CN112516974A - Water treatment nano-material composite membrane - Google Patents
Water treatment nano-material composite membrane Download PDFInfo
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- CN112516974A CN112516974A CN202011113184.4A CN202011113184A CN112516974A CN 112516974 A CN112516974 A CN 112516974A CN 202011113184 A CN202011113184 A CN 202011113184A CN 112516974 A CN112516974 A CN 112516974A
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 239000002131 composite material Substances 0.000 title claims abstract description 67
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 64
- 239000012528 membrane Substances 0.000 title claims abstract description 39
- 238000002156 mixing Methods 0.000 claims abstract description 103
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 72
- 229920001503 Glucan Polymers 0.000 claims abstract description 49
- 238000001035 drying Methods 0.000 claims abstract description 37
- 238000001914 filtration Methods 0.000 claims abstract description 34
- 239000011521 glass Substances 0.000 claims abstract description 31
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 27
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 27
- 239000002033 PVDF binder Substances 0.000 claims abstract description 17
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 17
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 17
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 17
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 17
- 229920002518 Polyallylamine hydrochloride Polymers 0.000 claims abstract description 16
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 9
- MLIWQXBKMZNZNF-KUHOPJCQSA-N (2e)-2,6-bis[(4-azidophenyl)methylidene]-4-methylcyclohexan-1-one Chemical compound O=C1\C(=C\C=2C=CC(=CC=2)N=[N+]=[N-])CC(C)CC1=CC1=CC=C(N=[N+]=[N-])C=C1 MLIWQXBKMZNZNF-KUHOPJCQSA-N 0.000 claims abstract description 8
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 8
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229920002125 Sokalan® Polymers 0.000 claims abstract description 7
- 239000004584 polyacrylic acid Substances 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims description 68
- 239000006185 dispersion Substances 0.000 claims description 35
- 239000000243 solution Substances 0.000 claims description 35
- 239000007788 liquid Substances 0.000 claims description 31
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 28
- 239000011259 mixed solution Substances 0.000 claims description 28
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 22
- 238000002360 preparation method Methods 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 12
- 229960001701 chloroform Drugs 0.000 claims description 12
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 10
- 229920002307 Dextran Polymers 0.000 claims description 10
- 238000004458 analytical method Methods 0.000 claims description 9
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 7
- 238000007790 scraping Methods 0.000 claims description 7
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims description 5
- 229910001626 barium chloride Inorganic materials 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 5
- 235000011152 sodium sulphate Nutrition 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 4
- 238000000034 method Methods 0.000 abstract description 10
- 229910021645 metal ion Inorganic materials 0.000 abstract description 7
- 239000010865 sewage Substances 0.000 abstract description 7
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 15
- 229910001385 heavy metal Inorganic materials 0.000 description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 8
- 238000005457 optimization Methods 0.000 description 7
- 238000001179 sorption measurement Methods 0.000 description 7
- 239000000654 additive Substances 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 6
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000001699 photocatalysis Effects 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- 125000003172 aldehyde group Chemical group 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 150000004753 Schiff bases Chemical group 0.000 description 1
- 239000004113 Sepiolite Substances 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- -1 ammonium ions Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000012826 global research Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229920002521 macromolecule Polymers 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
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 238000011197 physicochemical method Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 235000019355 sepiolite Nutrition 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 229910052902 vermiculite Inorganic materials 0.000 description 1
- 239000010455 vermiculite Substances 0.000 description 1
- 235000019354 vermiculite Nutrition 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
-
- 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
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
-
- 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
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- 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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/10—Catalysts being present on the surface of the membrane or in the pores
-
- 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
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- Materials Engineering (AREA)
- Water Supply & Treatment (AREA)
- Environmental & Geological Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Carbon And Carbon Compounds (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a water treatment nano-material composite membrane, and belongs to the technical field of sewage treatment. The method comprises the steps of oxidizing glucan with potassium periodate to obtain oxidized glucan, treating carbon nanotubes with polyacrylic acid and diethylenetriamine to obtain modified carbon nanotubes, mixing oxidized glucan with polyallylamine hydrochloride and modified carbon nanotubes for reaction to obtain microgel, mixing the microgel with tetrabutyl titanate, hydrolyzing, filtering to obtain modified microgel, mixing the modified microgel with polyvinylidene fluoride and polyvinylpyrrolidone to obtain a film forming solution, forming the film on a glass plate, uncovering the film, washing, and drying to obtain the water-treated nano material composite film. The water treatment nano material composite membrane prepared by the invention has good treatment capacity on water polluted by metal ions and organic matters.
Description
Technical Field
The invention relates to the technical field of sewage treatment, in particular to a water treatment nano-material composite membrane.
Background
With the development of industry, heavy metal pollution is more serious, the heavy metal wastewater pollution can have profound influence on the environment through the spread of food chain, and the heavy metal wastewater pollution is gradually the subject of global research. At present, the following two basic approaches are adopted for restoring and treating heavy metal pollution of water bodies: firstly, the bioavailability and the migration capacity of heavy metals in a water body are reduced; secondly, the heavy metals are thoroughly removed from the polluted water body, and the following three types are mainly adopted: chemical, physicochemical, and biological methods.
