CN116785937A - Water purification film and preparation method thereof - Google Patents
Water purification film and preparation method thereof Download PDFInfo
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- CN116785937A CN116785937A CN202210253183.2A CN202210253183A CN116785937A CN 116785937 A CN116785937 A CN 116785937A CN 202210253183 A CN202210253183 A CN 202210253183A CN 116785937 A CN116785937 A CN 116785937A
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- sol
- water purification
- alginate
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- water
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 238000000746 purification Methods 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000012528 membrane Substances 0.000 claims abstract description 45
- 235000010443 alginic acid Nutrition 0.000 claims abstract description 26
- 229920000615 alginic acid Polymers 0.000 claims abstract description 26
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229940072056 alginate Drugs 0.000 claims abstract description 24
- 238000003756 stirring Methods 0.000 claims abstract description 24
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 22
- 108010025899 gelatin film Proteins 0.000 claims abstract description 22
- 150000003242 quaternary ammonium salts Chemical group 0.000 claims abstract description 22
- 239000010865 sewage Substances 0.000 claims abstract description 20
- 239000003607 modifier Substances 0.000 claims abstract description 17
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- 150000001768 cations Chemical class 0.000 claims abstract description 12
- 238000005507 spraying Methods 0.000 claims abstract description 11
- 230000005588 protonation Effects 0.000 claims abstract description 10
- 238000009777 vacuum freeze-drying Methods 0.000 claims abstract description 8
- 229910021642 ultra pure water Inorganic materials 0.000 claims abstract description 7
- 239000012498 ultrapure water Substances 0.000 claims abstract description 7
- 238000004065 wastewater treatment Methods 0.000 claims abstract description 7
- 239000007787 solid Substances 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 16
- 229920002635 polyurethane Polymers 0.000 claims description 13
- 239000004814 polyurethane Substances 0.000 claims description 13
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- JBIROUFYLSSYDX-UHFFFAOYSA-M benzododecinium chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 JBIROUFYLSSYDX-UHFFFAOYSA-M 0.000 claims description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000000975 dye Substances 0.000 description 25
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 22
- 235000010413 sodium alginate Nutrition 0.000 description 22
- 239000000661 sodium alginate Substances 0.000 description 22
- 229940005550 sodium alginate Drugs 0.000 description 22
- 238000000926 separation method Methods 0.000 description 21
- 238000001179 sorption measurement Methods 0.000 description 20
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 18
- 230000000844 anti-bacterial effect Effects 0.000 description 17
- 239000008281 solid sol Substances 0.000 description 16
- 239000000463 material Substances 0.000 description 15
- 239000002351 wastewater Substances 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 125000000129 anionic group Chemical group 0.000 description 12
- 239000003921 oil Substances 0.000 description 12
- 235000019198 oils Nutrition 0.000 description 12
- 239000001110 calcium chloride Substances 0.000 description 10
- 229910001628 calcium chloride Inorganic materials 0.000 description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- 230000001580 bacterial effect Effects 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 238000003760 magnetic stirring Methods 0.000 description 7
- 238000007792 addition Methods 0.000 description 6
- 241000894006 Bacteria Species 0.000 description 5
- 239000003242 anti bacterial agent Substances 0.000 description 5
- 230000003115 biocidal effect Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 206010059866 Drug resistance Diseases 0.000 description 4
- 241000588724 Escherichia coli Species 0.000 description 4
- 241000191967 Staphylococcus aureus Species 0.000 description 4
- 150000001450 anions Chemical class 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 125000002091 cationic group Chemical group 0.000 description 4
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- 230000000845 anti-microbial effect Effects 0.000 description 3
- 229940088710 antibiotic agent Drugs 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000003502 gasoline Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 235000019476 oil-water mixture Nutrition 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- 239000003463 adsorbent Substances 0.000 description 2
- 229960001126 alginic acid Drugs 0.000 description 2
- 239000000783 alginic acid Substances 0.000 description 2
- 150000004781 alginic acids Chemical class 0.000 description 2
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 2
- 229910001626 barium chloride Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000003501 co-culture Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000005189 flocculation Methods 0.000 description 2
