CN114053881B - Preparation method of hydrogel filtering membrane for efficiently loading and catalyzing organic pollutants - Google Patents
Preparation method of hydrogel filtering membrane for efficiently loading and catalyzing organic pollutants Download PDFInfo
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- 239000000017 hydrogel Substances 0.000 title claims abstract description 32
- 238000001914 filtration Methods 0.000 title claims abstract description 31
- 239000012528 membrane Substances 0.000 title claims abstract description 27
- 239000002957 persistent organic pollutant Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000011068 loading method Methods 0.000 title claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 74
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 47
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910052621 halloysite Inorganic materials 0.000 claims abstract description 44
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 36
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 36
- 239000007864 aqueous solution Substances 0.000 claims abstract description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000243 solution Substances 0.000 claims abstract description 21
- 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 claims abstract description 20
- 235000010413 sodium alginate Nutrition 0.000 claims abstract description 20
- 229940005550 sodium alginate Drugs 0.000 claims abstract description 20
- 239000000661 sodium alginate Substances 0.000 claims abstract description 20
- 238000005266 casting Methods 0.000 claims abstract description 16
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 14
- 230000003197 catalytic effect Effects 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 9
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims abstract description 8
- 230000001276 controlling effect Effects 0.000 claims abstract description 8
- 238000004132 cross linking Methods 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 230000001105 regulatory effect Effects 0.000 claims abstract description 8
- 238000007790 scraping Methods 0.000 claims abstract description 8
- 238000002791 soaking Methods 0.000 claims abstract description 8
- 238000000967 suction filtration Methods 0.000 claims abstract description 8
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 6
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 6
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 239000011521 glass Substances 0.000 claims description 24
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 18
- 229910001447 ferric ion Inorganic materials 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 125000005613 guluronic acid group Chemical group 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 12
- 239000002071 nanotube Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- -1 lanthanum ions Chemical class 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 9
- 230000001112 coagulating effect Effects 0.000 claims description 7
- 238000002386 leaching Methods 0.000 claims description 7
- 238000001179 sorption measurement Methods 0.000 claims description 7
- 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 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 230000007062 hydrolysis Effects 0.000 claims description 6
- 238000006460 hydrolysis reaction Methods 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000005345 coagulation Methods 0.000 claims description 5
- 230000015271 coagulation Effects 0.000 claims description 5
- 239000003638 chemical reducing agent Substances 0.000 claims description 4
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 3
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 229930003268 Vitamin C Natural products 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 229910001422 barium ion Inorganic materials 0.000 claims description 3
- 229910001424 calcium ion Inorganic materials 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 235000019154 vitamin C Nutrition 0.000 claims description 3
- 239000011718 vitamin C Substances 0.000 claims description 3
- 238000004042 decolorization Methods 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 230000003115 biocidal effect Effects 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 5
- 229920005597 polymer membrane Polymers 0.000 abstract description 5
- 239000002245 particle Substances 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000010865 sewage Substances 0.000 abstract description 3
- 239000007788 liquid Substances 0.000 abstract description 2
- 230000007935 neutral effect Effects 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000003911 water pollution Methods 0.000 description 2
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- CZMAIROVPAYCMU-UHFFFAOYSA-N lanthanum(3+) Chemical compound [La+3] CZMAIROVPAYCMU-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 1
- 229940012189 methyl orange Drugs 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000001048 orange dye Substances 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/08—Polysaccharides
-
- 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
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
- B01J35/59—Membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
-
- 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
- B01D2323/00—Details relating to membrane preparation
- B01D2323/30—Cross-linking
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/343—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the pharmaceutical industry, e.g. containing antibiotics
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- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
Aiming at the problems that the finger-shaped holes of the traditional polymer membrane cause low catalytic efficiency, zero-valent iron is easy to oxidize and catalyst in the hydrogel is easy to run off, the invention reports a preparation method of the hydrogel filtering membrane for catalyzing organic pollutants with high-efficiency load. Firstly, mixing and dispersing purified halloysite and ferric chloride aqueous solution, then adding tetraethoxysilane, regulating and controlling pH value to hydrolyze the tetraethoxysilane to obtain silicon dioxide, then dropwise adding sodium borohydride solution to generate a halloysite/silicon dioxide dispersion liquid loaded with zero-valent iron, washing with ethanol to remove unreacted substances, and carrying out suction filtration and drying to obtain halloysite/silicon dioxide particles loaded with zero-valent iron. Dispersing halloysite/silicon dioxide particles loaded with zero-valent iron into sodium alginate aqueous solution to obtain casting solution, scraping the casting solution into a film, soaking the film into metal ion aqueous solution for crosslinking, and thus obtaining the hydrogel filtering film with high-efficiency load catalytic organic pollutants. The membrane has wide application prospect in the field of sewage treatment and environmental protection.