In heavy metal sewage treatment, the adsorption method in the physical method is the most common technical method, and mainly uses porous solid substances to adsorb pollutants in water to treat the wastewater. The traditional adsorbents comprise activated carbon, zeolite, vermiculite, sepiolite, diatom ooze, ceramsite and the like, wherein the ceramsite is a cheaper product for wastewater treatment, the conventional research ceramsite is generally prepared by adopting a sintering method and a baking-free method, but cannot meet the requirement of high-efficiency environment-friendly development, and particularly, the research on the phosphogypsum product for adsorbing heavy metal ions is paid attention by researchers because the soluble impurities in the phosphogypsum product are high in content and poor in overall performance.
In the prior art, the surface of a phosphogypsum product for heavy metal sewage adsorption treatment has the problems of surface pulverization due to high content of soluble impurities in the phosphogypsum, particularly high content of sodium, further reducing the strength and toughness of a phosphogypsum composite film product, further causing poor quality of the phosphogypsum product, poor weather resistance and corrosion resistance of the product, short service life and the like.
The traditional sewage treatment method has the problems of high cost, low efficiency, secondary pollution and the like. Researches show that the photocatalytic semiconductor nano oxide can degrade various pollutants by using ultraviolet rays, can oxidize and decompose hydrocarbons, surfactants, organic dyes, nitrogen-containing organic matters, organophosphorus insecticides, wood preservatives and the like in water, and can be used for sewage treatment. When the composite membrane prepared by the powder photocatalytic oxide is used for sewage treatment, the problems that the powder is difficult to recover, the light transmittance is influenced by the suspended powder and the like exist; therefore, in recent years, titanium dioxide films are frequently used for photocatalysis, but the problems of small contact area, low catalytic efficiency, short film service life and the like caused by the agglomeration of nano titanium dioxide exist.
Disclosure of Invention
The invention aims to provide a water treatment nano material composite membrane and a preparation method thereof, which aim to solve the problems in the prior art.
In order to achieve the purpose, the invention provides the following technical scheme:
the water treatment nano material composite membrane is characterized by mainly comprising the following raw material components in parts by weight: 40-70 parts of polyvinylidene fluoride, 4-10 parts of polyvinylpyrrolidone and 5-12 parts of nano titanium dioxide.
The water treatment nano material composite membrane is characterized by also comprising the following raw material components in parts by weight: 10-20 parts of microgel.
Preferably, the microgel is prepared from polyallylamine hydrochloride, modified carbon nanotubes and oxidized glucan; the oxidized glucan is prepared by treating glucan with potassium periodate; the modified carbon nano tube is prepared by modifying the carbon nano tube by polyacrylic acid and diethylenetriamine.
As optimization, the water treatment nano-material composite membrane mainly comprises the following raw material components in parts by weight: 65 parts of polyvinylidene fluoride, 8 parts of polyvinylpyrrolidone, 8 parts of nano titanium dioxide and 12 parts of microgel.
As optimization, the preparation method of the water treatment nano material composite membrane mainly comprises the following preparation steps:
(1) reacting glucan with potassium periodate, purifying to prepare oxidized glucan, and reacting the oxidized glucan with polyallylamine hydrochloride and modified carbon nanotubes to prepare microgel;
(2) mixing the microgel obtained in the step (1) with tetrabutyl titanate, adding trichloromethane and dilute nitric acid, stirring for reaction, filtering, and drying to obtain modified microgel;
(3) mixing the modified microgel obtained in the step (2) with a dimethylacetamide solution, adding polyvinylidene fluoride and polyvinylpyrrolidone, and stirring and mixing to obtain a film forming solution;
(4) coating the film-forming solution obtained in the step (3) on a glass plate by a scraper, immersing the glass plate in a gel bath, standing, taking out the glass plate, uncovering the film, washing and drying to obtain a water-treated nano material composite film;
(5) and (4) performing index analysis on the water treatment nano material composite membrane obtained in the step (4).