- 230000016615 flocculation Effects 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- -1 quaternary ammonium salt compounds Chemical class 0.000 description 2
- 239000001044 red dye Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- 208000035143 Bacterial infection Diseases 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004966 Carbon aerogel Substances 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 206010061218 Inflammation Diseases 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000728 ammonium alginate Substances 0.000 description 1
- 235000010407 ammonium alginate Nutrition 0.000 description 1
- KPGABFJTMYCRHJ-YZOKENDUSA-N ammonium alginate Chemical compound [NH4+].[NH4+].O1[C@@H](C([O-])=O)[C@@H](OC)[C@H](O)[C@H](O)[C@@H]1O[C@@H]1[C@@H](C([O-])=O)O[C@@H](O)[C@@H](O)[C@H]1O KPGABFJTMYCRHJ-YZOKENDUSA-N 0.000 description 1
- 229940124350 antibacterial drug Drugs 0.000 description 1
- 229920002118 antimicrobial polymer Polymers 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 208000022362 bacterial infectious disease Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920002988 biodegradable polymer Polymers 0.000 description 1
- 239000004621 biodegradable polymer Substances 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- WJYHCYBNUJVCEH-UHFFFAOYSA-N cyclohexane;ethoxyethane Chemical compound CCOCC.C1CCCCC1 WJYHCYBNUJVCEH-UHFFFAOYSA-N 0.000 description 1
- 230000002498 deadly effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 239000010840 domestic wastewater Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000004054 inflammatory process Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 244000000010 microbial pathogen Species 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 150000003904 phospholipids Chemical class 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 150000004804 polysaccharides Chemical class 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000010408 potassium alginate Nutrition 0.000 description 1
- 239000000737 potassium alginate Substances 0.000 description 1
- MZYRDLHIWXQJCQ-YZOKENDUSA-L potassium alginate Chemical compound [K+].[K+].O1[C@@H](C([O-])=O)[C@@H](OC)[C@H](O)[C@H](O)[C@@H]1O[C@@H]1[C@@H](C([O-])=O)O[C@@H](O)[C@@H](O)[C@H]1O MZYRDLHIWXQJCQ-YZOKENDUSA-L 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
-
- 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
- B01D61/38—Liquid-membrane separation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/12—Adsorbents being present on the surface of the membranes or in the pores
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/16—Membrane materials having positively charged functional groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/48—Antimicrobial properties
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Analytical Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to a water purification membrane and a preparation method thereof, belonging to the technical field of sewage and wastewater treatment. The invention discloses a preparation method of a water purification membrane, which comprises the following steps: s1, dissolving alginate in ultrapure water to prepare alginate sol, adding an acidulant into the alginate sol to carry out protonation, sequentially adding a modifier and a pore-forming agent, and stirring to obtain modified sol; the modifier is quaternary ammonium salt with cations; s2, spraying the modified sol on the ice surface of the frozen cross-linking agent solution to obtain solid membranous sol; s3, immersing the solid membranous sol into a cross-linking agent solution to obtain a gel film; s4, vacuum freeze-drying the gel film to obtain the water purification film. The invention also discloses a water purification membrane and application thereof in sewage and wastewater treatment.
Description
Technical Field
The invention belongs to the technical field of sewage and wastewater treatment, and relates to a water purification membrane and a preparation method thereof.
Background
With the development of economy and society, the water consumption of various industries has increased dramatically, resulting in an increasing discharge of sewage and wastewater. It is therefore highly desirable to know the source, nature and hazard of sewage and wastewater and to select appropriate treatment methods to improve the quality of the water in the environment. In recent years, researchers at home and abroad have studied more and more treatment methods of sewage and wastewater, and various treatment methods such as adsorption, membrane separation, chemical oxidation, flocculation, electrocatalytic degradation, photocatalytic oxidation, microbial degradation and the like have been proposed.
Oily wastewater is a common pollutant, and the discharge of the oily wastewater seriously threatens the physical health of people. The oil-water separation materials reported in recent years are largely classified into bulk adsorbent materials and membrane materials. The adsorbent materials such as biomass carbon aerogel and polymer foam are mainly suitable for adsorbing floating oil in water, and a great deal of manpower or additional power is required in the process of separating an oil-water mixture. The existing film materials have the following disadvantages: the preparation process is complex, the cost is high, and the water flux is low.
