CN117180989A - Organic-inorganic hybrid ultrafiltration membrane and preparation method thereof - Google Patents
Organic-inorganic hybrid ultrafiltration membrane and preparation method thereof Download PDFInfo
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- CN117180989A CN117180989A CN202311208053.8A CN202311208053A CN117180989A CN 117180989 A CN117180989 A CN 117180989A CN 202311208053 A CN202311208053 A CN 202311208053A CN 117180989 A CN117180989 A CN 117180989A
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- 239000012528 membrane Substances 0.000 title claims abstract description 158
- 238000000108 ultra-filtration Methods 0.000 title claims abstract description 102
- 238000002360 preparation method Methods 0.000 title claims abstract description 47
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 52
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000010457 zeolite Substances 0.000 claims abstract description 52
- 230000005764 inhibitory process Effects 0.000 claims abstract description 42
- 230000004907 flux Effects 0.000 claims abstract description 37
- 239000003607 modifier Substances 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229920002678 cellulose Polymers 0.000 claims abstract description 31
- 239000001913 cellulose Substances 0.000 claims abstract description 31
- 239000013335 mesoporous material Substances 0.000 claims abstract description 23
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 23
- 229920000469 amphiphilic block copolymer Polymers 0.000 claims abstract description 22
- -1 carboxyl carbon quantum dots Chemical compound 0.000 claims abstract description 20
- 239000000758 substrate Substances 0.000 claims abstract description 15
- 239000000126 substance Substances 0.000 claims abstract description 11
- 229920001661 Chitosan Polymers 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 54
- 238000003756 stirring Methods 0.000 claims description 43
- 238000005266 casting Methods 0.000 claims description 40
- 239000012690 zeolite precursor Substances 0.000 claims description 30
- 238000001816 cooling Methods 0.000 claims description 25
- 239000002096 quantum dot Substances 0.000 claims description 24
- 230000002829 reductive effect Effects 0.000 claims description 23
- 239000000463 material Substances 0.000 claims description 22
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 21
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 20
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 18
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 15
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- 239000002211 L-ascorbic acid Substances 0.000 claims description 10
- 235000000069 L-ascorbic acid Nutrition 0.000 claims description 10
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 10
- 229960004543 anhydrous citric acid Drugs 0.000 claims description 10
- 229960005070 ascorbic acid Drugs 0.000 claims description 10
- 238000000498 ball milling Methods 0.000 claims description 10
- 238000000502 dialysis Methods 0.000 claims description 10
- 238000004108 freeze drying Methods 0.000 claims description 10
- 239000011521 glass Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000003760 magnetic stirring Methods 0.000 claims description 10
- 239000003921 oil Substances 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- 239000002002 slurry Substances 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 9
- 241000169203 Eichhornia Species 0.000 claims description 8
- 239000000835 fiber Substances 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 230000003213 activating effect Effects 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- ZCMUTXVQMSILSV-UHFFFAOYSA-N 3-diazo-2-methylpropanenitrile Chemical compound N#CC(C)C=[N+]=[N-] ZCMUTXVQMSILSV-UHFFFAOYSA-N 0.000 claims description 5
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 5
- 229960000583 acetic acid Drugs 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 5
- 239000004202 carbamide Substances 0.000 claims description 5
- QKIUAMUSENSFQQ-UHFFFAOYSA-N dimethylazanide Chemical compound C[N-]C QKIUAMUSENSFQQ-UHFFFAOYSA-N 0.000 claims description 5
- HHEAADYXPMHMCT-UHFFFAOYSA-N dpph Chemical compound [O-][N+](=O)C1=CC([N+](=O)[O-])=CC([N+]([O-])=O)=C1[N]N(C=1C=CC=CC=1)C1=CC=CC=C1 HHEAADYXPMHMCT-UHFFFAOYSA-N 0.000 claims description 5
- 239000012362 glacial acetic acid Substances 0.000 claims description 5
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 239000004570 mortar (masonry) Substances 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- XTSYGTKEMXUYDV-UHFFFAOYSA-N propylsilyl prop-2-enoate Chemical compound CCC[SiH2]OC(=O)C=C XTSYGTKEMXUYDV-UHFFFAOYSA-N 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 238000007790 scraping Methods 0.000 claims description 5
- 229910000077 silane Inorganic materials 0.000 claims description 5
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 5
- 230000007480 spreading Effects 0.000 claims description 5
- 238000003892 spreading Methods 0.000 claims description 5
- 239000006228 supernatant Substances 0.000 claims description 5
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 5
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- 239000011800 void material Substances 0.000 claims description 2
- 239000013535 sea water Substances 0.000 abstract description 67
- 238000010612 desalination reaction Methods 0.000 abstract description 33
- 230000004048 modification Effects 0.000 abstract description 6
- 238000012986 modification Methods 0.000 abstract description 6
- 239000010408 film Substances 0.000 description 39
- 239000012535 impurity Substances 0.000 description 15
- 231100001240 inorganic pollutant Toxicity 0.000 description 14
- 150000002500 ions Chemical class 0.000 description 14
- 230000008569 process Effects 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 11
- 230000000694 effects Effects 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 238000011033 desalting Methods 0.000 description 6
- 239000013505 freshwater Substances 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 5
- 125000000524 functional group Chemical group 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 230000008021 deposition Effects 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 229920002301 cellulose acetate Polymers 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 239000003361 porogen Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002455 scale inhibitor Substances 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 239000013589 supplement Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910001410 inorganic ion Inorganic materials 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Classifications
-
- 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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The application provides an organic-inorganic hybrid membrane and a preparation method thereof, wherein the membrane forming substrate, chitosan, a pore-forming agent, a flux improver and a scale inhibition modifier are adopted, the membrane forming substrate is nano surface supported modified fluorinated beta zeolite, the flux modifier consists of an amphiphilic block copolymer and a nano silicon-based mesoporous material, the scale inhibition modifier consists of carboxyl carbon quantum dots and cellulose solution, the flux of pure water is obviously improved after the membrane forming substrate is formed by the organic-inorganic hybrid membrane forming substrate through the flux modifier, the generation rate of inorganic scale is obviously slowed down through the scale inhibition improver, and the inorganic scale is difficult to accumulate on the surface of an ultrafiltration membrane after the membrane forming substance is subjected to interface modification, so that seawater desalination can be continuously carried out.
Description
Technical Field
The application belongs to the field of ultrafiltration membranes, and particularly relates to an organic-inorganic hybrid ultrafiltration membrane and a preparation method thereof.
Background
In the prior art, the world population rises, the utilization rate of fresh water resources is low, the fresh water can be used as the world maximum fresh water resource after the seawater is desalted, but in the process of seawater desalination, inorganic pollution is easy to occur on the surface of the existing ultrafiltration membrane, namely, the ultrafiltration membrane is scaled on the surface of the ultrafiltration membrane, the ultrafiltration membrane holes are blocked, so that seawater desalination cannot be performed, the ultrafiltration membrane needs to be frequently replaced, further, the seawater desalination cost is obviously improved, the scaling condition of the surface of the ultrafiltration membrane is reduced by adding the scale inhibitor in the prior art, but the performance of the scale inhibitor is limited, the scaling speed of the surface of the ultrafiltration membrane is increased along with the increase of the concentration of various inorganic ions in the seawater, the consumption of the ultrafiltration membrane is increased, the continuous seawater desalination is not facilitated, and improvement is needed in the prior art.
