aminated ZIF-8 and polyvinyl alcohol and preparation method and application thereof
Technical Field
The invention belongs to the technical field of membrane separation, and particularly relates to a mixed matrix membrane of aminated ZIF-8 and polyvinyl alcohol, and a preparation method and application thereof.
Background
With the continuous development of society and the increasing progress of science and technology, the resource shortage, the environmental deterioration and the like have attracted great attention and become worldwide problems which are urgently needed to be solved. The key words of energy conservation, low carbon, environmental protection and the like are proposed one after another, and renewable, novel and clean energy becomes a research hotspot of countries in the world. The bio-ethanol can play a positive role in the sustainable development of energy supply as a petroleum substitute, and the use of the mixed gasoline containing 10 percent of ethanol can reduce the emission of harmful gases of automobiles. Fuel ethanol is a representative alternative to new energy sources, and ethanol dehydration is a key step in its industrial production. In the industrialized ethanol dehydration process, the pervaporation technology has the advantages of mild conditions, simple flow, low energy consumption, environmental friendliness and the like, and the key of the pervaporation membrane separation technology is to develop a high-performance pervaporation membrane.
The development of membrane materials is always the core and foundation for constructing high-efficiency separation membranes. In recent years, metal-organic framework Materials (MOFs) are used as a novel porous crystal material, have rich compositions and diversified pore channel structures, have the characteristic of selective adsorption on specific gas or liquid molecules, and provide a wide space for the optimal selection of membrane materials. It is therefore widely used in the field of liquid separation by pervaporation and vapor permeation, in addition to gas separation applications.
Zeolitic Imidazolate Framework (ZIFs) materials are known as an important branch of MOFs materials because they have the same bond angles and similar topologies as silicoaluminophosphate zeolite molecular sieves. ZIFs have good thermal and chemical stability, high specific surface area and porosity, adjustable pore structure and chemical properties, and are often used as membrane materials for gas or liquid separation.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a mixed matrix membrane of aminated ZIF-8 and polyvinyl alcohol, and a preparation method and application thereof. The invention aims to solve the problems that ZIF-8 agglomeration is caused due to poor compatibility and hydrophobicity between ZIF-8 and a polymer, a mixed matrix membrane has defects, the separation performance of the mixed matrix membrane is limited and the like, and provides a method for modifying ZIF-8 by utilizing a shell-ligand exchange reaction and introducing amino so as to remarkably improve the Trade Off effect between flux and selectivity.
The technical scheme provided by the invention is as follows:
a preparation method of a mixed matrix membrane of aminated ZIF-8 and polyvinyl alcohol comprises the following steps:
1) respectively dissolving 2-methylimidazole and zinc salt in absolute methanol to obtain a first ligand solution and a zinc salt solution; then quickly pouring the zinc salt solution into the first ligand solution, reacting for 0.5-1.5 h at the temperature of 23 +/-2 ℃, centrifuging, washing and drying to obtain ZIF-8;
2) dispersing the ZIF-8 obtained in the step 1) into absolute methanol, and performing ultrasonic treatment to obtain a uniform first suspension solution; heating and dissolving 2-aminobenzimidazole to obtain a second ligand solution; then quickly pouring the second ligand solution cooled to room temperature into the first suspension solution, fully stirring for reaction, centrifuging, washing and drying to obtain aminated ZIF-8;
3) preparing a polyvinyl alcohol solution;
4) dispersing the aminated ZIF-8 obtained in the step 2) into deionized water to obtain a second suspension solution, mixing the second suspension solution with the polyvinyl alcohol solution obtained in the step 3), stirring for full reaction, and then performing ultrasonic treatment, standing and degassing, film scraping and drying to obtain a mixed matrix membrane of the aminated ZIF-8 and the polyvinyl alcohol.
According to the technical scheme, the ZIF-8 is prepared firstly, and then 2-methylimidazole in the ZIF-8 is exchanged by adopting 2-aminobenzimidazole which is an organic ligand with amino, so that the amino is directly introduced into a framework to obtain the ZIF-8-NH2. Then a solution blending method is adopted, and ZIF-8-NH is utilized2Reacting with hydroxyl in polyvinyl alcohol to generate hydrogen bond to obtain ZIF-8-NH2Polyvinyl alcohol mixed basePlasma membranes. The mixed matrix membrane enhances the compatibility between ZIF-8 and polyvinyl alcohol as a substrate, and effectively relieves the Trade Off effect between flux and selectivity.