Biological contamination is one of the major threats facing human health, and in the fields of medical devices, drinking water, foods, textiles, etc., if improperly treated, can cause inflammation and even fatal diseases. Various antibiotics have been found and used to prevent bacterial infections, but overuse or even abuse of antibiotics accelerates the drug resistance variation of the strain, resulting in a significant decrease in the susceptibility of multiple resistant strains to most antibiotics. Therefore, it is critical to solve the problem to explore a new and effective antimicrobial material. The use of natural and biodegradable polymers as antibacterial agents to prevent bacterial growth has received considerable attention. Quaternary ammonium salt functionalized antimicrobial polymers are of considerable interest because of the cationic nature of the deadly effect of quaternary ammonium salt compounds on a variety of pathogenic microorganisms.
The anionic dye wastewater has huge discharge in recent years, and is characterized in that most of the anionic dye wastewater contains hydrophilic groups such as sulfonic acid groups, carboxyl groups and the like, has good hydrophilicity, and can be ionized in a solution to exist in an anionic form when being dissolved in water. And most anionic dyes contain azo groups, they are not easily subjected to oxidative catabolism due to the lack of electrons in nature. In the treatment process of anionic dye wastewater, flocculation/adsorption agents are more common at present, and are widely used due to low cost, but the dye adsorption effect is poor. The membrane separation technology is a method for removing macromolecular pollutants through separation membrane separation, thereby realizing purification. The ability to remove contaminants is generally indispensible from the size and surface charge of the pores of the membrane. The membrane separation technology has the advantages of low energy consumption and controllable treatment process; the disadvantage is that the cleaning of membrane contaminations makes the treatment costs high, which makes membrane separation technology impractical for large-scale implementation in the field of sewage and wastewater treatment. There is therefore a need to develop a low cost, efficient membrane material.
Chinese patent application text (publication No. CN 109926026A) discloses a gel film for decoloring ion exchange type printing and dyeing wastewater, which is prepared into a first network polymer skeleton by using natural polysaccharide polymers, a water-soluble cross-linking agent, an oxidant and a reducing agent; the polyvinyl alcohol, the acid polymerizable functional monomer, the graphene oxide, the water-soluble cross-linking agent, the oxidant and the reducing agent are used for preparing a second network polymer skeleton reaction solution, and the second network polymer skeleton reaction solution are mixed and reacted to obtain a finished gel film, so that the adsorption capacity can be improved, but the preparation process is complex, and the raw material cost is high; is unfavorable for mass production.
Disclosure of Invention
The invention aims at solving the problems in the prior art and provides a water purification film and a preparation method thereof, so that the water purification film has the functions of oil-water separation, antibiosis and anion dye adsorption, and is low in cost and high in efficiency.
The aim of the invention can be achieved by the following technical scheme:
a method of preparing a water purification membrane, the method comprising the steps of:
s1, dissolving alginate in ultrapure water to prepare alginate sol, adding an acidulant into the alginate sol to carry out protonation, sequentially adding a modifier and a pore-forming agent, and stirring to obtain modified sol; the modifier is quaternary ammonium salt with cations;
s2, spraying the modified sol on the ice surface of the frozen cross-linking agent solution to obtain solid membranous sol;
s3, immersing the solid membranous sol into a cross-linking agent solution to obtain a gel film;
s4, vacuum freeze-drying the gel film to obtain the water purification film.
The water purification membrane prepared by the invention is modified by mixing the quaternary ammonium salt with cations and the alginate, so that the antibacterial capability of the modified membrane is improved, and the biocompatibility is also improved; then divalent cations and aqueous polyurethane are added to make the membrane positive, so that electrostatic adsorption of anionic dye can be realized; the prepared water purification membrane has a high porous structure and water retention capacity and a large specific surface area; and contains a large number of hydroxyl and carboxyl, has super-hydrophilicity and underwater super-oleophobicity, and can realize oil-water separation. The water purifying film has the functions of oil-water separation, antibiosis and anion dye adsorption.
Preferably, the mass ratio of the alginate to the acidulant to the modifier to the pore-forming agent in the modified sol is 1: (0.01-2): (0.5-5): (0.1-3).
Further preferably, the mass ratio of the alginate to the acidulant is 1: (0.01-1).
Further preferably, the mass ratio of the modifier to the pore-forming agent is 2: (0.5-1.8).
Preferably, the alginate is one or more of sodium alginate, potassium alginate and ammonium alginate.