Disclosure of Invention
The application provides an organic-inorganic hybrid ultrafiltration membrane, which aims to solve the technical problems that in the prior art, inorganic pollution exists on the surface of the ultrafiltration membrane in the sea water desalting process, the surface of the ultrafiltration membrane still can scale along with the sea water desalting process, the sea water desalting process is hindered, the ultrafiltration membrane needs to be replaced frequently, and the sea water desalting cost is increased;
the second object of the application is to provide a method for preparing an organic-inorganic hybrid ultrafiltration membrane;
the third object of the application is to provide an application of the organic-inorganic hybrid ultrafiltration membrane in sea water desalination.
In order to achieve the first object, the present application adopts the following scheme:
an organic-inorganic hybrid ultrafiltration membrane comprises the following components in parts by weight:
the film forming substrate is nano surface supported modified fluorinated beta zeolite;
the flux modifier consists of the following components in parts by weight:
5-10 parts of amphiphilic block copolymer
5-8 parts of nano silicon-based mesoporous material;
the scale inhibition modifier comprises the following components in parts by weight:
10-15 parts of carboxyl carbon quantum dots
5-8 parts of cellulose solution.
Preferably, the preparation method of the nano surface supported modified fluorinated beta zeolite comprises the following steps:
step 101, putting beta zeolite into a muffle furnace, and activating for 3.5 hours under the conditions of vibration frequency of 100-250hz and 600-700 ℃ to obtain activated beta zeolite;
102, mixing activated beta zeolite, propyl acryloyloxy silane and N, N-dimethylamide according to a mass ratio of 8-12:2:3 sequentially adding into a reaction kettle, stirring at 100-200rpm for 10-20min, dropwise dripping DPPH, and introducing F at a rate of 1-5ml/min 2 Under the oil bath condition of 140 ℃, reacting for 12-24 hours to obtain the fluoridized beta zeolite precursor;
step 103, mixing the fluorinated beta zeolite precursor obtained in the step 102, GMA, benzene and diazo isobutyronitrile according to a mass ratio of 5-10:2-4:1:1 are sequentially put into a magnetic stirring kettle, reacted for 10 to 15 hours at the temperature of 60 to 75 ℃ and the rpm of 1800 to 2100, washed and dried by ethyl acetate, and then put into a ball mill for ball milling to 10 to 200nm, thus obtaining the nano surface supported modified fluorinated beta zeolite.
Preferably, the preparation method of the beta zeolite in the step 101 comprises the following steps:
step 201 tetraethylammonium hydroxide solution (18-25 w%) SiO 2 Powder and Al powder in the mass ratio of 1:5-8:2, putting the mixture into a stirring kettle, and stirring the mixture for 1 to 3 hours at room temperature and 1000 to 1800rpm to obtain zeolite precursor sol;
step 202, putting the zeolite precursor sol obtained in the step 201 into a high-pressure reaction kettle, reacting for 6-12 hours at the temperature of 300-500atm and the temperature of 100-200 ℃, and cooling and filtering to obtain a beta zeolite precursor;
and 203, putting the beta zeolite precursor obtained in the step 202 into a muffle furnace, heating to 850-990 ℃ at a heating rate of 10-15 ℃/min, calcining for 10-12h, stirring for 12-15h under the conditions of 125 ℃ oil bath and 100-250rpm, and cooling to room temperature to obtain the beta zeolite.
The practical implementation process adopts nano surface supported modified fluorinated beta zeolite and has the following advantages:
firstly, the fluorinated beta zeolite has a large number of micropores and mesoporous structures, has larger specific surface area and pore capacity, can effectively adsorb salt and impurities in the seawater, and can provide binding sites for the surface of the ultrafiltration membrane by nano surface support modification, so that the surface of the ultrafiltration membrane is combined with hydrogen bonds, the ultrafiltration membrane has repulsive force on inorganic impurity ions in the seawater, the retention rate of the inorganic impurity ions is improved in the process of pressurizing and desalting the seawater, and the adsorption performance of the fluorinated beta zeolite is further improved, so that the seawater desalination can be continuously carried out;
secondly, after the beta zeolite is fluorinated, micropores and mesoporous structures in the beta zeolite can pass through a molecular sieve effect and have strong electron withdrawing capability, pure water in the seawater can be driven to move to the other side of the ultrafiltration membrane through hydrogen bonds, inorganic impurity ions in the seawater are trapped, and after the beta zeolite is matched with a scale inhibition modifier supported on the surface, on one hand, the surface of the ultrafiltration membrane has repulsive force on the impurity ions in the seawater, the surface of the ultrafiltration membrane is not easy to be polluted by inorganic pollutants, scale is not easy to be formed, on the other hand, the scale inhibition modifier further enables the auxiliary capability of the inorganic pollutants on the ultrafiltration surface to be reduced, the scale inhibition of the ultrafiltration membrane can be improved, and the scale inhibition rate of the ultrafiltration membrane can be improved by matching with an intermittent supercharging seawater desalination method, so that the seawater desalination can be continuously carried out.
Preferably, the preparation method of the amphiphilic block copolymer comprises the following steps:
step 301, adding polypropylene ethanol, sodium ethoxide and allyl chloride into a stirred tank according to a mass ratio of 3:2:5, reacting for 10-30min at 40-60 ℃ and 100-300rpm, and condensing and refluxing for 3-5h at 113.5 ℃ to obtain a component A;
step 302, the component A, hexamethoxy silane and isopropanol prepared in the step 301 are mixed according to the mass ratio of 3-7:1:3, sequentially putting the materials into a reaction kettle, stirring for 10-20min at 30-50 ℃ and 50-200rpm, and then distilling under reduced pressure for 19min to obtain a component B;
step 303 component B, polyethylene glycol (M) n ＝1100-1500 Dimethylformamide and glacial acetic acid in a volume ratio of 5 to 15:2-7:1:3.3, putting the mixture into a reaction kettle, reacting for 5-7 hours at 80-120 ℃ and 100-200rpm, cooling to 92 ℃, distilling under reduced pressure at-0.1 mpa, using a dialysis bag with the molecular weight cut-off of 4500g/mol, intercepting for 5-10 times, and freeze-drying to obtain the amphiphilic block copolymer.
In the practical implementation process, the amphiphilic block copolymer has the following advantages: the amphiphilic block copolymer can form a hydrophilic channel inside the ultrafiltration membrane, microscopically drive pure water in the seawater to move to the other side of the ultrafiltration membrane, intercept inorganic impurity ions in the seawater, promote the interception rate and flux of the ultrafiltration membrane,
preferably, the void ratio of the nano silicon-based mesoporous material is 80-99%.