As optimization, the preparation method of the water treatment nano material composite membrane mainly comprises the following preparation steps:
(1) mixing glucan and water according to a mass ratio of 1: 25, adding potassium periodate with the mass of 0.9 time that of the glucan, stirring and reacting under the nitrogen atmosphere to obtain oxidized glucan mixed liquor, mixing the oxidized glucan mixed liquor with a barium chloride solution with the mass fraction of 15% according to the mass ratio of 1: 1.5, stirring, reacting, filtering, removing precipitate to obtain a pretreated oxidized glucan mixed solution, mixing the pretreated oxidized glucan mixed solution with a sodium sulfate solution with the mass fraction of 15% according to a mass ratio of 1: 1.6, stirring, reacting, filtering to obtain oxidized dextran dispersion, mixing polyallylamine hydrochloride and water according to a mass ratio of 1: 180, adding modified carbon nanotubes with the mass 1-2 times that of the polyallylamine hydrochloride, stirring and dispersing, adjusting the pH to 9.8 to obtain a mixed dispersion liquid, and mixing the mixed dispersion liquid with the oxidized glucan dispersion liquid according to the volume ratio of 1: 1, mixing, controlling the adding rate of oxidized glucan dispersion liquid to be 5-8 mL/min, stirring and reacting under the nitrogen atmosphere, and performing suction filtration and drying to obtain microgel;
(2) mixing the microgel obtained in the step (1) and trichloromethane according to a mass ratio of 1: 20, adding tetrabutyl titanate with the mass being 2-4 times that of the microgel, stirring and mixing to obtain a microgel mixed solution, mixing the microgel mixed solution with 10% nitric acid according to the mass ratio of 8:1, stirring and hydrolyzing, filtering, and drying to obtain modified microgel;
(3) mixing the modified microgel obtained in the step (2) with a dimethylacetamide solution with the mass fraction of 80% according to a mass ratio of 1: 20, mixing, adding polyvinylidene fluoride accounting for 3-4 times of the mass of the modified microgel and polyvinylpyrrolidone accounting for 0.3-0.4 time of the mass of the modified microgel, and stirring and mixing to obtain a film forming solution;
(4) scraping the film-forming liquid obtained in the step (3) on a glass plate by using a scraper with the thickness of 200 mu m, immersing the glass plate into a gel bath, standing for 2min at the temperature of 20 ℃, taking out the glass plate, uncovering the film, washing and drying to obtain a water-treated nano material composite film;
(5) and (4) performing index analysis on the water treatment nano material composite membrane obtained in the step (4).
As optimization, the modified carbon nanotube obtained in the step (1) is prepared by mixing the carbon nanotube with mixed acid liquor according to a mass ratio of 1: 40, stirring, reacting, filtering and drying to obtain an acidified carbon nano tube, wherein dicyclohexylcarbodiimide and 4-dimethylaminopyridine are mixed according to the mass ratio of 11: 1, mixing, adding N.N-dimethylformamide 60-80 times of the mass of dicyclohexylcarbodiimide and acidified carbon nanotubes 0.2 times of the mass of dicyclohexylcarbodiimide, stirring and dispersing to obtain a carbon nanotube dispersion liquid, and mixing the carbon nanotube dispersion liquid with polyacrylic acid according to a mass ratio of 60: 1, mixing, stirring and reacting under the nitrogen atmosphere, filtering and drying to obtain a pre-modified carbon nano tube, wherein the mass ratio of the pre-modified carbon nano tube to N, N-dimethylformamide is 1: 50, adding diethylenetriamine with the mass of 10 times of that of the pre-modified carbon nano tube, stirring for reaction, filtering and drying to obtain the modified carbon nano tube.
Preferably, the gel bath in the step (4) is deionized water.
Compared with the prior art, the invention has the beneficial effects that:
the microgel is added when the water treatment nano material composite membrane is prepared, and the microgel is combined with titanium dioxide; firstly, oxidized dextran reacts with the modified carbon nanotube and polyallylamine hydrochloride together when the microgel is prepared, because the adjacent hydroxyl on a dextran molecular chain can be converted into aldehyde group after the dextran is oxidized, and the modified carbon nanotube and the polyallylamine hydrochloride molecular chain are provided with primary amino groups, the modified carbon nanotube and the primary amino groups on the polyallylamine hydrochloride molecular chain can be crosslinked with the aldehyde group after the dextran is mixed with the oxidized dextran to form a microgel structure, because the crosslinked structure of the amino groups and the aldehyde groups has good adsorption performance on metal ions, and ammonium ions are remained on the polyallylamine hydrochloride in the microgel structure, so that the microgel has better adsorption performance on dye with negative charges, the metal ions and organic macromolecules with the negative charges can be adsorbed by the microgel, and the contact area between pollutants and titanium dioxide is further improved, the degradation efficiency of the product is improved, secondly, a microgel structure is added in the hydrolysis process of tetrabutyl titanate, and the microgel structure is easy to form a film on the surface of an inorganic substance, so that the film can be formed on the surface of nano titanium dioxide in the formation process of the nano titanium dioxide, the dispersibility of the nano titanium dioxide in the preparation process of the product is improved, the catalytic efficiency of the product is further improved, and meanwhile, the microgel is transparent, so that the microgel can not greatly influence the photocatalysis performance of the nano titanium dioxide when being coated with the nano titanium dioxide.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In order to more clearly illustrate the method provided by the present invention, the following examples are provided, and the method for testing each index of the water treatment nano material composite membrane prepared in the following examples is as follows:
degradation performance: the water treatment nano material composite membrane obtained in each example and the comparative example are used for simulating the degradation rate of waste water of 20mg/L methyl orange under the irradiation of visible light with the light intensity of 100mW/cm2 for 90 min.
Metal ion adsorption: the water treatment nano material composite membrane obtained in each example and the comparative example are placed in water with lead ion concentration of 5mg/L, and after standing for 90min, the lead ion concentration in the water is measured.