Description
Technical Field
The invention relates to a preparation method of a hydrogel filtering membrane for efficiently loading and catalyzing organic pollutants, belonging to the field of functional materials and membrane separation.
The invention relates to the technical fields of zero-valent iron preparation and loading, a filtering membrane, hydrogel and the like. In particular to a preparation method of a hydrogel filtering membrane for efficiently loading and catalyzing organic pollutants.
Background
Water resources are one of the most important material resources indispensable to human survival and development. However, with the continuous development of industry, water pollution is also becoming serious. Organic waste is a main aspect of water pollution, and organic pollutants in water are various in variety, complex in composition and toxic, and have great harm to the environment and human bodies. The traditional wastewater treatment methods comprise a physical adsorption method, a chemical method, a biological method, an electrochemical method and the like, but the treatment difficulty of the organic wastewater which is difficult to degrade is great at present, and the requirements of higher and higher environmental protection and technology are not met. Therefore, there is no way to seek efficient and cost effective treatment of organic pollutants.
Because of the characteristics of strong reducing capability, large specific surface area and the like, the zero-valent iron can effectively remove organic pollutants, and the zero-valent iron is loaded in carriers such as a polymer film and the like, so that the catalytic activity of the zero-valent iron can be enhanced. Sikhwivhilu Keneiloe et al graft polymerized acrylic acid or acrylic acid in situ polymerization onto PVDF membranes. The Fe/Ni bimetallic nanoparticles were then immobilized on PVDF membrane. The catalytic degradation performance of the nanocomposite film on methyl orange dye under acidic and neutral conditions was studied. The nano composite film prepared by in-situ polymerization has higher catalytic activity under both acidic and neutral conditions and lower metal leaching rate under neutral conditions, which is attributed to the uniform dispersion of the metal obtained by the method. The membrane can be used to treat neutral pH water containing organic contaminants.
However, the finger-shaped holes of the traditional polymer membrane can cause the problems of low catalytic efficiency, easy oxidation of zero-valent iron, easy loss of catalyst and the like. The polymer gel is a multi-element system composed of a polymer three-dimensional network and a solvent, the hydrogel film is a homogeneous film, has no finger-shaped holes, and can be used as an effective carrier to load zero-valent iron. Liu et al synthesized FeNPs-CaAlg hydrogel films. The result shows that the FeNPs-CaAlg membrane has good filtering performance on dye, the filtering flux is basically the same as that of pure water, and the filtering flux is hardly reduced with the filtering time. The initial removal rate of the FeNPs-CaAlg composite film on crystal violet can reach 96.4 percent. After 3 hours of filtration, the removal rate can still reach 78.4%.