Further preferred, the concentration of the alginate sol is 0.5-3wt.%.
At the above concentration, the prepared sol has good fluidity and toughness after film formation.
Preferably, the acidulant comprises one or more of hydrochloric acid, sulfuric acid, phosphoric acid and acetic acid.
The acidulant has the advantages of stronger acidity, lower adding cost, high dissociation speed and rapid decrease of pH value.
Further preferably, the pH of the solution after the addition of the acidulant is from 1 to 5.
Preferably, the quaternary ammonium salt having a cation includes one or more of tetrabutylammonium hydroxide, tetrabutylammonium chloride, dodecyldimethylbenzyl ammonium chloride and cetyltrimethylammonium bromide.
Further preferably, the quaternary ammonium salt with a cation is one or more of tetrabutylammonium hydroxide and tetrabutylammonium chloride.
Quaternary ammonium salts are a better antimicrobial component, and the antimicrobial mechanism includes: the cations destroy the cell structure of bacteria through the interaction of electrostatic force and hydrogen bond force with negative charge components (protein and phospholipid) on the cell wall or cell membrane of fungi, thereby achieving the purpose of physical antibiosis. The use of the quaternary ammonium salt compound has little influence on the drug resistance and the sensibility of bacteria; the quaternary ammonium salt antibacterial agent has broad-spectrum antibacterial property, high antibacterial strength, drug resistance, safety and good biocompatibility; environment-friendly and biodegradable; convenient use, good physical and chemical properties, and is simple and easy to obtain. However, although the quaternary ammonium salt has antibacterial property, the quaternary ammonium salt has certain strong oxidizing property, is relatively expensive, has influence on human safety, is used for modifying alginate, has rich source of the alginate and low cost, and can increase the antibacterial capability of the modified membrane and also increase the biocompatibility.
The quaternary ammonium salt is selected not only because the quaternary ammonium salt has an antibacterial effect, but also because the alginate can generate a neutralization reaction with the quaternary ammonium salt after protonation, the electrostatic effect is achieved, and the pore-forming agent is finally cooperated to form positive electricity, so that the quaternary ammonium salt is modified on an alginic acid molecular chain for dye adsorption and antibacterial effect, so that the quaternary ammonium salt has a cationic property, and interacts with negative charge components on bacteria to destroy the bacterial structure.
Preferably, the pore-forming agent is aqueous polyurethane.
Besides pore-forming effect, the aqueous polyurethane can also increase the flexibility and antibacterial property of the film.
Preferably, the cross-linking agent comprises one or more of copper chloride, barium chloride and calcium chloride.
Further preferably, the concentration of the crosslinker solution is 0.5-5wt.%.
Preferably, the protonation process time in step S1 is 0.2-3h.
Short protonation time can result in incomplete acidification, insufficient modification of quaternary ammonium salt, and poor antibacterial and anionic dye adsorption effects; the long protonation time can hydrolyze the alginate molecules, resulting in a decrease in the strength of the modified polymer.
Preferably, the stirring time after the modifier and the pore-forming agent are added in the step S1 is 1-10h.
Further preferably, the modifier is added and stirred for 1 to 6 hours.
Further preferably, the pore-forming agent is added and stirred for 0.5 to 4 hours.
Preferably, the number of spraying times in the step S2 is 40-60.
Preferably, the ice surface of the cross-linking agent solution in the step S2 is frozen by the cross-linking agent solution at the temperature of (-10) - (-30) DEG C.
Preferably, the cross-linking agent in the cross-linking agent solution in the steps S2 and S3 is one or more of copper chloride, barium chloride and calcium chloride.
Preferably, the vacuum freeze-drying temperature in the step S4 is (-60) DEG C- (-90) DEG C, and the drying time is 20-24 hours.
The invention also provides a water purification membrane.
Preferably, the water purification membrane has a surface average pore size of 40 to 60 μm.
Preferably, the thickness of the water purification film is 200-380 μm.
The invention also provides application of the water purification membrane in sewage and wastewater treatment.
The water purification membrane prepared by the invention can treat sewage and wastewater, wherein the sewage and wastewater comprise: oily sewage containing chloroform, cyclohexane, petroleum ether, toluene, gasoline, diesel oil and the like; domestic wastewater in which a variety of bacterial communities and microorganisms exist; a biological wastewater containing bacteria; dye-containing waste water from textile, printing and dyeing and paint industries.
