CN116139705A - Preparation method of MOFs mixed matrix membrane and application of MOFs mixed matrix membrane in polyphenol purification - Google Patents
Preparation method of MOFs mixed matrix membrane and application of MOFs mixed matrix membrane in polyphenol purification Download PDFInfo
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- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 84
- 150000008442 polyphenolic compounds Chemical class 0.000 title claims abstract description 55
- 235000013824 polyphenols Nutrition 0.000 title claims abstract description 55
- 238000000746 purification Methods 0.000 title claims abstract description 54
- 239000004941 mixed matrix membrane Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000002245 particle Substances 0.000 claims abstract description 46
- 239000007788 liquid Substances 0.000 claims abstract description 42
- 238000005374 membrane filtration Methods 0.000 claims abstract description 32
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000005266 casting Methods 0.000 claims abstract description 25
- 239000004695 Polyether sulfone Substances 0.000 claims abstract description 18
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229920006393 polyether sulfone Polymers 0.000 claims abstract description 18
- 239000011521 glass Substances 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 13
- 229920002584 Polyethylene Glycol 6000 Polymers 0.000 claims abstract description 11
- 229940093429 polyethylene glycol 6000 Drugs 0.000 claims abstract description 11
- 230000000694 effects Effects 0.000 claims abstract description 10
- 238000007790 scraping Methods 0.000 claims abstract description 7
- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000002791 soaking Methods 0.000 claims abstract description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000000843 powder Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000004090 dissolution Methods 0.000 claims description 10
- 229920000642 polymer Polymers 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000002474 experimental method Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 6
- 239000006228 supernatant Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 3
- 238000007865 diluting Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000000706 filtrate Substances 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 229920003208 poly(ethylene sulfide) Polymers 0.000 claims description 2
- 239000011159 matrix material Substances 0.000 claims 1
- 239000012528 membrane Substances 0.000 abstract description 29
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- 241000220225 Malus Species 0.000 description 30
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- 239000011148 porous material Substances 0.000 description 3
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- 102000004169 proteins and genes Human genes 0.000 description 2
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- 239000002033 PVDF binder Substances 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
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- 150000001720 carbohydrates Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
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- 239000000835 fiber Substances 0.000 description 1
- 229930003935 flavonoid Natural products 0.000 description 1
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- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
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- 229920000620 organic polymer Polymers 0.000 description 1
- 235000010987 pectin Nutrition 0.000 description 1
- 229920001277 pectin Polymers 0.000 description 1
- 239000001814 pectin Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 150000007965 phenolic acids Chemical class 0.000 description 1
- 229940068065 phytosterols Drugs 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0013—Casting processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D11/00—Solvent extraction
- B01D11/02—Solvent extraction of solids
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0011—Casting solutions therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
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Abstract
The invention discloses a preparation method of MOFs mixed matrix membrane and application thereof in polyphenol purification, belonging to the technical field of membrane separation, wherein the preparation method of MOFs mixed matrix membrane comprises the following steps: (1) preparation of MOFs particles: zinc acetate dihydrate is dissolved in a solvent to prepare a solution 1, terephthalic acid and triethylamine are dissolved in the solvent to prepare a solution 2, and the solution 1 is dropwise added into the solution 2 to prepare MOFs particles; (2) preparing a casting solution: soaking MOFs particles prepared in the step 1) in a solvent in advance, and adding polyether sulfone and polyethylene glycol-6000 to obtain a casting solution; (3) preparation of MOFs mixed matrix membrane: pouring the casting solution obtained in the step 2) on a glass plate, scraping a film by using a scraper, and soaking to form a film; compared with commercial PES (polyether sulfone) membranes, the MOFs mixed matrix membrane has the advantages that the purification effect of the membrane filtration polyphenol is improved, and the purification effect of the membrane filtration polyphenol feed liquid with different gradients can be improved by 10-20%.
Description
Technical Field
The invention relates to the technical field of membrane separation, in particular to a preparation method of MOFs mixed matrix membrane and application thereof in polyphenol purification.