Aiming at the problems of poor hydrophobic and polymer compatibility of ZIF-8, the invention introduces amino groups according to shell-ligand exchange reaction in the process of synthesizing ZIF-8 from the viewpoints of improving compatibility and improving hydrophilicity to obtain ZIF-8-NH2. As the skeleton shell of the ZIF-8 is connected with the naked amino group, the environmental condition of interface compatibility is provided, so that the ZIF-8-NH can generate hydrogen bond acting force with the hydroxyl in the PVA matrix and the ZIF-8-NH is enhanced2The polyvinyl alcohol interface compatibility improves the Trade Off effect between flux and selectivity.
Specifically, in the step 1), the molar ratio of the 2-methylimidazole to the zinc salt to the anhydrous methanol is 1 (7-9) to (600-800).
Preferably, in the step 1), the molar ratio of the 2-methylimidazole to the zinc salt to the anhydrous methanol is 1:8: 700.
Specifically, in the step 2), the molar ratio of ZIF-8 to 2-aminobenzimidazole to absolute methanol is 1: (1.8-2.2): (150-170).
Preferably, in the step 2), the molar ratio of ZIF-8 to 2-aminobenzimidazole to absolute methanol is 1:2: 160.
Specifically, the concentration of the polyvinyl alcohol solution is 8-10 wt%.
Specifically, the zinc salt is zinc nitrate hexahydrate.
Specifically, in the mixed matrix membrane of the aminated ZIF-8 and the polyvinyl alcohol, the doping amount of the aminated ZIF-8 is more than zero and less than or equal to 10 wt%.
The invention also provides a mixed matrix membrane of the aminated ZIF-8 and the polyvinyl alcohol prepared by the preparation method.
The invention also provides application of the mixed matrix membrane of the aminated ZIF-8 and the polyvinyl alcohol, which is used for separating ethanol from water.
Preferably, the method is used for separating ethanol and water at 38-42 ℃.
Compared with the prior art, the invention has the following beneficial effects:
the invention utilizes the advantages of large specific surface area, large pore diameter and adjustable pore diameter of MOFs materials to aminate the MOFs materials, and a mixed matrix membrane prepared from the MOFs materials and polyvinyl alcohol is used for ethanol dehydration, thereby improving the flux and the selectivity of the membrane. The membrane preparation process is simple, greatly improves the separation performance of the mixed matrix membrane, and has great development potential.
Drawings
FIG. 1 is a ZIF-8-NH reaction solution obtained in example 12And FTIR profile of ZIF-8;
FIG. 2 shows ZIF-8-NH prepared in example 12ZIF-8 and simulated ZIF-8 XRD patterns;
FIG. 3 is a graph of pervaporation performance of membranes prepared in example 1, comparative example 1, and example 2;
FIG. 4 is a graph of pervaporation performance of the membrane prepared in example 2.
Detailed Description
The principles and features of this invention are described below in conjunction with examples which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
Example 1:
step 1: respectively dissolving 2-methylimidazole and zinc nitrate hexahydrate in absolute methanol in a molar ratio of 1:8: 700. and (3) quickly pouring the zinc salt solution into the ligand solution, reacting for 1h at the temperature of 23 +/-2 ℃, and centrifuging, washing and drying to obtain the ZIF-8.
Step 2: dispersing the ZIF-8 obtained in the step 1 into absolute methanol, and performing ultrasonic treatment for 1h to obtain a uniform suspension; heating and dissolving 2-aminobenzimidazole at 70 ℃ to obtain a second ligand solution; then, the second ligand solution cooled to room temperature is quickly poured into the suspension, fully stirred for reaction, centrifuged, washed and dried to obtain ZIF-8-NH2The FTIR and XRD patterns are shown in figure 1 and figure 2.
And step 3: dispersing 5g of polyvinyl alcohol in deionized water, heating and stirring until the polyvinyl alcohol is completely dissolved to obtain a substrate solution with the mass fraction of 10 wt%.