Preferably, the preparation method of the nano silicon-based mesoporous material comprises the following steps: polymethyl hydrogen siloxane and absolute ethyl alcohol are mixed according to the mass ratio of 1:10-15 are put into a magnetic stirring kettle, stirred for 24-36 hours at room temperature and 1800-2500rpm, and then a proper amount of tetraethyl silicate is dropwise added, stirred for 1 hour at 2200-3000rpm, thus obtaining the porous gel; washing and drying the porous gel, and ball-milling to 50-200nm to obtain the nano silicon-based mesoporous material.
In the practical implementation process, the nano silicon-based mesoporous material has the advantages that the network structure inside the ultrafiltration membrane is enlarged by combining with the combining site of the nano surface supported modified fluorinated beta zeolite surface, so that a local hydrophilic area is formed on the ultrafiltration membrane surface, inorganic impurity ions in seawater are repelled, and the flux of the ultrafiltration membrane is increased.
Preferably, the preparation method of the carboxyl quantum dot comprises the following steps:
sequentially adding anhydrous citric acid, L-ascorbic acid and part of NaOH (18-25 w%) solution into a mortar, and grinding for 10-50min to obtain quantum dot slurry; sequentially adding the quantum dot slurry and the rest NaOH solution into a stirring kettle, reacting for 8-12 hours at 50-120rpm and room temperature, dialyzing for 3-5 times by using a dialysis bag with the molecular weight of 3500g/mol, and freeze-drying to obtain the carboxyl quantum dot.
Preferably, the mass ratio of the anhydrous citric acid, the L-ascorbic acid and the NaOH solution (18-25 w%) is 2-5:2-10:3.
in the practical implementation process, the carboxyl quantum dot ultrafiltration membrane has the following advantages in scale inhibition performance:
firstly, the carboxyl functional group on the surface of the carboxyl quantum dot ultrafiltration membrane has negative charge, and can be repulsive to positive point ions of inorganic impurities in seawater, so that the adsorption and deposition of inorganic pollutants on the surface of the ultrafiltration membrane are reduced, and the scaling degree is reduced.
Secondly, the carboxyl functional group of the carboxyl quantum dot ultrafiltration membrane can form a hydrogen bond with water molecules in the solvent to form a layer of hydration membrane, and the hydration membrane can prevent macromolecules and colloid particles from being adsorbed and adhered on the surface of the membrane, so that the pollution and blockage of the membrane are reduced; furthermore, the carboxyl functional group of the carboxyl quantum dot ultrafiltration membrane has higher hydrophilicity and can form a hydrogen bond with water molecules. The hydrophilicity can increase the activity of water molecules in the solution, so that the water molecules can more easily interact with scaling substances, and the adsorption and deposition of the scaling substances on the surface of the membrane are reduced.
Thirdly, dynamic balance exists between carboxyl functional groups on the surface of the carboxyl quantum dot ultrafiltration membrane and scaling substances in the solution. When the scaling species in the solution interact with the carboxyl functionality, a thin film is formed between them, which prevents further adsorption and deposition of the scaling species on the membrane surface.
Preferably, the preparation method of the cellulose solution comprises the following steps:
step 401, pre-soaking nano water hyacinth fibers in deionized water for 4 hours, cooling to 2-6 ℃, then putting the nano water hyacinth fibers into an ultrasonic dispersing machine, carrying out ultrasonic treatment for 10-20 minutes under the condition of 800-1000W, filtering and drying to obtain a cellulose pretreatment substance;
step 402, the cellulose pretreatment obtained in step 401 is treated by NaOH (12-18 w%) solution and urea solution (60-80 w%) according to the mass ratio of 10:3-5:2:4, putting the mixture into a low-temperature water bath kettle, reacting for 0.5-1.5 hours at the temperature of 5-10 ℃, and centrifuging at the speed of 4000rpm to obtain supernatant, thus obtaining the cellulose solution.
In the practical implementation process, the cellulose solution is used as the supplement of carboxyl quantum dots to supplement hydrogen bonds, negative ions and hydrogen bond substances for the surface of the ultrafiltration membrane, so that the repulsive force of the surface of the ultrafiltration membrane to inorganic impurity ions is further improved, the scaling rate of the inorganic impurity ions on the surface of the ultrafiltration membrane is reduced, and the continuous progress of the sea water desalination process is promoted.
In order to achieve the second object, the present application adopts the following scheme;
the preparation method of the organic-inorganic hybrid ultrafiltration membrane comprises the following steps:
step 501, putting a film forming substrate, chitosan, a pore-forming agent, a nano silicon-based mesoporous material and a proper amount of absolute ethyl alcohol into a stirring kettle, and stirring and reacting for 10-20 hours under the conditions of water bath at 80 ℃ and 420-800rpm to obtain a film casting solution;
step 502, spreading the casting film liquid obtained in the step 501 in a tray with the length of 50cm, the width of 30cm and the depth of 20cm, and dropwise adding the amphiphilic block copolymer, the carboxyl carbon quantum dots and the cellulose solution in sequence under the conditions of the vibration frequency of 300-600hz, the ambient pressure of 200-300kpa and the temperature of 50-60 ℃ to obtain flux scale inhibition modified casting film liquid;
step 503, cooling the flux scale inhibition modified membrane casting solution obtained in step 502 to 10-30 ℃, placing the membrane casting solution in a vacuum condition of-0.09 Mpa, and standing for 10-12h to obtain a preparation membrane casting solution;
and 504, placing the prepared film casting solution obtained in the step 503 on one side of a glass plate, placing an adjusting scraper on one side of the glass plate close to the prepared film casting solution, starting a film scraping machine, and standing for 30 seconds to obtain the organic-inorganic hybrid ultrafiltration film.
In order to achieve the third purpose, the organic-inorganic hybrid ultrafiltration membrane prepared by the application is applied to sea water desalination, intermittent pressurization and depressurization are carried out on the side of the ultrafiltration membrane, which is provided with sea water, and the scaling rate of the surface of the ultrafiltration membrane can be effectively reduced by matching with the ultrafiltration membrane.
More preferably, the specific steps of intermittent pressure increasing and decreasing are as follows: the side of the ultrafiltration membrane filled with seawater is pressurized to 500kpa at a rate of 10kpa/min, and then is depressurized to 300kpa at a rate of 5kpa/min, and the operation is performed in a reciprocating manner.
Compared with the prior art, the application has the following advantages:
1. the application provides an organic-inorganic hybrid membrane, which comprises a membrane forming base material, chitosan, a pore-forming agent, a flux modifier and a scale inhibition modifier, wherein the membrane forming base material is nano surface supported modified fluorinated beta zeolite, the flux modifier consists of an amphiphilic block copolymer and a nano silicon-based mesoporous material, the scale inhibition modifier consists of carboxyl carbon quantum dots and a cellulose solution, the flux modifier is used for obviously improving the flux of pure water after the membrane forming of the organic-inorganic hybrid membrane forming base material, the generation rate of inorganic scale is obviously slowed down by the scale inhibition modifier, and the inorganic scale is difficult to accumulate on the surface of an ultrafiltration membrane after the membrane forming material is subjected to interface modification, so that seawater desalination can be continuously carried out.
