CN108607529B - Organic-inorganic composite polluted water purification filter material and preparation method and application thereof - Google Patents
Organic-inorganic composite polluted water purification filter material and preparation method and application thereof Download PDFInfo
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- CN108607529B CN108607529B CN201810430241.8A CN201810430241A CN108607529B CN 108607529 B CN108607529 B CN 108607529B CN 201810430241 A CN201810430241 A CN 201810430241A CN 108607529 B CN108607529 B CN 108607529B
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- 239000000463 material Substances 0.000 title claims abstract description 100
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 239000002131 composite material Substances 0.000 title claims abstract description 45
- 238000000746 purification Methods 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 32
- 229920001661 Chitosan Polymers 0.000 claims abstract description 30
- 238000002156 mixing Methods 0.000 claims abstract description 26
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000012528 membrane Substances 0.000 claims abstract description 21
- 239000007864 aqueous solution Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000002253 acid Substances 0.000 claims abstract description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229920002523 polyethylene Glycol 1000 Polymers 0.000 claims abstract description 14
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000176 sodium gluconate Substances 0.000 claims abstract description 13
- 229940005574 sodium gluconate Drugs 0.000 claims abstract description 13
- 235000012207 sodium gluconate Nutrition 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 239000000654 additive Substances 0.000 claims abstract description 8
- 229920000875 Dissolving pulp Polymers 0.000 claims abstract description 6
- 230000000996 additive effect Effects 0.000 claims abstract description 5
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 5
- 229920002545 silicone oil Polymers 0.000 claims abstract description 5
- 239000003924 oil dispersant Substances 0.000 claims abstract description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 30
- 238000011069 regeneration method Methods 0.000 claims description 24
- 239000003344 environmental pollutant Substances 0.000 claims description 23
- 231100000719 pollutant Toxicity 0.000 claims description 23
- 230000008929 regeneration Effects 0.000 claims description 23
- BAECOWNUKCLBPZ-HIUWNOOHSA-N Triolein Natural products O([C@H](OCC(=O)CCCCCCC/C=C\CCCCCCCC)COC(=O)CCCCCCC/C=C\CCCCCCCC)C(=O)CCCCCCC/C=C\CCCCCCCC BAECOWNUKCLBPZ-HIUWNOOHSA-N 0.000 claims description 16
- PHYFQTYBJUILEZ-UHFFFAOYSA-N Trioleoylglycerol Natural products CCCCCCCCC=CCCCCCCCC(=O)OCC(OC(=O)CCCCCCCC=CCCCCCCCC)COC(=O)CCCCCCCC=CCCCCCCCC PHYFQTYBJUILEZ-UHFFFAOYSA-N 0.000 claims description 16
- PHYFQTYBJUILEZ-IUPFWZBJSA-N triolein Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CCCCCCCC)COC(=O)CCCCCCC\C=C/CCCCCCCC PHYFQTYBJUILEZ-IUPFWZBJSA-N 0.000 claims description 16
- 229940117972 triolein Drugs 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 13
- 229920002301 cellulose acetate Polymers 0.000 claims description 12
- 229910001385 heavy metal Inorganic materials 0.000 claims description 11
- 238000002791 soaking Methods 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 11
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 10
- MPCRDALPQLDDFX-UHFFFAOYSA-L Magnesium perchlorate Chemical group [Mg+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O MPCRDALPQLDDFX-UHFFFAOYSA-L 0.000 claims description 9
- 238000001179 sorption measurement Methods 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 229920005551 calcium lignosulfonate Polymers 0.000 claims description 6
- 239000012459 cleaning agent Substances 0.000 claims description 6
- 239000002957 persistent organic pollutant Substances 0.000 claims description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 5
- RYAGRZNBULDMBW-UHFFFAOYSA-L calcium;3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Ca+2].COC1=CC=CC(CC(CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O RYAGRZNBULDMBW-UHFFFAOYSA-L 0.000 claims description 5
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 5
- 238000011282 treatment Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 4
- 235000011152 sodium sulphate Nutrition 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- 229910021536 Zeolite Inorganic materials 0.000 claims description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 239000010457 zeolite Substances 0.000 claims description 2
- 238000010828 elution Methods 0.000 claims 1
- 230000001172 regenerating effect Effects 0.000 claims 1