Background
Apples are a high value fruit and the growing areas are mainly distributed in asia, america and europe. China is the largest apple producing area in the world. The apple contains rich nutrients such as polyphenols (phenolic acid and flavonoids), triterpenes and phytosterols, and also contains rich proteins, vitamins, sugar and microelements. As processing technology advances, apple byproduct yields increase, with the consequent increase in apple peel. Compared with apples, apple peel residues contain more abundant nutrients such as carbohydrates, pectin, proteins, fat, crude fibers and the like, and are also rich in various amino acids, microelements and polyphenols, but the current low utilization rate of the apple peel residues causes serious waste. Therefore, the application of apple peel slag is important, so that not only can the energy be reused, but also the additional yield of apples can be increased.
The membrane filtration method is to utilize the selective permeability of the membrane to realize the separation and purification of different components of the feed liquid. The membrane separation method requires selecting a filtration membrane having a suitable pore size according to the molecular weight of the separated substance. The mixed matrix membrane (Mixed matrix membrane, MMM) is a novel separation membrane in which an organic or inorganic filler is filled in a polymer, can successfully solve the problem that the membrane flux and the selectivity cannot be simultaneously improved, and has been widely used in the field of filtration and purification. However, in early attempts, researchers found that after filling, the filling phase and the dispersed phase formed voids, which reduced the separation performance of the membrane, and could not meet the current higher purification requirements, so the addition of a filling material with high performance was urgent in preparing high performance filtration membranes, such as metal organic frameworks (Metal organic framework, MOFs).
MOFs are novel materials composed of metal ions or metal clusters and organic ligands, and the special structure enables the porosity of the MOFs to be adjusted through the material components and the proportion of the MOFs. Compared with the common porous material, MOFs have the following characteristics: 1. high porosity; 2. large specific surface area and 3. The pore size can be adjusted.
At present, the polyphenol purification is commonly used in a membrane separation method, and mainly comprises two major categories of organic membranes and inorganic membranes according to the material of a filtering membrane. Organic polymer membranes (polyethersulfone and polyvinylidene fluoride) generally have short service lives, poor thermal stability and low selectivity, which limit their application in the field of membrane separation. While inorganic membranes (ceramic membranes and molecular sieve membranes) are difficult to prepare and have poor mechanical properties and stretchability. Both cannot overcome the bottleneck problem of simultaneous improvement of membrane flux and selectivity. According to the invention, the prepared MOFs particles are filled into PES to prepare the mixed matrix membrane with high purification performance, and the mixed matrix membrane is used for high-flux and high-selectivity filtration separation, especially for high-efficiency purification of polyphenol, and is beneficial to popularization of further industrial application of membrane filtration technology.
Disclosure of Invention
The invention aims to provide a preparation method of MOFs mixed matrix membrane and application thereof in polyphenol purification, so as to solve the problems in the prior art.
In order to achieve the above purpose, the present invention provides the following technical solutions:
a method for preparing MOFs mixed matrix membrane, comprising the following steps:
(1) Preparation of MOFs particles: zinc acetate dihydrate is dissolved in a solvent, stirred uniformly by using a magnetic stirrer, as a solution 1, terephthalic acid and triethylamine are dissolved in the solvent, stirred uniformly by using the magnetic stirrer, as a solution 2, the solution 1 is added into the solution 2 dropwise, stirred by using the magnetic stirrer until a uniformly dispersed solution is formed, and white precipitate is collected to prepare MOFs particles;
(2) Preparing a casting film liquid: soaking MOFs particles prepared in the step 1) in a solvent in advance, adding polyether sulfone and polyethylene glycol-6000 into the solvent, heating and stirring until the particles are completely dissolved to obtain a casting solution;
(3) Preparation of MOFs mixed matrix membranes: pouring the casting solution obtained in the step 2) on a glass plate, adjusting the height of a scraper to be 200 mu m, scraping the film by using the scraper, then quickly immersing the glass plate in deionized water to generate phase conversion to form a diaphragm, taking out the diaphragm, and then placing the diaphragm in the deionized water for storage for subsequent use.
As a further technical scheme of the invention: the solvent is N, N-dimethylformamide.