Example 1
A water treatment nano material composite membrane mainly comprises the following components in parts by weight: 65 parts of polyvinylidene fluoride, 8 parts of polyvinylpyrrolidone, 8 parts of nano titanium dioxide and 12 parts of microgel.
A preparation method of a water treatment nano material composite membrane mainly comprises the following preparation steps:
(1) mixing glucan and water according to a mass ratio of 1: 25, mixing the mixture in a flask, adding potassium periodate which is 0.9 time of the mass of glucan into the flask, introducing nitrogen into the flask at the speed of 45mL/min, stirring the mixture for reaction for 12 hours at the temperature of 35 ℃ in a dark place to obtain oxidized glucan mixed solution, mixing the oxidized glucan mixed solution with a barium chloride solution with the mass fraction of 15% according to the mass ratio of 1: 1.5, stirring and reacting for 50min at the temperature of 40 ℃ and the rotating speed of 300r/min, filtering, removing precipitates to obtain a pretreated oxidized glucan mixed solution, mixing the pretreated oxidized glucan mixed solution with a sodium sulfate solution with the mass fraction of 15% according to the mass ratio of 1: 1.6, stirring and reacting for 40min at the temperature of 35 ℃ and the rotating speed of 400r/min, filtering to obtain oxidized dextran dispersion, and mixing polyallylamine hydrochloride and water according to the mass ratio of 1: 180, adding modified carbon nano tubes with the mass 2 times that of the polyallylamine hydrochloride into the beaker, stirring and dispersing for 30min under the condition that the rotating speed is 600r/min, adjusting the pH value of materials in the beaker to 9.8 to obtain mixed dispersion liquid, mixing the mixed dispersion liquid and the oxidized glucan dispersion liquid according to the volume ratio of 1: 1, mixing the mixture in a three-neck flask, controlling the adding rate of oxidized glucan dispersion liquid to be 8mL/min, introducing nitrogen into the three-neck flask at the rate of 50mL/min, stirring and reacting for 2 hours at the temperature of 45 ℃ and the rotating speed of 320r/min, performing suction filtration to obtain a microgel blank, and drying the microgel blank for 2 hours at the temperature of 75 ℃ to obtain microgel;
(2) mixing the microgel obtained in the step (1) and trichloromethane according to a mass ratio of 1: 20, adding tetrabutyl titanate with the mass being 3 times of that of the microgel into the mixture of the microgel and the trichloromethane, stirring and mixing to obtain a microgel mixed solution, mixing the microgel mixed solution with 10 mass percent of nitric acid according to the mass ratio of 8:1, mixing, stirring and hydrolyzing for 2 hours at the temperature of 40 ℃ and the rotating speed of 300r/min, filtering to obtain a modified microgel blank, and drying the modified microgel blank for 2 hours at the temperature of 70 ℃ to obtain modified microgel;
(3) mixing the modified microgel obtained in the step (2) with a dimethylacetamide solution with the mass fraction of 80% according to a mass ratio of 1: 20, mixing the mixture in a stirrer, adding polyvinylidene fluoride accounting for 3 times of the mass of the modified microgel and polyvinylpyrrolidone accounting for 0.4 time of the mass of the modified microgel into the stirrer, and stirring and mixing to obtain a film forming solution;
(4) scraping the film forming solution obtained in the step (3) on a glass plate by using a scraper with the thickness of 200 mu m, immersing the glass plate into a gel bath, standing the glass plate for 2min at the temperature of 20 ℃, taking out the glass plate, uncovering the film to obtain a water-treated nano material composite film blank, washing the water-treated nano material composite film blank by using deionized water for 8 times, and drying the water-treated nano material composite film blank for 3h at the temperature of 60 ℃ to obtain a water-treated nano material composite film;
(5) and (4) performing index analysis on the water treatment nano material composite membrane obtained in the step (4).
As optimization, the modified carbon nanotube obtained in the step (1) is prepared by mixing the carbon nanotube with mixed acid liquor according to a mass ratio of 1: 40, stirring, reacting, filtering and drying to obtain an acidified carbon nano tube, wherein dicyclohexylcarbodiimide and 4-dimethylaminopyridine are mixed according to the mass ratio of 11: 1, adding N, N-dimethylformamide with the mass of 80 times that of dicyclohexylcarbodiimide and acidified carbon nanotubes with the mass of 0.2 time that of dicyclohexylcarbodiimide, stirring and dispersing to obtain a carbon nanotube dispersion liquid, and mixing the carbon nanotube dispersion liquid with polyacrylic acid according to a mass ratio of 60: 1, mixing, stirring and reacting under the nitrogen atmosphere, filtering and drying to obtain a pre-modified carbon nano tube, wherein the mass ratio of the pre-modified carbon nano tube to N, N-dimethylformamide is 1: 50, adding diethylenetriamine with the mass of 10 times of that of the pre-modified carbon nano tube, stirring for reaction, filtering and drying to obtain the modified carbon nano tube.