The inventor expands a series of researches on an alginate water purification film, and the invention improves the raw materials and the preparation method based on the prior art, thereby realizing the oil-water separation and simultaneously increasing the functions of antibiosis and anion dye adsorption.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the invention, quaternary ammonium salt, divalent cations of a cross-linking agent and aqueous polyurethane are introduced into the preparation method of the water purification membrane to form electropositivity, so that electrostatic adsorption of anionic dye is realized.
2. In the preparation method of the water purification membrane, the acidulant is added to generate a protonation process, and then the product is modified by the quaternary ammonium salt with cationic property, so that the high-efficiency broad-spectrum antibacterial property and antibacterial drug resistance are realized.
3. The water purification membrane prepared by the invention has hydrophilic underwater super oleophobic property, can realize oil-water separation, and has the separation efficiency of more than 99%.
4. The raw material cost of the water purification membrane is low, the process is mature, and the large-scale production can be realized.
5. The water purification membrane prepared by the invention can realize biodegradation, namely, the membrane can not cause secondary pollution to the environment after being abandoned.
Drawings
FIG. 1 is a scanning electron microscope image of a water purification film prepared in example 1 of the present invention.
FIG. 2 is a graph showing the contact angle of water with oil in the water purification film prepared in example 1 of the present invention.
FIG. 3 is a chart showing the antibacterial circle of the water purification film prepared in example 1 of the present invention against Staphylococcus aureus.
FIG. 4 is a chart showing the antibacterial circle of the water purification film prepared in example 1 of the present invention against Escherichia coli.
FIG. 5 is a graph showing the comparison of the front and rear of the adsorption of the anionic dye Congo red by the water purification film prepared in example 1 of the present invention.
Detailed Description
The following are specific examples of the present invention, and the technical solutions of the present invention are further described, but the present invention is not limited to these examples.
Example 1
1.5g of sodium alginate is dissolved in 100ml of deionized water, magnetic stirring is carried out for 30min, a sodium alginate solution with the concentration of 1.5wt.% is obtained, 0.05g of hydrochloric acid is added into the sodium alginate solution under stirring to acidify carboxyl groups, 1g of tetrabutylammonium hydroxide is added, magnetic stirring is carried out for 4h, and finally 0.5g of aqueous polyurethane is added, and magnetic stirring is carried out for 2h; spraying the obtained modified sol on the ice surface of 2.5wt.% calcium chloride cross-linking agent solution frozen at the temperature of minus 20 ℃ for 50 times to obtain solid sol; immersing the obtained solid sol into a 2.5wt.% calcium chloride solution at 4 ℃ to form a film, and then continuously immersing for 1h to obtain a gel film; the gel film obtained was freeze-dried in vacuo at-70℃for 24 hours to obtain a water purification film. The scanning electron microscope diagram of the prepared water purifying film is shown in figure 1; the water-purifying film prepared is shown in figure 2.
Bacteriostasis test:
the experiment of designing a bacteriostasis zone by taking gram-positive bacteria staphylococcus aureus as a model is carried out, the water purification membrane material prepared in the embodiment 1 is put into co-culture, and after 24 hours of culture at 37 ℃, the experiment result graph is shown in fig. 3, so that the water purification membrane material can be observed to have better bacteriostasis.
The experiment of designing a bacteriostasis zone by taking gram-negative bacteria escherichia coli as a model is carried out, the water purification membrane material prepared in the embodiment 1 is put into co-culture, and after 24 hours of culture at 37 ℃, the experiment result diagram is shown in fig. 4, so that the water purification membrane material can be observed to have better bacteriostasis.
Anionic dye adsorption test:
the congo red dye solution was poured into the water purification film prepared in example 1, and the color comparison chart before and after the dye solution is shown in fig. 5.