- 231100001240 inorganic pollutant Toxicity 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000002351 wastewater Substances 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- 229910002651 NO3 Inorganic materials 0.000 description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 6
- SXDBWCPKPHAZSM-UHFFFAOYSA-M bromate Inorganic materials [O-]Br(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-M 0.000 description 6
- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical compound OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 description 6
- 239000002270 dispersing agent Substances 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000004065 wastewater treatment Methods 0.000 description 3
- JLPUXFOGCDVKGO-TUAOUCFPSA-N (-)-geosmin Chemical compound C1CCC[C@]2(O)[C@@H](C)CCC[C@]21C JLPUXFOGCDVKGO-TUAOUCFPSA-N 0.000 description 2
- 239000001075 (4R,4aR,8aS)-4,8a-dimethyl-1,2,3,4,5,6,7,8-octahydronaphthalen-4a-ol Substances 0.000 description 2
- LFYXNXGVLGKVCJ-FBIMIBRVSA-N 2-methylisoborneol Chemical compound C1C[C@@]2(C)[C@](C)(O)C[C@@H]1C2(C)C LFYXNXGVLGKVCJ-FBIMIBRVSA-N 0.000 description 2
- LFYXNXGVLGKVCJ-UHFFFAOYSA-N 2-methylisoborneol Natural products C1CC2(C)C(C)(O)CC1C2(C)C LFYXNXGVLGKVCJ-UHFFFAOYSA-N 0.000 description 2
- DUIOKRXOKLLURE-UHFFFAOYSA-N 2-octylphenol Chemical compound CCCCCCCCC1=CC=CC=C1O DUIOKRXOKLLURE-UHFFFAOYSA-N 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- 238000011001 backwashing Methods 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- JLPUXFOGCDVKGO-UHFFFAOYSA-N dl-geosmin Natural products C1CCCC2(O)C(C)CCCC21C JLPUXFOGCDVKGO-UHFFFAOYSA-N 0.000 description 2
- DTGKSKDOIYIVQL-UHFFFAOYSA-N dl-isoborneol Natural products C1CC2(C)C(O)CC1C2(C)C DTGKSKDOIYIVQL-UHFFFAOYSA-N 0.000 description 2
- 239000003651 drinking water Substances 0.000 description 2
- 235000020188 drinking water Nutrition 0.000 description 2
- 231100000049 endocrine disruptor Toxicity 0.000 description 2
- 239000000598 endocrine disruptor Substances 0.000 description 2
- 229930001467 geosmin Natural products 0.000 description 2
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 230000002411 adverse Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000006196 deacetylation Effects 0.000 description 1
- 238000003381 deacetylation reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- JZZIHCLFHIXETF-UHFFFAOYSA-N dimethylsilicon Chemical compound C[Si]C JZZIHCLFHIXETF-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- DKAGJZJALZXOOV-UHFFFAOYSA-N hydrate;hydrochloride Chemical compound O.Cl DKAGJZJALZXOOV-UHFFFAOYSA-N 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
- 239000008204 material by function Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000000941 radioactive substance Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D39/00—Filtering material for liquid or gaseous fluids
- B01D39/14—Other self-supporting filtering material ; Other filtering material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D39/00—Filtering material for liquid or gaseous fluids
- B01D39/14—Other self-supporting filtering material ; Other filtering material
- B01D39/16—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D39/00—Filtering material for liquid or gaseous fluids
- B01D39/14—Other self-supporting filtering material ; Other filtering material
- B01D39/16—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres
- B01D39/1607—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres the material being fibrous
- B01D39/1615—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres the material being fibrous of natural origin
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/46—Materials comprising a mixture of inorganic and organic materials
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Water Treatment By Sorption (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention relates to the technical field of environmental protection, in particular to an organic-inorganic composite polluted water purification filter material and a preparation method and application thereof. Dissolving cellulose acetate with acetone, adding a dimethyl silicone oil dispersant, mixing uniformly, adding a mixed additive, mixing fully for 6-48h at 30-40 ℃ to obtain a composite membrane liquid, adding a treated filter material carrier according to the addition of 500 plus materials of 1000g/L, and stirring uniformly to obtain a filter material loaded with the composite membrane liquid; adding the filter material loaded with the composite membrane liquid into a chitosan dilute acid aqueous solution containing sodium gluconate and PEG1000, and uniformly mixing to obtain a water purification filter material; the water purifying filter material obtained by the method has stable property, and can simultaneously remove various organic and inorganic pollutants in water with excellent performance.