Aiming at the problems that the finger-shaped holes of the traditional polymer membrane cause low catalytic efficiency, zero-valent iron is easy to oxidize and catalyst in the hydrogel is easy to run off, the invention reports a preparation method of the hydrogel filtering membrane for catalyzing organic pollutants with high-efficiency load. Firstly, mixing and dispersing purified halloysite and ferric chloride aqueous solution, then adding tetraethoxysilane, regulating and controlling pH value to hydrolyze the tetraethoxysilane to obtain silicon dioxide, then dropwise adding sodium borohydride solution to generate a halloysite/silicon dioxide dispersion liquid loaded with zero-valent iron, washing with ethanol to remove unreacted substances, and carrying out suction filtration and drying to obtain halloysite/silicon dioxide particles loaded with zero-valent iron. Dispersing halloysite/silicon dioxide particles loaded with zero-valent iron into sodium alginate aqueous solution to obtain casting solution, scraping the casting solution into a film, soaking the film into metal ion aqueous solution for crosslinking, and thus obtaining the hydrogel filtering film with high-efficiency load catalytic organic pollutants. The membrane has wide application prospect in the field of sewage treatment and environmental protection.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to solve the technical problems that the catalytic efficiency is low, zero-valent iron is easy to oxidize, the catalyst in the hydrogel is easy to run off and the like caused by finger-shaped holes of the traditional polymer membrane.
The invention solves the problems of low catalytic efficiency, easy oxidation of zero-valent iron, easy loss of catalyst in hydrogel and the like caused by finger-shaped holes of the traditional polymer membrane, and provides a preparation method of a hydrogel filtering membrane for efficiently loading and catalyzing organic pollutants.
The invention provides a preparation method of a hydrogel filtering membrane for catalyzing organic pollutants with high-efficiency load, which is characterized by comprising the following steps:
a) Firstly, purifying halloysite by using a hydrochloric acid leaching method, uniformly dispersing the purified halloysite in a mixed solution of ethanol and water, adding an aqueous solution of ferric chloride, and fully adsorbing ferric ions on the surface of the halloysite under stirring; then adding ethyl orthosilicate into the mixed solution, regulating the pH value to hydrolyze the ethyl orthosilicate, and generating a layer of silicon dioxide on the surface of halloysite adsorbing ferric ions; then dropwise adding the prepared aqueous solution of the reducing agent to excessive amount, and fully reducing ferric ions into zero-valent iron under the condition of fully stirring and mixing; then washing with ethanol to remove unreacted substances, and carrying out suction filtration and drying under the protection of nitrogen to obtain the zero-valent iron loaded halloysite nanotube coated with silicon dioxide;
b) Ultrasonically dispersing the zero-valent iron-loaded halloysite nanotube coated with the silicon dioxide obtained in the step a) into deionized water, then selecting sodium alginate with the guluronic acid chain segment content of 50% -80%, preparing a mixture aqueous solution with the mass percentage concentration of 0.1% -5% of the sodium alginate as a casting solution, and defoaming for later use;
c) Preparing a metal ion aqueous solution as a coagulation bath;
d) Pouring the casting solution obtained in the step b) after standing and defoaming on a clean glass plate, scraping the glass plate with glass rods with copper wires wound at the two ends and with diameters of 50-1000 mu m, immediately soaking the glass plate and the scraped film in the coagulating bath obtained in the step c) for ionic crosslinking, taking out the film, washing unreacted ions with deionized water, and obtaining a hydrogel filtering film with high-efficiency load for catalyzing organic pollutants;
e) The loading amount of iron ions is controlled by changing the concentration and the adsorption time of the ferric trichloride aqueous solution, and the zero-valent iron stability of the coated silicon dioxide is improved by controlling the concentration of tetraethoxysilane and the amount of the generated silicon dioxide through hydrolysis regulation; the hydrogel filtering membrane obtained by selecting sodium alginate with high guluronic acid chain segment content has better strength and stability.
The reducing agent is any one or two or more of sodium borohydride, potassium borohydride and vitamin C, and the metal ions are any one or two or more of calcium ions, barium ions, lanthanum ions and aluminum ions.
The membrane obtained by the preparation method has wide application prospect in sewage treatment, dye decolorization, antibiotics and other organic pollutants removal.
Detailed Description
Specific embodiments of the present invention are described below, but the present invention is not limited by the embodiments.