Example 2
Dissolving 0.5g of sodium alginate in 100ml of deionized water, magnetically stirring for 30min to obtain sodium alginate sol with the concentration of 0.5wt.%, adding 0.02g of hydrochloric acid into the sodium alginate sol under stirring to acidify carboxyl, adding 2g of tetrabutylammonium chloride, magnetically stirring for 2h, and finally adding 1g of aqueous polyurethane, magnetically stirring for 2h; spraying the obtained modified sol on the ice surface of 2wt.% calcium chloride cross-linking agent solution frozen at the temperature of minus 10 ℃ for 20 times to obtain solid sol; immersing the obtained solid sol into a 2.5wt.% calcium chloride solution at 4 ℃ to form a film, and then continuously immersing for 1h to obtain a gel film; the gel film obtained was freeze-dried in vacuo at-70℃for 24 hours to obtain a water purification film.
Example 3
1.5g of sodium alginate is dissolved in 100ml of deionized water, magnetically stirred for 30min to obtain sodium alginate sol with the concentration of 1.5wt.%, 0.08g of hydrochloric acid is added into the sodium alginate sol to acidify carboxyl, 3g of dodecyl dimethyl benzyl ammonium chloride is added under stirring, magnetically stirred for 5h, and finally 2g of aqueous polyurethane is added to magnetically stir for 1h; spraying the obtained modified sol on the ice surface of 3wt.% calcium chloride cross-linking agent solution frozen at the temperature of minus 25 ℃ for 80 times to obtain solid sol; immersing the obtained solid sol into a calcium chloride solution with the temperature of 2 ℃ and the weight of 1.5 percent, and then continuously immersing for 1 hour to obtain a gel film; and (3) vacuum freeze-drying the obtained gel film at the temperature of-50 ℃ for 24 hours to obtain the water purification film.
Example 4
Dissolving 4g of sodium alginate in 100ml of deionized water, magnetically stirring for 30min to obtain sodium alginate sol with the concentration of 4wt.%, adding 0.08g of hydrochloric acid into the sodium alginate sol under stirring to acidify carboxyl, adding 1.5g of tetrabutylammonium chloride, magnetically stirring for 5h, and finally adding 1.4g of aqueous polyurethane, magnetically stirring for 1h; spraying the obtained modified sol on the ice surface of the frozen calcium chloride cross-linking agent solution at the temperature of minus 20 ℃ for 60 times to obtain solid sol; immersing the obtained solid sol into a 0.5wt.% calcium chloride solution at 4 ℃ to form a film, and then continuously immersing for 2 hours to obtain a gel film; the gel film obtained was freeze-dried in vacuo at-70℃for 24 hours to obtain a water purification film.
Example 5
1.5g of sodium alginate is dissolved in 100ml of deionized water, magnetic stirring is carried out for 30min, sodium alginate sol with the concentration of 1.5wt.% is obtained, 0.05g of hydrochloric acid is added into the sodium alginate sol under stirring to acidify carboxyl, 5g of tetrabutylammonium hydroxide and 3g of tetrabutylammonium chloride are added, magnetic stirring is carried out for 5h, and finally 2g of aqueous polyurethane is added for magnetic stirring for 1h; spraying the obtained modified sol on the ice surface of the frozen calcium chloride cross-linking agent solution at the temperature of minus 20 ℃ for 70 times to obtain solid sol; immersing the obtained solid sol into a 3.5wt.% calcium chloride solution at 4 ℃ to form a film, and then continuously immersing for 2 hours to obtain a gel film; and (3) vacuum freeze-drying the obtained gel film at the temperature of-50 ℃ for 24 hours to obtain the water purification film.
Example 6
Dissolving 2.5g of sodium alginate in 100ml of deionized water, magnetically stirring for 30min to obtain sodium alginate sol with the concentration of 2.5wt.%, adding 0.02g of hydrochloric acid into the sodium alginate sol under stirring to acidify carboxyl, adding 4g of tetrabutylammonium bromide, magnetically stirring for 5h, and finally adding 1.8g of aqueous polyurethane, magnetically stirring for 3h; spraying the obtained modified sol on the ice surface of the frozen calcium chloride cross-linking agent solution at the temperature of minus 20 ℃ for 50 times to obtain solid sol; immersing the obtained solid sol into a calcium chloride solution with the temperature of 3 ℃ and the weight of 1.5 percent, and then continuously immersing for 1 hour to obtain a gel film; and (3) vacuum freeze-drying the obtained gel membrane at the temperature of-80 ℃ for 24 hours to obtain the water purification membrane.