2. The application provides a preparation method of an organic-inorganic hybrid membrane, which is characterized in that a novel membrane forming substance is selected, and the membrane forming substance is modified by a flux modifier and a scale inhibition modifier vibration dropping liquid, so that after the membrane is formed, the flux of a filter hole to pure water is obviously improved, inorganic pollutants are difficult to accumulate on an ultrafiltration membrane, and the preparation method has the advantages of good scale inhibition effect, sustainable utilization and reduction of sea water desalination cost.
3. The application provides an application of an organic-inorganic hybrid membrane, which is characterized in that the organic-inorganic hybrid membrane is prepared into a plate shape, sea water desalination is carried out under the condition that the operation pressure difference is 500kpa, and an intermittent pressure increasing and reducing method is used for further reducing inorganic pollutants on the surface of an ultrafiltration membrane, so that the organic-inorganic hybrid membrane has the advantages of good scale inhibition effect, sustainable utilization and sea water desalination cost reduction.
Drawings
FIG. 1 is a graph showing the fresh water volume V of the fresh water side of the ultrafiltration membrane according to the test 3 of the present application as a function of the desalination time T of a seawater sample
Detailed Description
The application is further described below in connection with Table 1, specific examples 1-3 and comparative examples 1-3:
example 1.
(1) The preparation process of nanometer surface supported modified fluoridated beta zeolite includes the following steps:
step 101, putting beta zeolite into a muffle furnace, and activating for 3.5 hours under the condition of vibration frequency 152hz and 625 ℃ to obtain activated beta zeolite;
102, mixing activated beta zeolite, propyl acryloyloxy silane and N, N-dimethylamide according to a mass ratio of 8:2:3 sequentially adding into a reaction kettle, stirring at 122rpm for 10min, dropwise adding DPPH, and introducing F at a rate of 1.5ml/min 2 Under the oil bath condition of 140 ℃, reacting for 13 hours to obtain the fluoridized beta zeolite precursor;
step 103, mixing the fluorinated beta zeolite precursor obtained in the step 102, GMA, benzene and diazo isobutyronitrile according to a mass ratio of 6:2:1: and 1, sequentially putting the materials into a magnetic stirring kettle, reacting for 11 hours at the temperature of 62 ℃ and the speed of 1850rpm, washing and drying by ethyl acetate, and then putting the materials into a ball mill for ball milling to 50nm to obtain the nano surface supported modified fluorinated beta zeolite.
(2) The preparation method of the beta zeolite comprises the following steps:
step 201 tetraethylammonium hydroxide solution (18-25 w%) SiO 2 Powder and Al powder in a mass ratio of 1:6:2, putting the mixture into a stirring kettle, and stirring the mixture for 1.2 hours at room temperature and 1100rpm to obtain zeolite precursor sol;
step 202, putting the zeolite precursor sol obtained in the step 201 into a high-pressure reaction kettle, reacting for 6.5 hours at 300atm and 120 ℃, and cooling and filtering to obtain a beta zeolite precursor;
and 203, putting the beta zeolite precursor obtained in the step 202 into a muffle furnace at a heating rate of 11 ℃/min, heating to 850 ℃, calcining for 11 hours, stirring for 12 hours under the conditions of oil bath at 125 ℃ and 105rpm, and cooling to room temperature to obtain the beta zeolite.
(3) The preparation method of the amphiphilic block copolymer comprises the following steps:
step 301, adding polypropylene ethanol, sodium ethoxide and allyl chloride into a stirred tank according to a mass ratio of 3:2:5, reacting for 12min at 45 ℃ and 120rpm, and condensing and refluxing for 3h at 113.5 ℃ to obtain a component A;
step 302, the component A, hexamethoxy silane and isopropanol prepared in the step 301 are mixed according to the mass ratio of 3:1:3, sequentially putting the materials into a reaction kettle, stirring for 10min at 30 ℃ and 80rpm, and then distilling under reduced pressure for 19min to obtain a component B;
step 303 component B, polyethylene glycol (M) n =1150), dimethylformamide and glacial acetic acid in a volume ratio of 5:3:1:3.3, putting the mixture into a reaction kettle, reacting for 5 hours at 85 ℃ and 100rpm, cooling to 92 ℃, distilling under reduced pressure at-0.1 mpa, using a dialysis bag with the molecular weight cut-off of 4500g/mol, intercepting for 5 times, and freeze-drying to obtain the amphiphilic block copolymer.
(4) The preparation method of the nano silicon-based mesoporous material comprises the following steps:
polymethyl hydrogen siloxane and absolute ethyl alcohol are mixed according to the mass ratio of 1:10 is put into a magnetic stirring kettle, stirred for 24 hours at room temperature and 1800rpm, and then a proper amount of tetraethyl silicate is dropwise added, stirred for 1 hour at 2200rpm, thus obtaining the porous gel; washing and drying the porous gel, and ball-milling to 50nm to obtain the nano silicon-based mesoporous material.
(5) The preparation method of the carboxyl quantum dot comprises the following steps:
sequentially adding anhydrous citric acid, L-ascorbic acid and part of NaOH (18-25 w%) solution into a mortar, and grinding for 11min to obtain quantum dot slurry; sequentially adding the quantum dot slurry and the rest NaOH solution into a stirring kettle, reacting for 8 hours at the room temperature at 51rpm, dialyzing for 3 times by using a dialysis bag with the molecular weight of 3500g/mol, and freeze-drying to obtain the carboxyl quantum dot.
Wherein the mass ratio of the anhydrous citric acid to the L-ascorbic acid to the NaOH solution (18-25 w%) is 2:3.5:3.
(6) The preparation method of the cellulose solution comprises the following steps:
step 401, pre-soaking nano water hyacinth fibers in deionized water for 4 hours, cooling to 2.5 ℃, putting into an ultrasonic dispersing machine, performing ultrasonic treatment for 10 minutes under the condition of 600W, filtering and drying to obtain a cellulose pretreatment;
step 402. The cellulose pretreatment obtained in step 401, naOH (13.5 w%) solution, urea solution (61.5 w%) are mixed according to a mass ratio of 10:3:2:4, putting the mixture into a low-temperature water bath kettle, reacting for 0.5h at 5 ℃, and centrifuging at 4000rpm to obtain supernatant, thus obtaining the cellulose solution.
(7) The preparation method of the organic-inorganic hybrid ultrafiltration membrane comprises the following steps:
step 501, according to the mass portions shown in the table 1, putting a film forming substrate, chitosan, a pore-forming agent, a nano silicon-based mesoporous material and a proper amount of absolute ethyl alcohol into a stirring kettle, and stirring and reacting for 10 hours under the conditions of water bath at 80 ℃ and 420rpm to obtain a film casting solution;
step 502, spreading the casting film liquid obtained in the step 501 in a tray with the length of 50cm, the width of 30cm and the depth of 20cm, and sequentially and dropwise dripping an amphiphilic block copolymer, carboxyl carbon quantum dots and a cellulose solution under the conditions of the vibration frequency of 300hz, the ambient pressure of 200kpa and the temperature of 50 ℃ to obtain flux scale inhibition modified casting film liquid;
step 503, cooling the flux scale inhibition modified membrane casting solution obtained in step 502 to 10 ℃, placing the membrane casting solution in a vacuum condition of-0.09 Mpa, and standing for 10 hours to obtain a preparation membrane casting solution;
and 504, placing the prepared film casting solution obtained in the step 503 on one side of a glass plate, placing an adjusting scraper on one side of the glass plate close to the prepared film casting solution, starting a film scraping machine, and standing for 30 seconds to obtain the organic-inorganic hybrid ultrafiltration film.