Description
Technical Field
The invention relates to the technical field of environmental protection, in particular to an organic-inorganic composite polluted water purification filter material and a preparation method and application thereof.
Background
For a long time, the adsorption method and the flocculant addition method are the most important water treatment methods for removing lipophilic and hydrophilic pollutants, and are widely applied to various water supply or drainage treatments. Due to the developed pore structure and large specific surface area, the activated carbon is widely applied to drinking water and sewage treatment processes as an adsorbent. However, the activated carbon lacks selectivity for adsorbing organic matters in water, is easy to saturate, needs to be continuously regenerated in the using process, has poor effect of removing low-concentration organic matters, and is not ideal for removing low-content and lipophilic pollutants in the conventional water body at present. At present, the water quality is deeply purified by adopting an adsorption method, shell activated carbon is usually selected as a filtering material, and the regeneration is carried out by back washing with clean water. The shell activated carbon has low mechanical strength, and the re-adsorption efficiency of lipophilic pollutants after water backwashing is low, so that the service life is short. In addition, the flocculant reduces the turbidity and chromaticity of raw water and removes various macromolecular organic matters, certain heavy metals and radioactive substances by forming coarse flocs from colloids and suspended matters which are not easy to settle in water. However, the synthetic organic polymeric flocculant with good stability is high in price, and hydrolysis or degradation products can generate adverse effects on human health and ecological environment; the inorganic flocculant (aluminum salt and ferric salt or a copolymer of the aluminum salt and the ferric salt) with lower cost has certain toxicity and corrosivity; the bioflocculant is easily interfered by toxic substances in the treated water body, so the application range is limited. Therefore, it is necessary to develop a new adsorbent material with high efficiency and economy to selectively remove lipophilic and hydrophilic contaminants in drinking water at the same time in an extremely low content.
The research on the prior art documents finds that the development of the water purification filter material mainly focuses on how to improve the removal of single pollutants such as organic pollutants or inorganic pollutants, and the like, and the matched filter material recycling technology is relatively weak. So far, no report on the preparation and recycling method of the organic-inorganic composite polluted water purification filter material is found.
Disclosure of Invention
The invention aims to provide an organic-inorganic composite polluted water purification filter material and a preparation method thereof aiming at the defects of the prior art.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of a filter material for purifying organic-inorganic composite polluted water comprises the following steps:
1) dissolving cellulose acetate with acetone, adding dimethyl silicon oil dispersant with the final concentration of 0.1% (mass percentage), uniformly mixing, then adding a mixed additive, fully mixing at 30-40 ℃ for 6-48h to obtain a composite membrane liquid, then adding a treated filter material carrier according to the addition of 500 plus one 1000g/L, and uniformly stirring to obtain a filter material loaded with the composite membrane liquid; wherein, the mixed additive is cellulose acetate: acetone: magnesium perchlorate: anhydrous sodium sulfate: triolein ═ 1-2: 10-35: 0.2-0.5: 0.1-0.2: 0.2-4 (mass ratio);
2) adding the filter material loaded with the composite membrane liquid into a chitosan dilute acid aqueous solution containing sodium gluconate and PEG1000, and uniformly mixing to obtain a water purification filter material; wherein the mass ratio of the filter material loaded with the composite membrane liquid to the chitosan in the dilute acid aqueous solution is 30-60: 1.
the treated filter material carrier is prepared by soaking the filter material carrier in 1% calcium lignosulfonate water solution for 4-24h, washing with water until the water body is clear, and drying for later use.
The filter material carrier is ceramsite, gravel, iron ore filter material or zeolite.
The chitosan concentration in the chitosan diluted acid water solution containing sodium gluconate and PEG1000 is 1-10 wt%; wherein the dilute acid is hydrochloric acid or acetic acid with concentration of 1-2%; wherein, sodium gluconate: PEG 1000: the mass ratio of the chitosan is 1: 1: 10.
wherein the degree of deacetylation of chitosan is > 50%.