Example 1.
a) Firstly, purifying halloysite by using a hydrochloric acid leaching method, uniformly dispersing the purified halloysite in a mixed solution of ethanol and water, adding an aqueous solution of ferric chloride, and fully adsorbing ferric ions on the surface of the halloysite under stirring; then adding ethyl orthosilicate into the mixed solution, regulating the pH value to hydrolyze the ethyl orthosilicate, and generating a layer of silicon dioxide on the surface of halloysite adsorbing ferric ions; then dropwise adding the prepared sodium borohydride aqueous solution to an excessive amount, and fully reducing ferric ions into zero-valent iron under the condition of fully stirring and mixing; then washing with ethanol to remove unreacted substances, and carrying out suction filtration and drying under the protection of nitrogen to obtain the zero-valent iron loaded halloysite nanotube coated with silicon dioxide;
b) Ultrasonically dispersing the zero-valent iron-loaded halloysite nanotube coated with the silicon dioxide obtained in the step a) into deionized water, then selecting sodium alginate with the guluronic acid chain segment content of 50%, preparing a mixture aqueous solution with the mass percent concentration of 2% of sodium alginate as a casting solution, and defoaming for later use;
c) Preparing a calcium ion aqueous solution as a coagulation bath;
d) Pouring the casting solution obtained in the step b) after standing and defoaming on a clean glass plate, scraping the glass plate with glass rods with both ends wound with copper wires with the diameter of 100 mu m, immediately soaking the glass plate and the scraped film in the coagulation bath obtained in the step c) for ionic crosslinking, taking out the film, washing out unreacted ions with deionized water, and obtaining a hydrogel filtering film with high-efficiency load for catalyzing organic pollutants;
e) The loading amount of iron ions is controlled by changing the concentration and the adsorption time of the ferric trichloride aqueous solution, and the zero-valent iron stability of the coated silicon dioxide is improved by controlling the concentration of tetraethoxysilane and the amount of the generated silicon dioxide through hydrolysis regulation; the hydrogel filtering membrane obtained by selecting sodium alginate with high guluronic acid chain segment content has better strength and stability.
Example 2.
a) Firstly, purifying halloysite by using a hydrochloric acid leaching method, uniformly dispersing the purified halloysite in a mixed solution of ethanol and water, adding an aqueous solution of ferric chloride, and fully adsorbing ferric ions on the surface of the halloysite under stirring; then adding ethyl orthosilicate into the mixed solution, regulating the pH value to hydrolyze the ethyl orthosilicate, and generating a layer of silicon dioxide on the surface of halloysite adsorbing ferric ions; then dropwise adding the prepared potassium borohydride aqueous solution to an excessive amount, and fully reducing ferric ions into zero-valent iron under the condition of fully stirring and mixing; then washing with ethanol to remove unreacted substances, and carrying out suction filtration and drying under the protection of nitrogen to obtain the zero-valent iron loaded halloysite nanotube coated with silicon dioxide;
b) Ultrasonically dispersing the zero-valent iron-loaded halloysite nanotube coated with the silicon dioxide obtained in the step a) into deionized water, then selecting sodium alginate with 60% of guluronic acid chain segment content, preparing a mixture aqueous solution with 3% of sodium alginate by mass percentage concentration as a casting solution, and defoaming for later use;
c) Preparing barium ion water solution as coagulating bath;
d) Pouring the casting solution obtained in the step b) after standing and defoaming on a clean glass plate, scraping the glass plate with a glass rod with two ends wound with copper wires with the diameter of 300 mu m, immediately soaking the glass plate and the scraped film in the coagulating bath obtained in the step c) for ionic crosslinking, taking out the film, washing unreacted ions with deionized water, and obtaining a hydrogel filtering film with high-efficiency load for catalyzing organic pollutants;
e) The loading amount of iron ions is controlled by changing the concentration and the adsorption time of the ferric trichloride aqueous solution, and the zero-valent iron stability of the coated silicon dioxide is improved by controlling the concentration of tetraethoxysilane and the amount of the generated silicon dioxide through hydrolysis regulation; the hydrogel filtering membrane obtained by selecting sodium alginate with high guluronic acid chain segment content has better strength and stability.