And 4, step 4: ZIF-8-NH in the step 22Dispersing in deionized water to obtain a suspension solution. Mixing the dispersed suspension withAnd 3, mixing the polyvinyl alcohol solution in the step 3, and fully reacting by stirring. Standing, degassing, scraping a film and drying to obtain ZIF-8-NH2A/polyvinyl alcohol mixed matrix membrane PZN.
Comparative example 1:
10g of polyvinyl alcohol was dispersed in deionized water, and heated with stirring until completely dissolved, to give 100ml of a base solution. 0.5g of APTES and 1ml of hydrochloric acid solution (1mol/L) were added to the base solution, and sufficiently stirred. And standing, degassing, scraping a film and drying to obtain the cross-linked polyvinyl alcohol film PA.
Comparative example 2:
ultrasonically dispersing a ZIF-8 nanocrystal material in deionized water to obtain a suspension; and mixing the dispersed suspension with 10 wt% of polyvinyl alcohol solution, and fully reacting by stirring. And standing, degassing, scraping and drying to obtain the ZIF-8/polyvinyl alcohol mixed matrix membrane PZ.
The three membranes prepared in example 1, comparative example 1 and comparative example 2 were subjected to pervaporation testing in a laboratory home-made unit, with a vacuum environment on the downstream side of the membrane, less than 1 mbar. The experimental temperatures were 30 deg.C, 40 deg.C, 50 deg.C, respectively, and the feed liquid composition was ethanol/water (85/15 wt%). The test results are shown in table 1 below:
table 1: alcohol dehydration Performance testing of membranes
Figure BDA0003066856260000051
From the results of example 1, it can be seen that the operating conditions have an effect on the pervaporation performance of the mixed matrix membrane. As the operating temperature increases, the permeate flux of all mixed matrix membranes increases. However, the permeability of water molecules decreases greatly with increasing temperature and the permeability of ethanol molecules increases slightly, so that the separation factor decreases with increasing temperature.
Example 2:
step 1: 3.346g of 2-methylimidazole and 1.5g of zinc nitrate hexahydrate are dissolved in anhydrous methanol respectively, and then a zinc salt solution is poured into a ligand solution quickly and fully reacts for 1 hour at room temperature. And centrifuging, washing and drying to obtain ZIF-8.
Step 2: and (3) weighing 208mg of ZIF-8 in the step (1), dispersing into absolute methanol, and performing ultrasonic treatment for 1h to obtain a suspension solution. 965mg of 2-aminobenzimidazole was then dissolved in anhydrous methanol under heating, cooled to room temperature, and then poured quickly into the suspension to react well. Obtaining ZIF-8-NH by centrifuging, washing and drying2。
And step 3: mixing different masses of ZIF-8-NH2Dispersing in deionized water, and ultrasonically dispersing for 1 h. Dispersing ZIF-8-NH2And mixing the suspension with a PVA solution prepared in advance in a certain mass fraction, stirring the mixed solution vigorously for 12 hours, and then carrying out ultrasonic dispersion for 1 hour. Then standing and degassing the casting solution for 12h, performing ultrasonic defoaming for 2h, scraping the film on a PET plate by using a scraper, and drying to obtain four different ZIF-8-NH2Content (2.5 wt%, 5 wt%, 7.5 wt%, 10 wt%, respectively) of the mixed matrix film.