The organic-inorganic composite polluted water purification filter material is prepared according to the method.
An application of a purifying filter material for organic-inorganic composite polluted water, and an application of the purifying filter material in water purification.
The purifying filter material is applied to the adsorption removal of organic pollutants and heavy metals in water.
A regeneration method of purification filter material for organic-inorganic composite polluted water comprises mixing water purification filter material saturated with adsorbed pollutant with regeneration cleaning agent, and shaking at 20-40 deg.C for 20-120min to elute pollutant; and soaking the washed and eluted solution in a regeneration solution for 5-20min, and then drying to obtain the purified filter material after regeneration treatment.
The regeneration liquid is fully mixed for 6-48h at the temperature of 30-40 ℃ to obtain the regeneration liquid with the mass ratio of 1-2: 10-35: 0.1-3.5: 0.2-0.5: 0.2-4 cellulose acetate: 80-90% acetic acid aqueous solution: and (3) chitosan: magnesium chloride: triolein mixed liquor; the regenerated cleaning agent is dilute acid water solution and/or alcohols (methanol, ethanol and the like).
The principle is as follows: according to the invention, the lipophilic organic pollutants are enriched by using the triolein according to the principle of similarity and compatibility, and the hydrophilicity of the surface of the cellulose acetate membrane can promote the mass transfer process of solutes in an aqueous solution. Meanwhile, the surface of the filter material is wrapped with a chitosan film, hydrophilic pollutants are enriched by utilizing the fact that the surface of the chitosan contains various hydrophilic functional groups such as hydroxyl, carboxyl and the like through the adsorption and coordination effect, and the embedded lipoid particles and the chitosan film are easy to deposit on the surface of the filter material carrier due to the rich pore structure. Finally, the novel composite water purification filter material is obtained and used for purifying water and simultaneously removing various pollutants such as organic pollutants, heavy metals and the like.
The invention has the advantages that:
1) the prepared filter material can simultaneously remove organic and inorganic composite pollutants, and belongs to a multipurpose environment-friendly material. The water environment pollution is often expressed as composite pollution of organic matters and inorganic matters, and the surfaces of the water purifying filter materials are simultaneously wrapped with lipophilic granular materials and hydrophilic film materials, so that various organic pollutants, heavy metals and other inorganic pollutants can be simultaneously removed. The water purifying filter material obtained by the method has stable property, and can simultaneously remove various organic and inorganic pollutants in water with excellent performance.
2) The preparation process of the filter material is simple, and different functional materials are loaded on the surface layer of the filter material only through a simple soaking-coating process. The preparation process does not use strong acid and strong alkali, and does not adopt high-temperature and high-pressure environment, and the calcium lignosulphonate, the triolein, the cellulose acetate, the PEG1000, the chitosan, the acetic acid and the like required by the preparation have wide sources, low price and low material preparation cost.
3) The filter material is easy to recover and regenerate. The water purification material with saturated adsorption can select different regeneration cleaning agents according to the property of adsorbed pollutants, and the adsorption performance of the material can be quickly recovered to the original level by soaking the treated water purification material in the regeneration liquid.
Detailed Description
The present invention is further illustrated by the following examples, which, however, are not intended to limit the scope of the invention.
Example 1
Dissolving cellulose acetate by using acetone, then adding a dimethyl silicone oil dispersing agent, uniformly mixing to ensure that the final concentration of the dispersing agent in the dissolved solution is 0.1% by mass, adding additives, namely magnesium perchlorate, anhydrous sodium sulfate and triolein, after uniformly mixing, and fully mixing for 10 hours at 35 ℃ to obtain a composite membrane liquid for later use. Wherein, cellulose acetate: acetone: magnesium perchlorate: anhydrous sodium sulfate: triolein is 1.6: 20: 0.5: 0.2: 3 (mass ratio);
soaking the purchased ceramsite filter material in 1% calcium lignosulfonate aqueous solution by mass concentration for 10 hours, washing with water until the water body is clear, drying, adding the ceramsite filter material into the composite membrane liquid according to the addition of 500g/L, uniformly stirring and collecting solid substances; then adding the mixture into a 6 wt% chitosan dilute acid (1% acetic acid) aqueous solution containing sodium gluconate and PEG1000, wherein the weight ratio of sodium gluconate: PEG 1000: the mass ratio of the chitosan is 1: 1: 10, the mass ratio of the chitosan to the composite membrane-loaded liquid filter material is 1: and 40, stirring and mixing for 5min, collecting the solid modified filter material, and drying to obtain the water purification filter material.