Preferably, the gel bath in the step (4) is deionized water.
Example 2
A water treatment nano material composite membrane mainly comprises the following components in parts by weight: 65 parts of polyvinylidene fluoride, 8 parts of polyvinylpyrrolidone, 8 parts of nano titanium dioxide and 12 parts of microgel.
A preparation method of a water treatment nano material composite membrane mainly comprises the following preparation steps:
(1) mixing glucan and water according to a mass ratio of 1: 25, mixing the mixture in a flask, adding potassium periodate which is 0.9 time of the mass of glucan into the flask, introducing nitrogen into the flask at the speed of 45mL/min, stirring the mixture for reaction for 12 hours at the temperature of 35 ℃ in a dark place to obtain oxidized glucan mixed solution, mixing the oxidized glucan mixed solution with a barium chloride solution with the mass fraction of 15% according to the mass ratio of 1: 1.5, stirring and reacting for 50min at the temperature of 40 ℃ and the rotating speed of 300r/min, filtering, removing precipitates to obtain a pretreated oxidized glucan mixed solution, mixing the pretreated oxidized glucan mixed solution with a sodium sulfate solution with the mass fraction of 15% according to the mass ratio of 1: 1.6, stirring and reacting for 40min at the temperature of 35 ℃ and the rotating speed of 400r/min, filtering to obtain oxidized dextran dispersion, and mixing polyallylamine hydrochloride and water according to the mass ratio of 1: 180, stirring and dispersing for 30min under the condition that the rotating speed is 400r/min, adjusting the pH of the materials in the beaker to 9.8 to obtain a mixed dispersion liquid, mixing the mixed dispersion liquid and the oxidized glucan dispersion liquid according to the volume ratio of 1: 1, mixing the mixture in a three-neck flask, controlling the adding rate of oxidized glucan dispersion liquid to be 8mL/min, introducing nitrogen into the three-neck flask at the rate of 50mL/min, stirring and reacting for 2 hours at the temperature of 45 ℃ and the rotating speed of 320r/min, performing suction filtration to obtain a microgel blank, and drying the microgel blank for 2 hours at the temperature of 75 ℃ to obtain microgel;
(2) mixing the microgel obtained in the step (1) and trichloromethane according to a mass ratio of 1: 20, adding tetrabutyl titanate with the mass being 3 times of that of the microgel into the mixture of the microgel and the trichloromethane, stirring and mixing to obtain a microgel mixed solution, mixing the microgel mixed solution with 10 mass percent of nitric acid according to the mass ratio of 8:1, mixing, stirring and hydrolyzing for 2 hours at the temperature of 40 ℃ and the rotating speed of 300r/min, filtering to obtain a modified microgel blank, and drying the modified microgel blank for 2 hours at the temperature of 70 ℃ to obtain modified microgel;
(3) mixing the modified microgel obtained in the step (2) with a dimethylacetamide solution with the mass fraction of 80% according to a mass ratio of 1: 20, mixing the mixture in a stirrer, adding polyvinylidene fluoride accounting for 3 times of the mass of the modified microgel and polyvinylpyrrolidone accounting for 0.4 time of the mass of the modified microgel into the stirrer, and stirring and mixing to obtain a film forming solution;
(4) scraping the film forming solution obtained in the step (3) on a glass plate by using a scraper with the thickness of 200 mu m, immersing the glass plate into a gel bath, standing the glass plate for 2min at the temperature of 20 ℃, taking out the glass plate, uncovering the film to obtain a water-treated nano material composite film blank, washing the water-treated nano material composite film blank by using deionized water for 8 times, and drying the water-treated nano material composite film blank for 3h at the temperature of 60 ℃ to obtain a water-treated nano material composite film;
(5) and (4) performing index analysis on the water treatment nano material composite membrane obtained in the step (4).
As optimization, the modified carbon nanotube obtained in the step (1) is prepared by mixing the carbon nanotube with mixed acid liquor according to a mass ratio of 1: 40, stirring, reacting, filtering and drying to obtain an acidified carbon nano tube, wherein dicyclohexylcarbodiimide and 4-dimethylaminopyridine are mixed according to the mass ratio of 11: 1, adding N, N-dimethylformamide with the mass of 80 times that of dicyclohexylcarbodiimide and acidified carbon nanotubes with the mass of 0.2 time that of dicyclohexylcarbodiimide, stirring and dispersing to obtain a carbon nanotube dispersion liquid, and mixing the carbon nanotube dispersion liquid with polyacrylic acid according to a mass ratio of 60: 1, mixing, stirring and reacting under the nitrogen atmosphere, filtering and drying to obtain a pre-modified carbon nano tube, wherein the mass ratio of the pre-modified carbon nano tube to N, N-dimethylformamide is 1: 50, adding diethylenetriamine with the mass of 10 times of that of the pre-modified carbon nano tube, stirring for reaction, filtering and drying to obtain the modified carbon nano tube.
Preferably, the gel bath in the step (4) is deionized water.