Example 3.
a) Firstly, purifying halloysite by using a hydrochloric acid leaching method, uniformly dispersing the purified halloysite in a mixed solution of ethanol and water, adding an aqueous solution of ferric chloride, and fully adsorbing ferric ions on the surface of the halloysite under stirring; then adding ethyl orthosilicate into the mixed solution, regulating the pH value to hydrolyze the ethyl orthosilicate, and generating a layer of silicon dioxide on the surface of halloysite adsorbing ferric ions; then dropwise adding the prepared vitamin C aqueous solution to an excessive amount, and fully reducing ferric ions into zero-valent iron under the condition of fully stirring and mixing; then washing with ethanol to remove unreacted substances, and carrying out suction filtration and drying under the protection of nitrogen to obtain the zero-valent iron loaded halloysite nanotube coated with silicon dioxide;
b) Ultrasonically dispersing the zero-valent iron-loaded halloysite nanotube coated with the silicon dioxide obtained in the step a) into deionized water, then selecting sodium alginate with the content of guluronic acid chain segments of 70%, preparing a mixture aqueous solution with the mass percent concentration of 4% of sodium alginate as a casting solution, and defoaming for later use;
c) Preparing lanthanum ion water solution as coagulating bath;
d) Pouring the casting solution obtained in the step b) after standing and defoaming on a clean glass plate, scraping the glass plate with a glass rod with two ends wound with copper wires with the diameter of 500 mu m, immediately soaking the glass plate and the scraped film in the coagulating bath obtained in the step c) for ionic crosslinking, taking out the film, washing unreacted ions with deionized water, and obtaining a hydrogel filtering film with high-efficiency load for catalyzing organic pollutants;
e) The loading amount of iron ions is controlled by changing the concentration and the adsorption time of the ferric trichloride aqueous solution, and the zero-valent iron stability of the coated silicon dioxide is improved by controlling the concentration of tetraethoxysilane and the amount of the generated silicon dioxide through hydrolysis regulation; the hydrogel filtering membrane obtained by selecting sodium alginate with high guluronic acid chain segment content has better strength and stability.
Example 4.
a) Firstly, purifying halloysite by using a hydrochloric acid leaching method, uniformly dispersing the purified halloysite in a mixed solution of ethanol and water, adding an aqueous solution of ferric chloride, and fully adsorbing ferric ions on the surface of the halloysite under stirring; then adding ethyl orthosilicate into the mixed solution, regulating the pH value to hydrolyze the ethyl orthosilicate, and generating a layer of silicon dioxide on the surface of halloysite adsorbing ferric ions; then dropwise adding the prepared sodium borohydride aqueous solution to an excessive amount, and fully reducing ferric ions into zero-valent iron under the condition of fully stirring and mixing; then washing with ethanol to remove unreacted substances, and carrying out suction filtration and drying under the protection of nitrogen to obtain the zero-valent iron loaded halloysite nanotube coated with silicon dioxide;
b) Ultrasonically dispersing the zero-valent iron-loaded halloysite nanotube coated with the silicon dioxide obtained in the step a) into deionized water, then selecting sodium alginate with the guluronic acid chain segment content of 80%, preparing a mixture aqueous solution with the mass percent concentration of 1% of the sodium alginate as a casting solution, and defoaming for later use;
c) Preparing an aluminum ion aqueous solution as a coagulation bath;
d) Pouring the casting solution obtained in the step b) after standing and defoaming on a clean glass plate, scraping the glass plate with a glass rod with two ends wound with copper wires with the diameter of 600 mu m, immediately soaking the glass plate and the scraped film in the coagulating bath obtained in the step c) for ionic crosslinking, taking out the film, washing unreacted ions with deionized water, and obtaining a hydrogel filtering film with high-efficiency load for catalyzing organic pollutants;
e) The loading amount of iron ions is controlled by changing the concentration and the adsorption time of the ferric trichloride aqueous solution, and the zero-valent iron stability of the coated silicon dioxide is improved by controlling the concentration of tetraethoxysilane and the amount of the generated silicon dioxide through hydrolysis regulation; the hydrogel filtering membrane obtained by selecting sodium alginate with high guluronic acid chain segment content has better strength and stability.