As a further technical scheme of the invention: in step 1), the mass ratio between terephthalic acid and triethylamine in the solution 2 was 1.3:2.2.
as a further technical scheme of the invention: in step 2), the mass ratio between the added PES and polyethylene glycol-6000 is 2:1, the MOFs particles are 2.5-10% of the polymer mass.
As a further technical scheme of the invention: in step 2), after adding polyethersulfone and polyethylene glycol-6000, stirring at 600 r/min at 70℃for 6 hours until complete dissolution, and standing for 12 hours.
The invention also aims to provide an application of the MOFs mixed matrix membrane in polyphenol purification, wherein the MOFs mixed matrix membrane is prepared by the preparation method of the MOFs mixed matrix membrane, and the application of the MOFs mixed matrix membrane in polyphenol purification comprises the following steps:
preparing apple peel powder: drying fresh apple peel, and then grinding and crushing the apple peel in a crusher;
preparing a membrane filtration feed liquid: dissolving apple powder in alcohol water solution, ultrasonically crushing cells, collecting supernatant, and diluting the concentration;
membrane filtration purification experiment: adopting membrane filtration equipment comprising a computer, an electronic balance, a ultrafilter cup and an air compressor, pouring feed liquid into the ultrafilter cup, opening the air compressor after sealing, adjusting the output pressure of the air compressor, and simultaneously opening the computer to record balance data, wherein when no feed liquid remains in the ultrafilter cup, the membrane filtration purification process is finished;
and (3) analyzing the purification effect of membrane filtration: and collecting filtrate in the beaker, measuring various physical and chemical index parameters, comparing the parameters with initial parameters of the feed liquid, and calculating the membrane filtration purification rate.
Compared with the prior art, the invention has the beneficial effects that: according to the invention, the prepared MOFs particles are filled into PES to prepare the mixed matrix membrane with high purification performance, the mixed matrix membrane is used for high-flux and high-selectivity filtration separation, and particularly is applied to high-efficiency purification of polyphenol.
Drawings
Fig. 1 is a schematic structural view of a membrane filtration apparatus employed in an embodiment of the present invention.
Reference numerals annotate: 1-computer, 2-electronic balance, 3-ultrafilter cup, 4-air compressor.
Detailed Description
The technical scheme of the patent is further described in detail below with reference to the specific embodiments.
Example 1
A method for preparing MOFs mixed matrix membrane, comprising the following steps:
(1) Preparation of MOFs particles: 4.3g of zinc acetate dihydrate was dissolved in 125mL of N, N-dimethylformamide and stirred using a magnetic stirrer at 500 r/min for 5min to complete dissolution as solution 1.1.3g of terephthalic acid and 2.2g of triethylamine were dissolved in 100mL of N, N-dimethylformamide, and stirred using a magnetic stirrer at 500 r/min for 5min to complete dissolution as solution 2. Solution 1 was added dropwise to solution 2, stirred using magnetic stirring at 500 r/min to form a uniformly dispersed solution, further centrifuged at 3000 r/min for 10min using a centrifuge, and the white precipitate was collected to prepare MOFs particles.
(2) Preparing a casting film liquid: immersing 0.1g MOFs particles prepared in the step (1) in 18.9g N, N-dimethylformamide for 12 hours in advance, stirring the particles uniformly by using a magnetic stirrer at 500 r/min for 5min, adding 4g PES and 2g polyethylene glycol-6000 into the mixture until the particles are completely dissolved, configuring the MOFs particles to account for 2.5-10% of the mass of the polymer, and heating and stirring the mixture for 6 hours until the particles are completely dissolved to obtain the casting solution.
(3) Preparation of MOFs mixed matrix membranes: the casting solution is stirred at 600 r/min for 6h to be completely dissolved at 70 ℃, then is kept stand for 12h, is poured on a glass plate, the height of a scraper is adjusted to 200 mu m, the glass plate is quickly soaked in deionized water after the scraper is used for scraping a film, a film is formed after the casting solution is subjected to phase conversion in water, and the film is taken out and then is placed in the deionized water for storage for subsequent use.