Four ZIF-8-NH with different contents are prepared2the/PVA (PZN for short) film is used for pervaporation test in a self-made device in a laboratory, and the downstream side of the film is in a vacuum environment and is less than 1 mbar. The experimental temperature was 40 ℃ and the feed solution composition was ethanol/water (85/15 wt%). The test results are shown in table 2:
table 2: alcohol dehydration Performance test of PZN film
Figure BDA0003066856260000061
As can be seen from the results of example 2, along with ZIF-8-NH2The mass fraction is increased from 2.5 percent to 10 percent, and the permeation flux is along with ZIF-8-NH2The content is increased to stably increase, the separation factor is increased, and when the content exceeds 7.5%, the separation factor is rapidly reduced due to agglomeration of particles and occurrence of defects. When ZIF-8-NH2When the content is 7.5 percent, in the process of separating 85 percent ethanol water solution at 40 ℃, the separation factor reaches a larger value of 230, simultaneously the Trade Off effect is overcome, and the flux also reaches a considerable value of 250g/m2·h。
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (9)

1. A preparation method of a mixed matrix membrane of aminated ZIF-8 and polyvinyl alcohol is characterized by comprising the following steps:
1) respectively dissolving 2-methylimidazole and zinc salt in absolute methanol to obtain a first ligand solution and a zinc salt solution; then quickly pouring the zinc salt solution into the first ligand solution, reacting for 0.5-1.5 h at the temperature of 23 +/-2 ℃, centrifuging, washing and drying to obtain ZIF-8;
2) dispersing the ZIF-8 obtained in the step 1) into absolute methanol, and performing ultrasonic treatment to obtain a uniform first suspension solution; heating and dissolving 2-aminobenzimidazole to obtain a second ligand solution; then quickly pouring the second ligand solution cooled to room temperature into the first suspension solution, fully stirring for reaction, centrifuging, washing and drying to obtain aminated ZIF-8;
3) preparing a polyvinyl alcohol solution;
4) dispersing the aminated ZIF-8 obtained in the step 2) into deionized water to obtain a second suspension solution, mixing the second suspension solution with the polyvinyl alcohol solution obtained in the step 3), stirring for full reaction, and then performing ultrasonic treatment, standing and degassing, film scraping and drying to obtain a mixed matrix membrane of the aminated ZIF-8 and the polyvinyl alcohol.
2. The method for preparing a mixed matrix membrane of aminated ZIF-8 and polyvinyl alcohol as claimed in claim 1, wherein in step 1), the molar ratio of 2-methylimidazole, zinc salt and absolute methanol is 1 (7-9) to (600-800).
3. The method for preparing a mixed matrix membrane of aminated ZIF-8 and polyvinyl alcohol according to claim 1, wherein the molar ratio of ZIF-8, 2-aminobenzimidazole and anhydrous methanol in step 2) is 1: (1.8-2.2): (150-170).
4. The method for preparing a mixed matrix film of an aminated ZIF-8 and polyvinyl alcohol according to claim 1, wherein the concentration of the polyvinyl alcohol solution is 8 to 10 wt%.
5. The method for preparing a mixed matrix membrane of aminated ZIF-8 and polyvinyl alcohol as claimed in claim 1, wherein: the zinc salt is zinc nitrate hexahydrate.
6. The method for preparing a mixed matrix film of aminated ZIF-8 and polyvinyl alcohol as claimed in any one of claims 1 to 5, wherein: in the mixed matrix membrane of the aminated ZIF-8 and the polyvinyl alcohol, the doping amount of the aminated ZIF-8 is more than zero and less than or equal to 10 wt%.
7. A mixed matrix film of aminated ZIF-8 and polyvinyl alcohol prepared according to the preparation method of any one of claims 1 to 6.
8. Use of the aminated ZIF-8 mixed matrix film with polyvinyl alcohol according to claim 7, characterized in that: used for separating ethanol from water.
9. The use of the aminated ZIF-8 mixed matrix film with polyvinyl alcohol of claim 8, wherein: the method is used for separating ethanol and water at 38-42 ℃.
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CN115873265A (en) * 2022-12-30 2023-03-31 佛山市顺德区阿波罗环保器材有限公司 Amination modified ZIF-8 material and preparation method thereof

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CN113861462A (en) * 2021-09-15 2021-12-31 苏州美盈森环保科技有限公司 Preparation method of environment-friendly packaging material and packaging material
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CN114177788A (en) * 2021-12-01 2022-03-15 河北大学 ZIF-8 tube modified ultrathin nano composite membrane, and preparation method and application thereof
CN115006994A (en) * 2022-05-11 2022-09-06 武汉工程大学 Preparation method of high-hydrophilicity composite membrane for alcohol dehydration
CN115253725A (en) * 2022-08-23 2022-11-01 太原理工大学 Mixed matrix membrane based on amino modified MOF material and preparation method and application thereof
CN115253725B (en) * 2022-08-23 2023-06-30 太原理工大学 Mixed matrix membrane based on amino modified MOF material, and preparation method and application thereof
CN115873265A (en) * 2022-12-30 2023-03-31 佛山市顺德区阿波罗环保器材有限公司 Amination modified ZIF-8 material and preparation method thereof
CN115873265B (en) * 2022-12-30 2023-09-15 佛山市顺德区阿波罗环保器材有限公司 Amination modified ZIF-8 material and preparation method thereof

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