Example 3
A water treatment nano material composite membrane mainly comprises the following components in parts by weight: 65 parts of polyvinylidene fluoride, 8 parts of polyvinylpyrrolidone, 8 parts of nano titanium dioxide and 12 parts of microgel.
A preparation method of a water treatment nano material composite membrane mainly comprises the following preparation steps:
(1) mixing glucan and water according to a mass ratio of 1: 25, mixing the mixture in a flask, adding potassium periodate which is 0.9 time of the mass of glucan into the flask, introducing nitrogen into the flask at the speed of 45mL/min, stirring the mixture for reaction for 12 hours at the temperature of 35 ℃ in a dark place to obtain oxidized glucan mixed solution, mixing the oxidized glucan mixed solution with a barium chloride solution with the mass fraction of 15% according to the mass ratio of 1: 1.5, stirring and reacting for 50min at the temperature of 40 ℃ and the rotating speed of 300r/min, filtering, removing precipitates to obtain a pretreated oxidized glucan mixed solution, mixing the pretreated oxidized glucan mixed solution with a sodium sulfate solution with the mass fraction of 15% according to the mass ratio of 1: 1.6, stirring and reacting for 40min at the temperature of 35 ℃ and the rotating speed of 400r/min, filtering to obtain oxidized dextran dispersion, and mixing polyallylamine hydrochloride and water according to the mass ratio of 1: 180, adding modified carbon nano tubes with the mass 2 times that of the polyallylamine hydrochloride into the beaker, stirring and dispersing for 30min under the condition that the rotating speed is 600r/min, adjusting the pH value of materials in the beaker to 9.8 to obtain mixed dispersion liquid, mixing the mixed dispersion liquid and the oxidized glucan dispersion liquid according to the volume ratio of 1: 1, mixing the mixture in a three-neck flask, controlling the adding rate of oxidized glucan dispersion liquid to be 8mL/min, introducing nitrogen into the three-neck flask at the rate of 50mL/min, stirring and reacting for 2 hours at the temperature of 45 ℃ and the rotating speed of 320r/min, performing suction filtration to obtain a microgel blank, and drying the microgel blank for 2 hours at the temperature of 75 ℃ to obtain microgel;
(2) tetrabutyl titanate and trichloromethane are mixed according to the mass ratio of 3: 20, stirring and mixing to obtain tetrabutyl titanate mixed liquor, mixing the tetrabutyl titanate mixed liquor with 10 mass percent nitric acid according to a mass ratio of 8:1, mixing, stirring and hydrolyzing for 2 hours at the temperature of 40 ℃ and the rotating speed of 300r/min, filtering to obtain a nano titanium dioxide blank, and drying the nano titanium dioxide blank for 2 hours at the temperature of 70 ℃ to obtain nano titanium dioxide;
(3) mixing the microgel obtained in the step (1) with a dimethylacetamide solution with the mass fraction of 80% according to a mass ratio of 1: 20, mixing the mixture in a stirrer, adding polyvinylidene fluoride with the mass of the microgel being 3 times that of the microgel, adding the nano titanium dioxide obtained in the step (2) with the mass of the microgel being 0.3 times that of the microgel and polyvinylpyrrolidone with the mass of the microgel being 0.4 times that of the microgel into the stirrer, and stirring and mixing the mixture to obtain a film forming solution;
(4) scraping the film forming solution obtained in the step (3) on a glass plate by using a scraper with the thickness of 200 mu m, immersing the glass plate into a gel bath, standing the glass plate for 2min at the temperature of 20 ℃, taking out the glass plate, uncovering the film to obtain a water-treated nano material composite film blank, washing the water-treated nano material composite film blank by using deionized water for 8 times, and drying the water-treated nano material composite film blank for 3h at the temperature of 60 ℃ to obtain a water-treated nano material composite film;
(5) and (4) performing index analysis on the water treatment nano material composite membrane obtained in the step (4).
As optimization, the modified carbon nanotube obtained in the step (1) is prepared by mixing the carbon nanotube with mixed acid liquor according to a mass ratio of 1: 40, stirring, reacting, filtering and drying to obtain an acidified carbon nano tube, wherein dicyclohexylcarbodiimide and 4-dimethylaminopyridine are mixed according to the mass ratio of 11: 1, adding N, N-dimethylformamide with the mass of 80 times that of dicyclohexylcarbodiimide and acidified carbon nanotubes with the mass of 0.2 time that of dicyclohexylcarbodiimide, stirring and dispersing to obtain a carbon nanotube dispersion liquid, and mixing the carbon nanotube dispersion liquid with polyacrylic acid according to a mass ratio of 60: 1, mixing, stirring and reacting under the nitrogen atmosphere, filtering and drying to obtain a pre-modified carbon nano tube, wherein the mass ratio of the pre-modified carbon nano tube to N, N-dimethylformamide is 1: 50, adding diethylenetriamine with the mass of 10 times of that of the pre-modified carbon nano tube, stirring for reaction, filtering and drying to obtain the modified carbon nano tube.
Preferably, the gel bath in the step (4) is deionized water.