Use of MOFs mixed matrix membranes in the purification of polyphenols comprising the steps of:
(4) Preparing apple peel powder: the collected fresh apple peel was dried in an oven at 105 ℃ to its constant weight and the moisture content was determined. It was ground into powder using a pulverizer for 1 minute.
(5) Preparing a membrane filtration feed liquid: apple powder and 25% alcohol water solution are prepared into apple peel polyphenol extraction solution according to the proportion of 1:10, and then 450W ultrasonic treatment is performed for 30min to strengthen the extraction of peel polyphenol. The extract obtained was centrifuged at 3000 r/min for 10min. The supernatant was diluted by a corresponding multiple using 25% aqueous alcohol.
(6) Membrane filtration purification experiment: and (3) adopting membrane filtering equipment comprising a computer 1, an electronic balance 2, an ultrafiltration cup 3 and an air compressor 4, pouring feed liquid into the ultrafiltration cup 3, opening the air compressor 4 after sealing, adjusting the experimental pressure to 2.6bar, simultaneously opening the computer 1 to record balance data, and collecting purified liquid in a beaker for subsequent use after the purification test is finished when no feed liquid remains in the ultrafiltration cup 3, namely the membrane filtering purification process is finished.
(7) And (3) analyzing the purification effect of membrane filtration: measuring the polyphenol concentration and the solid concentration of the purified liquid, comparing the polyphenol concentration with the index parameters corresponding to the feed liquid, and determining the polyphenol concentration by comparing the polyphenol concentration with a polyphenol standard curve; the solids concentration was determined by the constant weight method.
Example 2
A method for preparing MOFs mixed matrix membrane, comprising the following steps:
(1) Preparation of MOFs particles: 4.3g of zinc acetate dihydrate was dissolved in 125mL of N, N-dimethylformamide and stirred using a magnetic stirrer at 500 r/min for 5min to complete dissolution as solution 1.1.3g of terephthalic acid and 2.2g of triethylamine were dissolved in 100mL of N, N-dimethylformamide, and stirred using a magnetic stirrer at 500 r/min for 5min to complete dissolution as solution 2. Solution 1 was added dropwise to solution 2, stirred using magnetic stirring at 500 r/min to form a uniformly dispersed solution, further centrifuged at 3000 r/min for 10min using a centrifuge, and the white precipitate was collected to prepare MOFs particles.
(2) Preparing a casting film liquid: immersing 0.2g MOFs particles prepared in the step (1) in 18.8g N, N-dimethylformamide for 12 hours in advance, stirring the particles uniformly by using a magnetic stirrer at 500 r/min for 5min, adding 4g PES and 2g polyethylene glycol-6000 into the mixture until the particles are completely dissolved, configuring the MOFs particles to account for 2.5-10% of the mass of the polymer, and heating and stirring the mixture for 6 hours until the particles are completely dissolved to obtain the casting solution.
(3) Preparation of MOFs mixed matrix membranes: the casting solution is stirred at 600 r/min for 6h to be completely dissolved at 70 ℃, then is kept stand for 12h, is poured on a glass plate, the height of a scraper is adjusted to 200 mu m, the glass plate is quickly soaked in deionized water after the scraper is used for scraping a film, a film is formed after the casting solution is subjected to phase conversion in water, and the film is taken out and then is placed in the deionized water for storage for subsequent use.
Use of MOFs mixed matrix membranes in the purification of polyphenols comprising the steps of:
(4) Preparing apple peel powder: the collected fresh apple peel was dried in an oven at 105 ℃ to its constant weight and the moisture content was determined. It was ground into powder using a pulverizer for 1 minute.
(5) Preparing a membrane filtration feed liquid: apple powder and 25% alcohol water solution are prepared into apple peel polyphenol extraction solution according to the proportion of 1:10, and then 450W ultrasonic treatment is performed for 30min to strengthen the extraction of peel polyphenol. The extract obtained was centrifuged at 3000 r/min for 10min. The supernatant was diluted by a corresponding multiple using 25% aqueous alcohol.