Example 2.
(1) The preparation process of nanometer surface supported modified fluoridated beta zeolite includes the following steps:
step 101, putting beta zeolite into a muffle furnace, and activating for 3.5 hours under the condition of vibration frequency 175hz and 650 ℃ to obtain activated beta zeolite;
102, mixing activated beta zeolite, propyl acryloyloxy silane and N, N-dimethylamide according to a mass ratio of 9:2:3 sequentially adding into a reaction kettle, stirring at 150rpm for 10min, dropwise adding DPPH, and introducing F at a rate of 2.5ml/min 2 Under the condition of 140 ℃ oil bath, the reactionAfter 18h, obtaining a fluorinated beta zeolite precursor;
step 103, mixing the fluorinated beta zeolite precursor obtained in the step 102, GMA, benzene and diazo isobutyronitrile according to a mass ratio of 7:3:1: and 1, sequentially putting the materials into a magnetic stirring kettle, reacting for 12 hours at 70 ℃ and 1900rpm, washing and drying by ethyl acetate, and then putting the materials into a ball mill for ball milling to 80nm to obtain the nano surface supported modified fluorinated beta zeolite.
(2) The preparation method of the beta zeolite comprises the following steps:
step 201 tetraethylammonium hydroxide solution (22 w%), siO 2 Powder and Al powder in a mass ratio of 1:6:2, putting the mixture into a stirring kettle, and stirring the mixture for 2 hours at the room temperature and 1300rpm to obtain zeolite precursor sol;
step 202, putting the zeolite precursor sol obtained in the step 201 into a high-pressure reaction kettle, reacting for 8 hours at 400tm and 150 ℃, and cooling and filtering to obtain a beta zeolite precursor;
and 203, putting the beta zeolite precursor obtained in the step 202 into a muffle furnace at a heating rate of 12 ℃/min, heating to 900 ℃, calcining for 11 hours, stirring for 13 hours under the conditions of oil bath at 125 ℃ and 200rpm, and cooling to room temperature to obtain the beta zeolite.
(3) The preparation method of the amphiphilic block copolymer comprises the following steps:
step 301, adding polypropylene ethanol, sodium ethoxide and allyl chloride into a stirred tank according to a mass ratio of 3:2:5, reacting for 20min at 50 ℃ and 200rpm, and condensing and refluxing for 4h at 113.5 ℃ to obtain a component A;
step 302, the component A, hexamethoxy silane and isopropanol prepared in the step 301 are mixed according to the mass ratio of 5:1:3, sequentially putting the materials into a reaction kettle, stirring the materials for 15min at 40 ℃ and 150rpm, and then performing reduced pressure distillation for 19min to obtain a component B;
step 303 component B, polyethylene glycol (M) n =1250), dimethylformamide and glacial acetic acid in a volume ratio of 10:5:1:3.3, putting into a reaction kettle, reacting at 100 ℃ and 100-200rpm for 5-7h, cooling to 92 ℃, distilling under reduced pressure at-0.1 mpaAnd (3) using a dialysis bag with the molecular weight cut-off of 4500g/mol, and freeze-drying after 8 times of cut-off to obtain the amphiphilic block copolymer.
(4) The preparation method of the nano silicon-based mesoporous material comprises the following steps:
polymethyl hydrogen siloxane and absolute ethyl alcohol are mixed according to the mass ratio of 1:12 into a magnetic stirring kettle, stirring at room temperature and 2200rpm for 30 hours, dropwise adding a proper amount of tetraethyl silicate, stirring at 2800rpm for 1 hour to obtain porous gel; washing and drying the porous gel, and ball-milling to 150nm to obtain the nano silicon-based mesoporous material.
(5) The preparation method of the carboxyl quantum dot comprises the following steps:
sequentially adding anhydrous citric acid, L-ascorbic acid and part of NaOH (22 w%) solution into a mortar, and grinding for 40min to obtain quantum dot slurry; sequentially adding the quantum dot slurry and the rest NaOH solution into a stirring kettle, reacting for 10 hours at 100rpm and room temperature, dialyzing for 4 times by using a dialysis bag with the molecular weight of 3500g/mol, and freeze-drying to obtain the carboxyl quantum dot.
Wherein the mass ratio of the anhydrous citric acid, the L-ascorbic acid and the NaOH solution (20 w%) is 3:8:3.
(6) The preparation method of the cellulose solution comprises the following steps:
step 401, pre-soaking nano water hyacinth fibers in deionized water for 4 hours, cooling to 4 ℃, putting into an ultrasonic dispersing machine, performing ultrasonic treatment for 15 minutes under the condition of 900W, and filtering and drying to obtain a cellulose pretreatment;
step 402, the cellulose pretreatment obtained in step 401, naOH (16 w%) solution and urea solution (70 w%) are mixed according to the mass ratio of 5:2:1:2, putting the mixture into a low-temperature water bath pot, reacting for 1h at 8 ℃, and centrifuging at 4000rpm to obtain supernatant, thus obtaining the cellulose solution.
(7) The preparation method of the organic-inorganic hybrid ultrafiltration membrane comprises the following steps:
step 501, according to the weight portions shown in table 1, putting a film forming substrate, chitosan, a pore-forming agent, a nano silicon-based mesoporous material and a proper amount of absolute ethyl alcohol into a stirring kettle, and stirring and reacting for 15 hours under the conditions of water bath at 80 ℃ and 780rpm to obtain a film casting solution;
step 502, spreading the casting film liquid obtained in the step 501 in a tray with the length of 50cm, the width of 30cm and the depth of 20cm, and sequentially and dropwise dripping an amphiphilic block copolymer, carboxyl carbon quantum dots and a cellulose solution under the conditions of the vibration frequency of 450hz, the ambient pressure of 250kpa and the temperature of 55 ℃ to obtain flux scale inhibition modified casting film liquid;
step 503, cooling the flux scale inhibition modified membrane casting solution obtained in step 502 to 20 ℃, placing the membrane casting solution in a vacuum condition of-0.09 Mpa, and standing for 11 hours to obtain a preparation membrane casting solution;
and 504, placing the prepared film casting solution obtained in the step 503 on one side of a glass plate, placing an adjusting scraper on one side of the glass plate close to the prepared film casting solution, starting a film scraping machine, and standing for 30 seconds to obtain the organic-inorganic hybrid ultrafiltration film.
Example 3.