Example 7
Dissolving 2.5g of sodium alginate in 100ml of deionized water, magnetically stirring for 30min to obtain sodium alginate sol with the concentration of 2.5wt.%, adding 5.5g of hydrochloric acid into the sodium alginate sol under stirring to acidify carboxyl, adding 1.5g of tetrabutylammonium chloride, magnetically stirring for 5h, and finally adding 6g of aqueous polyurethane, magnetically stirring for 1h; spraying the obtained modified sol on the ice surface of the frozen calcium chloride cross-linking agent solution at the temperature of minus 20 ℃ for 40 times to obtain solid sol; immersing the obtained solid sol into a 2.5wt.% calcium chloride solution at 4 ℃ to form a film, and then continuously immersing for 2 hours to obtain a gel film; and (3) vacuum freeze-drying the obtained gel membrane at the temperature of-80 ℃ for 24 hours to obtain the water purification membrane.
Application examples 8 to 14
The water purification films prepared in examples 1 to 7 were each prepared into a cup.
And (3) sewage preparation:
preparing first-class sewage: 5g of cyclohexane and 0.5g of nonionic surfactant are added into 100ml of ultrapure water, and the chloroform mixed phase oil-water mixture is obtained by intense magnetic stirring. Preparing second-class sewage: a bacterial suspension was prepared by shaking 50. Mu.L of a solution of 8000. Mu.g/mL of Staphylococcus aureus and Escherichia coli in 50mL of ultrapure water. Preparing third class sewage: 1mg of Congo red was added to 20ml of ultrapure water and a 50mg/L Congo red dye solution was prepared with vigorous shaking.
The three types of sewage were poured into the cups prepared in application examples 8 to 14.
And the oil-water separation efficiency R, the dye removal efficiency AE and the bacteria removal efficiency RP are calculated according to the following formulas, and specific data are shown in Table 1.
Calculation formula (R,%) of oil-water separation efficiency:
wherein C is f And C o The oil concentration in the filtrate and the oil-water mixture, respectively.
Calculation formula of dye removal efficiency (AE,%):
c in the formula a 、C b Dye concentrations before and after adsorption, respectively.
Bacterial removal efficiency (RP,%):
c in the formula a 、C b The bacterial concentrations before and after filtration, respectively.
Comparative example 1
Compared with example 1, the difference is that 1g of alginate is added into 100ml of ultrapure water, the mixture is stirred vigorously by magnetic force for 30min, an acidulant, a modifier and a pore-forming agent are not added, the uniform sol is directly sprayed for 60 times on ice frozen at the temperature of minus 20 ℃ of a calcium chloride cross-linking agent solution, then the obtained solid sol is immersed into a calcium chloride solution with the temperature of 4 ℃ and the weight of 2.5% for film formation, and then the solid sol is further immersed for 2h to obtain a gel film; the gel film obtained was freeze-dried in vacuo at-50℃for 24 hours to give an alginate film. The prepared sewage passes through the membrane material, and the oil-water separation efficiency R, the dye adsorption efficiency AE and the bacterial removal efficiency RP are calculated, and specific data are shown in Table 1.
Table 1, three types of measurement results of removal rate of sewage through water purification film
Table description: r is R 1 、R 2 、R 3 The oil-water separation efficiency is measured repeatedly for three times; AE (AE) 1 、AE 2 、AE 3 The adsorption rate of the anionic dye is measured repeatedly for three times; RP (RP) s And RP (RP) e The removal rates of staphylococcus aureus and escherichia coli, respectively.
From the test results in the above table, it can be seen that: in comparative example 1, since no protonizing modification was performed, the oil-water separation efficiency, the dye adsorption efficiency and the antibacterial rate were low. In the example 4 (11), the addition amount of the modifier is too small, the cationic degree is reduced, and the dye adsorption and the antibacterial efficiency of the modified water purification membrane are slightly reduced; in the embodiment 5 (12), the addition amount of the modifier is excessive, the cationization degree is increased, and the antibacterial efficiency of the modified water purification membrane is slightly increased; in the embodiment 6 (13), the addition amount of the acidulant is too small, the protonation of the alginate is incomplete, the modifier cannot be successfully modified, and the antibacterial efficiency is slightly reduced; in the embodiment 7 (14), the addition amount of the acidulant is excessive, so that alginic acid molecules are broken, and each function of the modified film is reduced; and the ratio of modifier to pore former is smaller, resulting in further degradation of performance.