(6) Membrane filtration purification experiment: and (3) adopting membrane filtering equipment comprising a computer 1, an electronic balance 2, an ultrafiltration cup 3 and an air compressor 4, pouring feed liquid into the ultrafiltration cup 3, opening the air compressor 4 after sealing, adjusting the experimental pressure to 2.6bar, simultaneously opening the computer 1 to record balance data, and collecting purified liquid in a beaker for subsequent use after the purification test is finished when no feed liquid remains in the ultrafiltration cup 3, namely the membrane filtering purification process is finished.
(7) And (3) analyzing the purification effect of membrane filtration: measuring the polyphenol concentration and the solid concentration of the purified liquid, comparing the polyphenol concentration with the index parameters corresponding to the feed liquid, and determining the polyphenol concentration by comparing the polyphenol concentration with a polyphenol standard curve; the solids concentration was determined by the constant weight method.
Example 3
A method for preparing MOFs mixed matrix membrane, comprising the following steps:
(1) Preparation of MOFs particles: 4.3g of zinc acetate dihydrate was dissolved in 125mL of N, N-dimethylformamide and stirred using a magnetic stirrer at 500 r/min for 5min to complete dissolution as solution 1.1.3g of terephthalic acid and 2.2g of triethylamine were dissolved in 100mL of N, N-dimethylformamide, and stirred using a magnetic stirrer at 500 r/min for 5min to complete dissolution as solution 2. Solution 1 was added dropwise to solution 2, stirred using magnetic stirring at 500 r/min to form a uniformly dispersed solution, further centrifuged at 3000 r/min for 10min using a centrifuge, and the white precipitate was collected to prepare MOFs particles.
(2) Preparing a casting film liquid: immersing 0.3g MOFs particles prepared in the step (1) in 18.7g N, N-dimethylformamide for 12 hours in advance, stirring the particles uniformly by using a magnetic stirrer at 500 r/min for 5min, adding 4g PES and 2g polyethylene glycol-6000 into the mixture until the particles are completely dissolved, configuring the MOFs particles to account for 2.5-10% of the mass of the polymer, and heating and stirring the mixture for 6 hours until the particles are completely dissolved to obtain the casting solution.
(3) Preparation of MOFs mixed matrix membranes: the casting solution is stirred at 600 r/min for 6h to be completely dissolved at 70 ℃, then is kept stand for 12h, is poured on a glass plate, the height of a scraper is adjusted to 200 mu m, the glass plate is quickly soaked in deionized water after the scraper is used for scraping a film, a film is formed after the casting solution is subjected to phase conversion in water, and the film is taken out and then is placed in the deionized water for storage for subsequent use.
Use of MOFs mixed matrix membranes in the purification of polyphenols comprising the steps of:
(4) Preparing apple peel powder: the collected fresh apple peel was dried in an oven at 105 ℃ to its constant weight and the moisture content was determined. It was ground into powder using a pulverizer for 1 minute.
(5) Preparing a membrane filtration feed liquid: apple powder and 25% alcohol water solution are prepared into apple peel polyphenol extraction solution according to the proportion of 1:10, and then 450W ultrasonic treatment is performed for 30min to strengthen the extraction of peel polyphenol. The extract obtained was centrifuged at 3000 r/min for 10min. The supernatant was diluted by a corresponding multiple using 25% aqueous alcohol.
(6) Membrane filtration purification experiment: and (3) adopting membrane filtering equipment comprising a computer 1, an electronic balance 2, an ultrafiltration cup 3 and an air compressor 4, pouring feed liquid into the ultrafiltration cup 3, opening the air compressor 4 after sealing, adjusting the experimental pressure to 2.6bar, simultaneously opening the computer 1 to record balance data, and collecting purified liquid in a beaker for subsequent use after the purification test is finished when no feed liquid remains in the ultrafiltration cup 3, namely the membrane filtering purification process is finished.
(7) And (3) analyzing the purification effect of membrane filtration: measuring the polyphenol concentration and the solid concentration of the purified liquid, comparing the polyphenol concentration with the index parameters corresponding to the feed liquid, and determining the polyphenol concentration by comparing the polyphenol concentration with a polyphenol standard curve; the solids concentration was determined by the constant weight method.