(1) The preparation process of nanometer surface supported modified fluoridated beta zeolite includes the following steps:
step 101, putting beta zeolite into a muffle furnace, and activating for 3.5 hours under the condition of vibration frequency 250hz and 700 ℃ to obtain activated beta zeolite;
step 102, activating beta zeolite, propyl acryloyloxy silane and N, N-dimethylamide according to a mass ratio of 12:2:3 sequentially adding into a reaction kettle, stirring at 200rpm for 20min, dropwise adding DPPH, and introducing F at a rate of 5ml/min 2 Under the oil bath condition of 140 ℃, reacting for 24 hours to obtain the fluorinated beta zeolite precursor;
step 103, mixing the fluorinated beta zeolite precursor obtained in the step 102, GMA, benzene and diazo isobutyronitrile according to a mass ratio of 10:4:1: and 1, sequentially putting the materials into a magnetic stirring kettle, reacting for 15 hours at 75 ℃ and 2100rpm, washing and drying by ethyl acetate, and then putting the materials into a ball mill for ball milling to 150nm to obtain the nano surface supported modified fluorinated beta zeolite.
(2) The preparation method of the beta zeolite comprises the following steps:
step 201 tetraethylammonium hydroxide solution (25 w%), siO 2 Powder and Al powder in a mass ratio of 1:8:2, putting the mixture into a stirring kettle, and stirring the mixture for 3 hours at room temperature and 1800rpm to obtain zeolite precursor sol;
step 202, putting the zeolite precursor sol obtained in the step 201 into a high-pressure reaction kettle, reacting for 12 hours at 500atm and 200 ℃, and cooling and filtering to obtain a beta zeolite precursor;
and 203, putting the beta zeolite precursor obtained in the step 202 into a muffle furnace at a heating rate of 15 ℃/min, heating to 990 ℃, calcining for 12 hours, stirring for 15 hours under the conditions of 125 ℃ oil bath and 250rpm, and cooling to room temperature to obtain the beta zeolite.
(3) The preparation method of the amphiphilic block copolymer comprises the following steps:
step 301, adding polypropylene ethanol, sodium ethoxide and allyl chloride into a stirred tank according to a mass ratio of 3:2:5, reacting for 30min at 60 ℃ and 300rpm, and condensing and refluxing for 5h at 113.5 ℃ to obtain a component A;
step 302, the component A, hexamethoxy silane and isopropanol prepared in the step 301 are mixed according to the mass ratio of 7:1:3, sequentially putting the materials into a reaction kettle, stirring for 20min at 50 ℃ and 200rpm, and then distilling for 19min under reduced pressure to obtain a component B;
step 303 component B, polyethylene glycol (M) n =1500), dimethylformamide and glacial acetic acid in a volume ratio of 15:7:1:3.3, putting the mixture into a reaction kettle, reacting for 7 hours at 120 ℃ and 200rpm, cooling to 92 ℃, distilling under reduced pressure at-0.1 mpa, using a dialysis bag with the molecular weight cut-off of 4500g/mol, intercepting for 10 times, and freeze-drying to obtain the amphiphilic block copolymer.
(4) The preparation method of the nano silicon-based mesoporous material comprises the following steps:
polymethyl hydrogen siloxane and absolute ethyl alcohol are mixed according to the mass ratio of 1:15 is put into a magnetic stirring kettle, stirred for 36 hours at room temperature and 2500rpm, and then a proper amount of tetraethyl silicate is dropwise added, stirred for 1 hour at 3000rpm, thus obtaining the porous gel; washing and drying the porous gel, and ball-milling to 200nm to obtain the nano silicon-based mesoporous material.
(5) The preparation method of the carboxyl quantum dot comprises the following steps:
sequentially adding anhydrous citric acid, L-ascorbic acid and part of NaOH (25 w%) solution into a mortar, and grinding for 50min to obtain quantum dot slurry; sequentially adding the quantum dot slurry and the rest NaOH solution into a stirring kettle, reacting for 12 hours at 120rpm and room temperature, dialyzing for 5 times by using a dialysis bag with the molecular weight of 3500g/mol, and freeze-drying to obtain the carboxyl quantum dot.
Wherein the mass ratio of the anhydrous citric acid, the L-ascorbic acid and the NaOH solution (18-25 w%) is 5:2-10:3.
(6) The preparation method of the cellulose solution comprises the following steps:
step 401, pre-soaking nano water hyacinth fibers in deionized water for 4 hours, cooling to 6 ℃, then putting the nano water hyacinth fibers into an ultrasonic dispersing machine, carrying out ultrasonic treatment for 20 minutes under the condition of 1000W, and filtering and drying to obtain a cellulose pretreatment;
step 402, the cellulose pretreatment obtained in step 401, naOH (18 w%) solution and urea solution (80 w%) are mixed according to a mass ratio of 10:5:2:4, putting the mixture into a low-temperature water bath kettle, reacting for 1.5 hours at the temperature of 10 ℃, and centrifuging to obtain supernatant liquid at the speed of 4000rpm to obtain the cellulose solution.
(7) The preparation method of the organic-inorganic hybrid ultrafiltration membrane comprises the following steps:
step 501, according to the weight portions shown in table 1, putting a film forming substrate, chitosan, a pore-forming agent, a nano silicon-based mesoporous material and a proper amount of absolute ethyl alcohol into a stirring kettle, and stirring and reacting for 20 hours under the conditions of water bath at 80 ℃ and 800rpm to obtain a film casting solution;
step 502, spreading the casting film liquid obtained in the step 501 in a tray with the length of 50cm, the width of 30cm and the depth of 20cm, and sequentially and dropwise dripping an amphiphilic block copolymer, carboxyl carbon quantum dots and a cellulose solution under the conditions of the vibration frequency of 600hz, the ambient pressure of 300kpa and the temperature of 60 ℃ to obtain flux scale inhibition modified casting film liquid;
step 503, cooling the flux scale inhibition modified membrane casting solution obtained in step 502 to 30 ℃, placing the membrane casting solution in a vacuum condition of-0.09 Mpa, and standing for 12 hours to obtain a preparation membrane casting solution;
and 504, placing the prepared film casting solution obtained in the step 503 on one side of a glass plate, placing an adjusting scraper on one side of the glass plate close to the prepared film casting solution, starting a film scraping machine, and standing for 30 seconds to obtain the organic-inorganic hybrid ultrafiltration film.
Comparative example 1.
The film-forming substrate of example 3 was replaced with a cellulose acetate ester, and the remaining components were kept unchanged.
Comparative example 2.
The flux modifier of example 3 was removed and the content of film forming substrate and porogen was increased with the remaining components remaining unchanged.
Comparative example 3.
The scale inhibiting modifier in example 3 is removed, the content of the film forming base material and the pore-forming agent is increased, and the rest components are kept unchanged.
Comparative example 4.
The chitosan in example 3 was removed and the content of film forming substrate and porogen was raised, the remaining components remaining unchanged.
TABLE 1 composition table of the components in parts by weight for examples 1-3 and comparative examples 1-4
The scale inhibition capability test of inorganic pollutants in the sea water desalination process of calcium carbonate, calcium sulfate, magnesium sulfate and the like is carried out according to GB/T16632-2019 and SY/T5673-93 in examples 1-3 and comparative examples 1-4; the test results are shown in table 1 below.