The prepared water purification film is subjected to underwater oil contact angle test, and the specific test method comprises the following steps: fixing the prepared film material on a glass slide, immersing in water, and then dropwise adding chloroform, petroleum ether, gasoline, cyclohexane and toluene; the underwater oil contact angle test is carried out by using a water contact angle tester, oil drops are dropped at three different positions, the underwater oil contact angle is recorded, the average value is taken, and the underwater oleophobic performance of the separation material is evaluated. Examples 1 to 7 were prepared to obtain the measurement results of underwater oil contact angle of the water purification film having the oil-water separation, antibacterial, anionic dye adsorption functions as shown in Table 2.
Table 2, measurement results of underwater oil contact angle of water purifying film
| Toluene (toluene) | Petroleum ether | Cyclohexane | Chloroform (chloroform) | Gasoline | |
| Example 1 | 154.1° | 155.6° | 153.2° | 155.5° | 154.1° |
| Example 2 | 156.7° | 155.3° | 152.1° | 153.7° | 156.2° |
| Example 3 | 155.1° | 154.3° | 153.2° | 155.6° | 154.9° |
| Example 4 | 154.6° | 155.7° | 153.9° | 156.1° | 155.2° |
| Example 5 | 153.9° | 154.8° | 154.2° | 152.6° | 153.4° |
| Example 6 | 154.6° | 155.6° | 155.2° | 153.9° | 154.5° |
| Example 7 | 155.8° | 154.7° | 153.6° | 154.3° | 156.8° |
As can be seen from Table 2, the contact angles of the water purification films prepared in examples 1-7 on the underwater oil of different oils are all over 150 degrees, the underwater super-oleophobic level is achieved, and the water purification films can be effectively prevented from being polluted by the oils.
In conclusion, the invention realizes oil-water separation, antibiosis and anion dye adsorption simultaneously by modifying the alginate material, quaternary ammonium salt, divalent cations and aqueous polyurethane to form a film; the preparation method is simple and safe; the prepared water purification film can be used for realizing sewage and wastewater treatment.
The specific embodiments described herein are offered by way of example only to illustrate the spirit of the invention. Those skilled in the art may make various modifications or additions to the described embodiments or substitutions thereof without departing from the spirit of the invention or exceeding the scope of the invention as defined in the accompanying claims.
Claims (10)
1. A method for preparing a water purification membrane, comprising the steps of:
s1, dissolving alginate in ultrapure water to prepare alginate sol, adding an acidulant into the alginate sol to carry out protonation, sequentially adding a modifier and a pore-forming agent, and stirring to obtain modified sol; the modifier is quaternary ammonium salt with cations;
s2, spraying the modified sol on the ice surface of the frozen cross-linking agent solution to obtain solid membranous sol;
s3, immersing the solid membranous sol into a cross-linking agent solution to obtain a gel film;
s4, vacuum freeze-drying the gel film to obtain the water purification film.
2. The preparation method according to claim 1, wherein the mass ratio of alginate, acidulant, modifier and pore-forming agent in the modified sol is 1: (0.01-2): (0.5-5): (0.1-3).
3. The preparation method according to claim 1 or 2, wherein the mass ratio of the modifier to the pore-forming agent is 2: (0.5-1.8).
4. The method of claim 1, wherein the acidulant comprises one or more of hydrochloric acid, sulfuric acid, phosphoric acid, and acetic acid.
5. The method of claim 1, wherein the quaternary ammonium salt having a cation comprises one or more of tetrabutylammonium hydroxide, tetrabutylammonium chloride, dodecyldimethylbenzyl ammonium chloride, and cetyltrimethylammonium bromide.
6. The method according to claim 5, wherein the quaternary ammonium salt having a cation is one or more of tetrabutylammonium hydroxide and tetrabutylammonium chloride.
7. The method of claim 1, wherein the pore former is an aqueous polyurethane.
8. The method of claim 1, wherein the protonation process time in step S1 is 0.2-3h.
9. A water purification membrane produced by the production method according to claim 1, wherein the average pore diameter of the surface of the water purification membrane is 40 to 60 μm, and the thickness of the water purification membrane is 200 to 380 μm.
10. Use of a water purification membrane according to claim 9 in sewage, wastewater treatment.
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