Example 4
A method for preparing MOFs mixed matrix membrane, comprising the following steps:
(1) Preparation of MOFs particles: 4.3g of zinc acetate dihydrate was dissolved in 125mL of N, N-dimethylformamide and stirred using a magnetic stirrer at 500 r/min for 5min to complete dissolution as solution 1.1.3g of terephthalic acid and 2.2g of triethylamine were dissolved in 100mL of N, N-dimethylformamide, and stirred using a magnetic stirrer at 500 r/min for 5min to complete dissolution as solution 2. Solution 1 was added dropwise to solution 2, stirred using magnetic stirring at 500 r/min to form a uniformly dispersed solution, further centrifuged at 3000 r/min for 10min using a centrifuge, and the white precipitate was collected to prepare MOFs particles.
(2) Preparing a casting film liquid: immersing 0.4g MOFs particles prepared in the step (1) in 18.6g N, N-dimethylformamide for 12 hours in advance, stirring the MOFs particles uniformly by using a magnetic stirrer at 500 r/min for 5min, adding 4g PES and 2g polyethylene glycol-6000 into the MOFs particles until the MOFs particles are completely dissolved, configuring the MOFs particles to account for 2.5-10% of the mass of the polymer, and heating and stirring the MOFs particles for 6 hours until the MOFs particles are completely dissolved, thus obtaining the casting film liquid.
(3) Preparation of MOFs mixed matrix membranes: the casting solution is stirred at 600 r/min for 6h to be completely dissolved at 70 ℃, then is kept stand for 12h, is poured on a glass plate, the height of a scraper is adjusted to 200 mu m, the glass plate is quickly soaked in deionized water after the scraper is used for scraping a film, a film is formed after the casting solution is subjected to phase conversion in water, and the film is taken out and then is placed in the deionized water for storage for subsequent use.
Use of MOFs mixed matrix membranes in the purification of polyphenols comprising the steps of:
(4) Preparing apple peel powder: the collected fresh apple peel was dried in an oven at 105 ℃ to its constant weight and the moisture content was determined. It was ground into powder using a pulverizer for 1 minute.
(5) Preparing a membrane filtration feed liquid: apple powder and 25% alcohol water solution are prepared into apple peel polyphenol extraction solution according to the proportion of 1:10, and then 450W ultrasonic treatment is performed for 30min to strengthen the extraction of peel polyphenol. The extract obtained was centrifuged at 3000 r/min for 10min. The supernatant was diluted by a corresponding multiple using 25% aqueous alcohol.
(6) Membrane filtration purification experiment: and (3) adopting membrane filtering equipment comprising a computer 1, an electronic balance 2, an ultrafiltration cup 3 and an air compressor 4, pouring feed liquid into the ultrafiltration cup 3, opening the air compressor 4 after sealing, adjusting the experimental pressure to 2.6bar, simultaneously opening the computer 1 to record balance data, and collecting purified liquid in a beaker for subsequent use after the purification test is finished when no feed liquid remains in the ultrafiltration cup 3, namely the membrane filtering purification process is finished.
(7) And (3) analyzing the purification effect of membrane filtration: measuring the polyphenol concentration and the solid concentration of the purified liquid, comparing the polyphenol concentration with the index parameters corresponding to the feed liquid, and determining the polyphenol concentration by comparing the polyphenol concentration with a polyphenol standard curve; the solids concentration was determined by the constant weight method.
The experimental data obtained for the use of the MOFs mixed matrix membranes prepared in examples 1-4 above in polyphenol purification are shown in Table 1 below.