The following tests were performed simultaneously:
test 1. Membrane flux test: the filtration capacity of the organic-inorganic hybrid membrane for pure water is applied for comment: compounding the prepared organic-inorganic hybrid membrane into an ultrafiltration membrane with the length of 50cm and the width of 20cm and the thickness of 1cm, soaking the ultrafiltration membrane with deionized water, loading the ultrafiltration membrane into a membrane energy detector, setting the pressure difference of two sides of the ultrafiltration membrane to be 0.5MPa under the room temperature condition, pre-pressing the ultrafiltration membrane until the fluid state of a seawater sample is stable under the pressure, and measuring the volume of the seawater sample passing through the membrane within a certain time;
membrane flux size was calculated by a=v 1 /V 2 * T, wherein A is membrane flux, V 1 Is the volume of the seawater sample passing through in unit time T, V 2 Is the volume of the ultrafiltration membrane; the test results are shown in table 1 below.
Test 2. Hold-up test: under the conditions of 0.5MPa and room temperature, placing a seawater sample and an ultrafiltration membrane into a membrane performance detector to respectively measure the conductivities of the seawater sample and deionized water, and calculating the rejection rate of the membrane to the seawater sample by using the following formula: j=d1-d 2/d1 x 100% and the test results are shown in table 2 below.
TABLE 2 results of national standard test for examples 1-3 and comparative examples 1-4 and test 1-2
Test 3. The prepared ultrafiltration membrane is placed in a seawater desalination pond, a seawater sample is continuously injected into one side of the seawater desalination pond, the volume change of the desalinated seawater at the other side of the ultrafiltration membrane is measured, the scale inhibition capability is evaluated, and a fresh water liquid outlet capability curve is drawn, as shown in the following figure 1.
As can be seen from the above table 2,
the scale inhibition efficiency is reduced after the film forming material is replaced by cellulose acetate in comparative example 1, because the fluorinated beta zeolite has a large number of micropores and mesopores, has larger specific surface area and pore capacity, can effectively adsorb salt and impurities in seawater, and the nano surface support modification can provide binding sites for the surface of the ultrafiltration membrane, so that the surface of the ultrafiltration membrane is combined with hydrogen bonds, the ultrafiltration membrane has repulsive force on inorganic impurity ions in the seawater, the retention rate of the inorganic impurity ions is improved in the process of pressurizing and desalting the seawater, and the adsorption performance of the fluorinated beta zeolite is further increased, so that the seawater desalination can be carried out continuously; after the beta zeolite is fluorinated, the micropore and mesoporous structure in the beta zeolite can pass through the molecular sieve effect and has strong electron-withdrawing capability, pure water in the seawater can be driven to move to the other side of the ultrafiltration membrane through hydrogen bonds, inorganic impurity ions in the seawater are trapped, and after the beta zeolite is matched with the scale inhibition modifier supported on the surface, on one hand, the surface of the ultrafiltration membrane has repulsive force on the impurity ions in the seawater, the surface of the ultrafiltration membrane is not easy to be polluted by inorganic pollutants, scale is not easy to be formed, on the other hand, the scale inhibition modifier further enables the auxiliary capability of the inorganic pollutants on the ultrafiltration surface to be reduced, the scale cannot be increased, and the scale inhibition rate of the ultrafiltration membrane can be improved by matching with an intermittent pressurizing seawater desalination method, so that the seawater desalination can be continuously carried out.
As can be seen from fig. 1, in the process of sea water desalination, the process of sea water desalination can be continuously performed, dynamic balance is presented after desalination is performed for a certain time, the scale inhibition performance of the surface of the ultrafiltration membrane is stable, hydrophilic channels are distributed in the membrane, the ultrafiltration membrane can continuously pass through pure water in a sea water sample, inorganic pollutants in the sea water are trapped, and the ultrafiltration membrane is not easy to be blocked by scale formation on the ultrafiltration membrane, so that sea water desalination is prevented; in comparative examples 2 and 3, the flux modifier and the scale inhibition modifier are removed respectively, after the flux modifier and the scale inhibition modifier are removed, the hydrophilic channels in the ultrafiltration membrane are obviously reduced, and inorganic pollutants can proliferate in the ultrafiltration membrane pores towards the outer surface of the ultrafiltration membrane, so that the seawater desalination is hindered; after the removal of the inorganic pollutants, the positive charges on the surface of the ultrafiltration membrane are reduced, the repulsive force to cations in the seawater is reduced, and the inorganic pollutants are easy to proliferate on the surface of the ultrafiltration membrane to block the seawater desalination process; in comparative example 4, chitosan was removed, and the flux modifier and the scale inhibition modifier lack binding sites, and cannot be connected to the surface of the film forming substrate, so that a hydrophilic channel and a positively charged water film cannot be formed in the ultrafiltration membrane, and seawater desalination was hindered.
The application provides an organic-inorganic hybrid membrane, which comprises a membrane forming base material, chitosan, a pore-forming agent, a flux modifier and a scale inhibition modifier, wherein the membrane forming base material is nano surface supported modified fluorinated beta zeolite, the flux modifier consists of an amphiphilic block copolymer and a nano silicon-based mesoporous material, the scale inhibition modifier consists of carboxyl carbon quantum dots and a cellulose solution, the flux modifier is used for obviously improving the flux of pure water after the membrane forming of the organic-inorganic hybrid membrane forming base material, the generation rate of inorganic scale is obviously slowed down by the scale inhibition modifier, and the inorganic scale is difficult to accumulate on the surface of an ultrafiltration membrane after the membrane forming material is subjected to interface modification, so that seawater desalination can be continuously carried out.
The application provides a preparation method of an organic-inorganic hybrid membrane, which is characterized in that a novel membrane forming substance is selected, and the membrane forming substance is modified by a flux modifier and a scale inhibition modifier vibration dropping liquid, so that after the membrane is formed, the flux of a filter hole to pure water is obviously improved, inorganic pollutants are difficult to accumulate on an ultrafiltration membrane, and the preparation method has the advantages of good scale inhibition effect, sustainable utilization and reduction of sea water desalination cost.
The application provides an application of an organic-inorganic hybrid membrane, which is characterized in that the organic-inorganic hybrid membrane is prepared into a plate shape, sea water desalination is carried out under the condition that the operation pressure difference is 500kpa, and an intermittent pressure increasing and reducing method is used for further reducing inorganic pollutants on the surface of an ultrafiltration membrane, so that the organic-inorganic hybrid membrane has the advantages of good scale inhibition effect, sustainable utilization and sea water desalination cost reduction.
The foregoing description of the preferred embodiments of the application is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the application.
Claims (10)
1. The organic-inorganic hybrid ultrafiltration membrane is characterized by comprising the following components in parts by weight:
the film forming substrate is nano surface supported modified fluorinated beta zeolite;
the flux modifier consists of the following components in parts by weight:
5-10 parts of amphiphilic block copolymer
5-8 parts of nano silicon-based mesoporous material;
the scale inhibition modifier comprises the following components in parts by weight:
10-15 parts of carboxyl carbon quantum dots
5-8 parts of cellulose solution.