Claims (3)
1. The preparation method of the hydrogel filtering membrane for catalyzing organic pollutants with high-efficiency load is characterized by comprising the following steps of:
a) Firstly, purifying halloysite by using a hydrochloric acid leaching method, uniformly dispersing the purified halloysite in a mixed solution of ethanol and water, adding an aqueous solution of ferric chloride, and fully adsorbing ferric ions on the surface of the halloysite under stirring; then adding ethyl orthosilicate into the mixed solution, regulating the pH value to hydrolyze the ethyl orthosilicate, and generating a layer of silicon dioxide on the surface of halloysite adsorbing ferric ions; the prepared aqueous reducing agent solution is then added dropwise to an excess,
reducing ferric ions into zero-valent iron under the condition of fully stirring and mixing; then washing with ethanol to remove unreacted substances, and carrying out suction filtration and drying under the protection of nitrogen to obtain the zero-valent iron loaded halloysite nanotube coated with silicon dioxide;
b) Ultrasonically dispersing the zero-valent iron-loaded halloysite nanotube coated with the silicon dioxide obtained in the step a) into deionized water, then selecting sodium alginate with the guluronic acid chain segment content of 50% -80%, preparing a mixture aqueous solution with the mass percentage concentration of 0.1% -5% of the sodium alginate as a casting solution, and defoaming for later use;
c) Preparing a metal ion aqueous solution as a coagulation bath; the metal ions are any one or a mixture of two or more of calcium ions, barium ions, lanthanum ions and aluminum ions;
d) Pouring the casting solution obtained in the step b) after standing and defoaming on a clean glass plate, scraping the glass plate with glass rods with copper wires wound at the two ends and with diameters of 50-1000 mu m, immediately soaking the glass plate and the scraped film in the coagulating bath obtained in the step c) for ionic crosslinking, taking out the film, washing unreacted ions with deionized water, and obtaining a hydrogel filtering film with high-efficiency load for catalyzing organic pollutants;
e) The loading amount of iron ions is controlled by changing the concentration and the adsorption time of the ferric trichloride aqueous solution, and the zero-valent iron stability of the coated silicon dioxide is improved by controlling the concentration of tetraethoxysilane and the amount of the generated silicon dioxide through hydrolysis regulation; the hydrogel filtering membrane obtained by selecting sodium alginate with high guluronic acid chain segment content has better strength and stability.
2. The method for preparing a hydrogel filtering membrane for catalyzing organic pollutants with high-efficiency load as claimed in claim 1, wherein the reducing agent is any one or a mixture of two or more of sodium borohydride, potassium borohydride and vitamin C.
3. The use of a membrane obtained by the method for preparing a hydrogel filtration membrane for high-efficiency loading catalytic organic pollutants according to claim 1 in oil-water separation, dye decolorization and antibiotic removal.
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| CN109260970A (en) * | 2018-11-19 | 2019-01-25 | 天津工业大学 | A kind of preparation method of high-intensity inorganic doping calcium alginate hydrogel filter membrane |
| CN111111607A (en) * | 2018-10-31 | 2020-05-08 | 中国地质大学（北京） | Preparation method and application of modified kaolinite and nano zero-valent iron/modified kaolinite composite material |
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| CN104759635A (en) * | 2015-03-12 | 2015-07-08 | 中国科学院福建物质结构研究所 | Preparation method of load type nanometer zero-valent iron composite material |
| CN111111607A (en) * | 2018-10-31 | 2020-05-08 | 中国地质大学（北京） | Preparation method and application of modified kaolinite and nano zero-valent iron/modified kaolinite composite material |
| CN109260970A (en) * | 2018-11-19 | 2019-01-25 | 天津工业大学 | A kind of preparation method of high-intensity inorganic doping calcium alginate hydrogel filter membrane |
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