TABLE 1
| Examples | Yield of polyphenols (%) | Solid rejection (%) |
| 1 | 64.8 | 9.8 |
| 2 | 71.5 | 6.8 |
| 3 | 69.8 | 8.6 |
| 4 | 68.6 | 9.6 |
To sum up: the invention provides a preparation method of MOFs mixed matrix membrane and application thereof in polyphenol purification, the MOFs mixed matrix membrane prepared by the preparation method has practical significance when being practically applied to polyphenol purification, compared with a commercial PES membrane, the purification effect of membrane filtration on polyphenol is improved, the purification effect of the membrane filtration on polyphenol feed liquid with different gradients can be improved by 10-20%, and the preparation method of the MOFs mixed matrix membrane is simple to operate, safe and environment-friendly. According to the invention, the prepared MOFs particles are filled into PES to prepare the mixed matrix membrane with high purification performance, and the mixed matrix membrane is used for high-flux and high-selectivity filtration separation, especially for high-efficiency purification of polyphenol, and is beneficial to popularization of further industrial application of membrane filtration technology.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Furthermore, it should be understood that although the present disclosure describes embodiments, not every embodiment is provided with a separate embodiment, and that this description is provided for clarity only, and that the disclosure is not limited to the embodiments described in detail below, and that the embodiments described in the examples may be combined as appropriate to form other embodiments that will be apparent to those skilled in the art.
Claims (6)
1. A method for preparing a MOFs mixed matrix membrane, comprising the steps of:
(1) Preparation of MOFs particles: zinc acetate dihydrate is dissolved in a solvent, stirred uniformly, and used as a solution 1, terephthalic acid and triethylamine are dissolved in the solvent, stirred uniformly by using a magnetic stirrer, and used as a solution 2, the solution 1 is added into the solution 2 dropwise, stirred until a uniformly dispersed solution is formed, and white precipitate is collected to prepare MOFs particles;
(2) Preparing a casting film liquid: soaking MOFs particles prepared in the step 1) in a solvent in advance, adding polyether sulfone and polyethylene glycol-6000 into the solvent, heating and stirring until the particles are completely dissolved to obtain a casting solution;
(3) Preparation of MOFs mixed matrix membranes: pouring the casting solution obtained in the step 2) on a glass plate, adjusting the height of a scraper to be 200 mu m, scraping the film by using the scraper, then quickly immersing the glass plate in deionized water to generate phase conversion to form a diaphragm, taking out the diaphragm, and then placing the diaphragm in the deionized water for storage for subsequent use.
2. The method for preparing a mixed matrix membrane of MOFs according to claim 1, wherein the solvent is N, N-dimethylformamide.
3. The method for preparing a MOFs mixed matrix film according to claim 1, wherein in step 1), the mass ratio between terephthalic acid and triethylamine in the solution 2 is 1.3:2.2.
4. the preparation method of MOFs mixed matrix membrane according to claim 1, wherein in step 2), the mass ratio of PES and polyethylene glycol-6000 is 2:1, the MOFs particles are 2.5-10% of the polymer mass.
5. The method for preparing a mixed matrix membrane of MOFs according to claim 1, wherein in the step 2), after adding polyethersulfone and polyethylene glycol-6000, stirring at 600 r/min at 70 ℃ for 6 hours until complete dissolution, and standing for 12 hours.
6. The use of a MOFs mixed matrix membrane in purification of polyphenols, wherein the MOFs mixed matrix membrane is prepared by the preparation method of a MOFs mixed matrix membrane according to any one of claims 1-5, and the use of the MOFs mixed matrix membrane in purification of polyphenols comprises the following steps:
preparing apple peel powder: drying fresh apple peel, and then grinding and crushing the apple peel in a crusher;
preparing a membrane filtration feed liquid: dissolving apple powder in alcohol water solution, ultrasonically crushing cells, collecting supernatant, and diluting the concentration;
membrane filtration purification experiment: adopting membrane filtration equipment comprising a computer, an electronic balance, a ultrafilter cup and an air compressor, pouring feed liquid into the ultrafilter cup, opening the air compressor after sealing, adjusting the output pressure of the air compressor, and simultaneously opening the computer to record balance data, wherein when no feed liquid remains in the ultrafilter cup, the membrane filtration purification process is finished;
and (3) analyzing the purification effect of membrane filtration: and collecting filtrate in the beaker, measuring various physical and chemical index parameters, comparing the parameters with initial parameters of the feed liquid, and calculating the membrane filtration purification rate.
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