2. The organic-inorganic hybrid ultrafiltration membrane according to claim 1, wherein the preparation method of the nano-surface supported modified fluorinated beta zeolite comprises the following steps:
step 101, putting beta zeolite into a muffle furnace, and activating for 3.5 hours under the conditions of vibration frequency of 100-250hz and 600-700 ℃ to obtain activated beta zeolite;
step 102, sequentially adding activated beta zeolite, propyl acryloyloxy silane and N, N-dimethylamide into a reaction kettle, stirring for 10-20min at 100-200rpm, dropwise adding DPPH, and introducing F 2 Under the oil bath condition of 140 ℃, reacting for 12-24 hours to obtain the fluoridized beta zeolite precursor;
step 103, sequentially adding the fluorinated beta zeolite precursor, GMA, benzene and diazo isobutyronitrile obtained in the step 102 into a magnetic stirring kettle, reacting for 10-15 hours at the temperature of 60-75 ℃ and the rpm of 1800-2100rpm, washing and drying by ethyl acetate, and then adding into a ball mill for ball milling to 10-200nm to obtain the nano surface supported modified fluorinated beta zeolite.
3. An organic-inorganic hybrid ultrafiltration membrane according to claim 2, wherein the preparation method of the zeolite beta in step 101 comprises the following steps:
step 201 tetraethylammonium hydroxide solution (18-25 w%) SiO 2 Putting the powder and Al powder into a stirring kettle, and stirring for 1-3h at room temperature and 1000-1800rpm to obtain zeolite precursor sol;
step 202, putting the zeolite precursor sol obtained in the step 201 into a high-pressure reaction kettle, reacting for 6-12 hours at the temperature of 300-500atm and the temperature of 100-200 ℃, and cooling and filtering to obtain a beta zeolite precursor;
and 203, putting the beta zeolite precursor obtained in the step 202 into a muffle furnace, heating to 850-990 ℃ at a heating rate of 10-15 ℃/min, calcining for 10-12h, stirring for 12-15h under the conditions of 125 ℃ oil bath and 100-250rpm, and cooling to room temperature to obtain the beta zeolite.
4. The organic-inorganic hybrid ultrafiltration membrane according to claim 1, wherein the preparation method of the amphiphilic block copolymer comprises the following steps:
step 301, putting the polypropylene ethanol, sodium ethoxide and allyl chloride into a stirring kettle, reacting for 10-30min at 40-60 ℃ and 100-300rpm, and condensing and refluxing for 3-5h at 113.5 ℃ to obtain a component A;
step 302, the component A, hexamethoxy silane and isopropanol prepared in the step 301 are mixed according to the mass ratio of 3-7:1:3, sequentially putting the materials into a reaction kettle, stirring for 10-20min at 30-50 ℃ and 50-200rpm, and then distilling under reduced pressure for 19min to obtain a component B;
step 303 component B, polyethylene glycol (M) n =1100-1500), dimethylformamide and glacial acetic acid in a volume ratio of 5-15:2-7:1:3.3, putting the mixture into a reaction kettle, reacting for 5-7 hours at 80-120 ℃ and 100-200rpm, cooling to 92 ℃, distilling under reduced pressure at-0.1 mpa, intercepting by using a dialysis bag, and freeze-drying to obtain the amphiphilic block copolymer.
5. The organic-inorganic hybrid ultrafiltration membrane according to claim 1, wherein the void fraction of the nano silicon-based mesoporous material is 80-99%.
6. The organic-inorganic hybrid ultrafiltration membrane according to claim 5, wherein the preparation method of the nano silicon-based mesoporous material comprises the following steps: polymethyl hydrogen siloxane and absolute ethyl alcohol are mixed according to the mass ratio of 1:10-15 are put into a magnetic stirring kettle, stirred for 24-36 hours at room temperature and 1800-2500rpm, and then a proper amount of tetraethyl silicate is dropwise added, stirred for 1 hour at 2200-3000rpm, thus obtaining the porous gel; washing and drying the porous gel, and ball-milling to 50-200nm to obtain the nano silicon-based mesoporous material.
7. The organic-inorganic hybrid ultrafiltration membrane according to claim 1, wherein the preparation method of the carboxyl quantum dots comprises the following steps:
sequentially adding anhydrous citric acid, L-ascorbic acid and part of NaOH (18-25 w%) solution into a mortar, and grinding for 10-50min to obtain quantum dot slurry; sequentially adding the quantum dot slurry and the rest NaOH solution into a stirring kettle, reacting for 8-12 hours at 50-120rpm and room temperature, dialyzing for 3-5 times by using a dialysis bag, and freeze-drying to obtain the carboxyl quantum dot.
8. An organic-inorganic hybrid ultrafiltration membrane according to claim 7, wherein the mass ratio of the anhydrous citric acid, L-ascorbic acid and NaOH solution (18-25 w%) is 2-5:2-10:3.
9. an organic-inorganic hybrid ultrafiltration membrane according to claim 1, wherein the preparation method of the cellulose solution comprises the steps of:
step 401, pre-soaking nano water hyacinth fibers in deionized water for 4 hours, cooling to 2-6 ℃, then putting the nano water hyacinth fibers into an ultrasonic dispersing machine, carrying out ultrasonic treatment for 10-20 minutes under the condition of 800-1000W, filtering and drying to obtain a cellulose pretreatment substance;
step 402, the cellulose pretreatment obtained in step 401 is treated by NaOH (12-18 w%) solution and urea solution (60-80 w%) according to the mass ratio of 10:3-5:2:4, putting the mixture into a low-temperature water bath kettle, reacting for 0.5-1.5 hours at the temperature of 5-10 ℃, and centrifuging at the speed of 4000rpm to obtain supernatant, thus obtaining the cellulose solution.
10. The method for preparing an organic-inorganic hybrid ultrafiltration membrane according to any one of claims 1 to 9, comprising the steps of:
step 501, putting a film forming substrate, chitosan, a pore-forming agent, a nano silicon-based mesoporous material and a proper amount of absolute ethyl alcohol into a stirring kettle, and stirring and reacting for 10-20 hours under the conditions of water bath at 80 ℃ and 420-800rpm to obtain a film casting solution;
step 502, spreading the casting film liquid obtained in the step 501 in a tray with the length of 50cm, the width of 30cm and the depth of 20cm, and dropwise adding the amphiphilic block copolymer, the carboxyl carbon quantum dots and the cellulose solution in sequence under the conditions of the vibration frequency of 300-600hz, the ambient pressure of 200-300kpa and the temperature of 50-60 ℃ to obtain flux scale inhibition modified casting film liquid;
step 503, cooling the flux scale inhibition modified membrane casting solution obtained in step 502 to 10-30 ℃, placing the membrane casting solution in a vacuum condition of-0.09 Mpa, and standing for 10-12h to obtain a preparation membrane casting solution;
and 504, placing the prepared film casting solution obtained in the step 503 on one side of a glass plate, placing an adjusting scraper on one side of the glass plate close to the prepared film casting solution, starting a film scraping machine, and standing for 30 seconds to obtain the organic-inorganic hybrid ultrafiltration film.
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