Example 4
A water treatment nano material composite membrane mainly comprises the following components in parts by weight: 65 parts of polyvinylidene fluoride, 8 parts of polyvinylpyrrolidone, 8 parts of nano titanium dioxide and 12 parts of modified carbon nano tubes.
A preparation method of a water treatment nano material composite membrane mainly comprises the following preparation steps:
(1) mixing the modified carbon nano tube and trichloromethane according to the mass ratio of 1: 20, adding tetrabutyl titanate with the mass 3 times that of the modified carbon nano tube into the mixture of the microgel and the trichloromethane, stirring and mixing to obtain a modified carbon nano tube mixed solution, mixing the modified carbon nano tube mixed solution with 10% of nitric acid according to the mass ratio of 8:1, mixing, stirring and hydrolyzing for 2 hours at the temperature of 40 ℃ and the rotating speed of 300r/min, filtering to obtain an additive blank, and drying the additive blank for 2 hours at the temperature of 70 ℃ to obtain the additive;
(2) mixing the additive obtained in the step (1) with a dimethylacetamide solution with the mass fraction of 80% according to a mass ratio of 1: 20, mixing the mixture in a stirrer, adding polyvinylidene fluoride accounting for 3 times of the mass of the additive and polyvinylpyrrolidone accounting for 0.4 time of the mass of the additive into the stirrer, and stirring and mixing to obtain a film forming solution;
(3) scraping the film forming solution obtained in the step (2) on a glass plate by using a scraper with the thickness of 200 mu m, immersing the glass plate into a gel bath, standing the glass plate for 2min at the temperature of 20 ℃, taking out the glass plate, uncovering the film to obtain a water-treated nano material composite film blank, washing the water-treated nano material composite film blank by using deionized water for 8 times, and drying the water-treated nano material composite film blank for 3h at the temperature of 60 ℃ to obtain a water-treated nano material composite film;
(4) and (4) performing index analysis on the water treatment nano material composite membrane obtained in the step (3).
Preferably, the gel bath in the step (4) is deionized water.
Comparative example
A water treatment nano material composite membrane mainly comprises the following components in parts by weight: 65 parts of polyvinylidene fluoride, 8 parts of polyvinylpyrrolidone and 8 parts of nano titanium dioxide.
A preparation method of a water treatment nano material composite membrane mainly comprises the following preparation steps:
(1) tetrabutyl titanate and trichloromethane are mixed according to the mass ratio of 3: 20, stirring and mixing to obtain tetrabutyl titanate mixed liquor, mixing the tetrabutyl titanate mixed liquor with 10 mass percent nitric acid according to a mass ratio of 8:1, mixing, stirring and hydrolyzing for 2 hours at the temperature of 40 ℃ and the rotating speed of 300r/min, filtering to obtain a nano titanium dioxide blank, and drying the nano titanium dioxide blank for 2 hours at the temperature of 70 ℃ to obtain nano titanium dioxide;
(2) mixing the nano titanium dioxide obtained in the step (1) with a dimethylacetamide solution with the mass fraction of 80% according to a mass ratio of 1: 50, mixing in a stirrer, adding polyvinylidene fluoride with the mass of 8 times of that of the nano titanium dioxide and polyvinylpyrrolidone with the mass of 2 times of that of the nano titanium dioxide into the stirrer, and stirring and mixing to obtain a film forming solution;
(3) scraping the film forming solution obtained in the step (2) on a glass plate by using a scraper with the thickness of 200 mu m, immersing the glass plate into a gel bath, standing the glass plate for 2min at the temperature of 20 ℃, taking out the glass plate, uncovering the film to obtain a water-treated nano material composite film blank, washing the water-treated nano material composite film blank by using deionized water for 8 times, and drying the water-treated nano material composite film blank for 3h at the temperature of 60 ℃ to obtain a water-treated nano material composite film;
(4) and (4) performing index analysis on the water treatment nano material composite membrane obtained in the step (3).
Preferably, the gel bath in the step (1) is deionized water.
Examples of effects
The following table 1 shows the analysis results of the water treatment nano material composite membrane using examples 1 to 4 of the present invention and comparative example.
TABLE 1
From the comparison of the experimental data of example 1 and comparative example in table 1, it can be found that the addition of the microgel can effectively improve the treatment effect of the product on polluted water when the water-treated nano-material composite membrane is prepared, and from the comparison of the experimental data of example 1 and example 2, when the microgel is prepared without adding the modified carbon nanotube, the schiff base structure having the adsorption property to the metal ion in the microgel is reduced, thereby reducing the adsorption effect of the product on the metal ion, and from the comparison of the experimental data of example 1 and example 3, it can be found that when the microgel is not mixed with the nano-titania and is directly added into the product, the dispersibility of the nano-titania is not good, thereby reducing the degradation property of the product on organic matters, and from the comparison of the experimental data of example 1 and example 4, the microgel is not added when the water-treated nano-material composite membrane is prepared, the dispersibility of the nano titanium dioxide is poor, so that the treatment effect of the product on metal ions and organic matters is poor.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims (1)
1. A water treatment nano-material composite membrane is characterized in that: the material mainly comprises the following raw material components in parts by weight: 65 parts of polyvinylidene fluoride, 8 parts of polyvinylpyrrolidone, 8 parts of nano titanium dioxide and 12 parts of microgel;
the composite membrane mainly comprises the following preparation steps:
(1) mixing glucan and water according to a mass ratio of 1: 25, mixing the mixture in a flask, adding potassium periodate which is 0.9 time of the mass of glucan into the flask, introducing nitrogen into the flask at the speed of 45mL/min, stirring the mixture for reaction for 12 hours at the temperature of 35 ℃ in a dark place to obtain oxidized glucan mixed solution, mixing the oxidized glucan mixed solution with a barium chloride solution with the mass fraction of 15% according to the mass ratio of 1: 1.5, stirring and reacting for 50min at the temperature of 40 ℃ and the rotating speed of 300r/min, filtering, removing precipitates to obtain a pretreated oxidized glucan mixed solution, mixing the pretreated oxidized glucan mixed solution with a sodium sulfate solution with the mass fraction of 15% according to the mass ratio of 1: 1.6, stirring and reacting for 40min at the temperature of 35 ℃ and the rotating speed of 400r/min, filtering to obtain oxidized dextran dispersion, and mixing polyallylamine hydrochloride and water according to the mass ratio of 1: 180, adding modified carbon nano tubes with the mass 2 times that of the polyallylamine hydrochloride into the beaker, stirring and dispersing for 30min under the condition that the rotating speed is 600r/min, adjusting the pH value of materials in the beaker to 9.8 to obtain mixed dispersion liquid, mixing the mixed dispersion liquid and the oxidized glucan dispersion liquid according to the volume ratio of 1: 1, mixing the mixture in a three-neck flask, controlling the adding rate of oxidized glucan dispersion liquid to be 8mL/min, introducing nitrogen into the three-neck flask at the rate of 50mL/min, stirring and reacting for 2 hours at the temperature of 45 ℃ and the rotating speed of 320r/min, performing suction filtration to obtain a microgel blank, and drying the microgel blank for 2 hours at the temperature of 75 ℃ to obtain microgel;
(2) mixing the microgel obtained in the step (1) and trichloromethane according to a mass ratio of 1: 20, adding tetrabutyl titanate with the mass being 3 times of that of the microgel into the mixture of the microgel and the trichloromethane, stirring and mixing to obtain a microgel mixed solution, mixing the microgel mixed solution with 10 mass percent of nitric acid according to the mass ratio of 8:1, mixing, stirring and hydrolyzing for 2 hours at the temperature of 40 ℃ and the rotating speed of 300r/min, filtering to obtain a modified microgel blank, and drying the modified microgel blank for 2 hours at the temperature of 70 ℃ to obtain modified microgel;
(3) mixing the modified microgel obtained in the step (2) with a dimethylacetamide solution with the mass fraction of 80% according to a mass ratio of 1: 20, mixing the mixture in a stirrer, adding polyvinylidene fluoride accounting for 3 times of the mass of the modified microgel and polyvinylpyrrolidone accounting for 0.4 time of the mass of the modified microgel into the stirrer, and stirring and mixing to obtain a film forming solution;
(4) scraping the film forming solution obtained in the step (3) on a glass plate by using a scraper with the thickness of 200 mu m, immersing the glass plate into a gel bath, standing the glass plate for 2min at the temperature of 20 ℃, taking out the glass plate, uncovering the film to obtain a water-treated nano material composite film blank, washing the water-treated nano material composite film blank by using deionized water for 8 times, and drying the water-treated nano material composite film blank for 3h at the temperature of 60 ℃ to obtain a water-treated nano material composite film;
(5) performing index analysis on the water treatment nano material composite membrane obtained in the step (4);
the modified carbon nano tube in the step (1) is prepared by mixing a carbon nano tube and a mixed acid solution according to a mass ratio of 1: 40, stirring, reacting, filtering and drying to obtain an acidified carbon nano tube, wherein dicyclohexylcarbodiimide and 4-dimethylaminopyridine are mixed according to the mass ratio of 11: 1, adding N, N-dimethylformamide with the mass of 80 times that of dicyclohexylcarbodiimide and acidified carbon nanotubes with the mass of 0.2 time that of dicyclohexylcarbodiimide, stirring and dispersing to obtain a carbon nanotube dispersion liquid, and mixing the carbon nanotube dispersion liquid with polyacrylic acid according to a mass ratio of 60: 1, mixing, stirring and reacting under the nitrogen atmosphere, filtering and drying to obtain a pre-modified carbon nano tube, wherein the mass ratio of the pre-modified carbon nano tube to N, N-dimethylformamide is 1: 50, mixing, adding diethylenetriamine with the mass 10 times of that of the pre-modified carbon nano tube, stirring for reaction, filtering and drying to obtain the modified carbon nano tube;
and (4) the gel bath is deionized water.
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