The composite material prepared by the method is used for removing pollutants in wastewater, and specifically, a water purification filter material is added into wastewater (bisphenol A100 mu g L) containing phenolic endocrine disruptors and heavy metals according to the proportion of 3 percent (mass ratio)-1Nonyl phenol 100 mu g/L, octyl phenol 100 mu g/L and zinc 3mg/L), the removal rate of the pollutants is more than 95 percent.
Mixing the water purification filter material after wastewater treatment with a regeneration cleaning agent (methanol: 1% hydrochloric acid water solution: 60: 40(v/v)), and shaking at 40 ℃ for 120min to elute pollutants; then soaking the water purification filter material in a regeneration liquid for 20min, and then drying to obtain a regenerated water purification filter material; the regeneration liquid is a mixed solution which is fully mixed for 24 hours at the temperature of 30 ℃, and the mixed solution is prepared from the following components in percentage by mass: 20: 0.2: 0.5: 3 cellulose acetate: 85% acetic acid aqueous solution: and (3) chitosan: magnesium chloride: and (3) triolein mixed liquor.
Using the above regeneration to obtain a compositeThe material is used for removing pollutants in wastewater, and specifically, a water purification filter material is added into wastewater (bisphenol A100 mu g L) containing phenolic endocrine disruptors and heavy metals according to the proportion of 3 percent (mass ratio)-1Nonyl phenol 100 mu g/L, octyl phenol 100 mu g/L and zinc 3mg/L), the removal rate of the pollutants is more than 95 percent.
Example 2
Dissolving cellulose acetate by using acetone, then adding a dimethyl silicone oil dispersing agent, uniformly mixing to ensure that the final concentration of the dispersing agent in the dissolved solution is 0.1% by mass, adding additives, namely magnesium perchlorate, anhydrous sodium sulfate and triolein, after uniformly mixing, and fully mixing for 6 hours at the temperature of 30 ℃ to obtain a composite membrane liquid for later use. Wherein, cellulose acetate: acetone: magnesium perchlorate: anhydrous sodium sulfate: triolein is 1: 10: 0.3: 0.12: 4 (mass ratio);
soaking the purchased ceramsite filter material in 1% calcium lignosulfonate aqueous solution by mass concentration for 24 hours, washing with water until the water body is clear, drying, adding the ceramsite filter material into the composite membrane liquid according to the addition of 1000g/L, uniformly stirring and collecting solid substances; and then adding the mixture into 1 wt% chitosan dilute acid (2% acetic acid) aqueous solution containing sodium gluconate and PEG1000, wherein the weight ratio of sodium gluconate: PEG 1000: the mass ratio of the chitosan is 1: 1: 10, the mass ratio of the chitosan to the composite membrane-loaded liquid filter material is 1: and 60, stirring and mixing for 10min, collecting the solid modified filter material, and drying to obtain the water purification filter material.
The composite material prepared by the method is used for removing pollutants in wastewater, and specifically, a water purification filter material is added into water containing odor substances, bromate and nitrate (300 ng/L of geosmin, 100ng/L of 2-methylisoborneol, 1 microgram/L of bromate and 5mg/L of nitrate) according to the proportion of 1.5% (mass ratio), the removal rate of the odor substances is more than 95%, and the removal rate of the bromate and the nitrate is more than 90%.
Mixing the water purification filter material after wastewater treatment with methanol, and shaking at 35 ℃ for 60min to elute pollutants; then soaking the water purification filter material in a regeneration liquid for 10min, and then drying to obtain a regenerated water purification filter material; the regeneration liquid is a mixed solution which is fully mixed for 6 hours at the temperature of 40 ℃, and the mixed solution is prepared from the following components in percentage by mass: 10: 0.1: 0.3: 4 cellulose acetate: 80% acetic acid aqueous solution: and (3) chitosan: magnesium chloride: and (3) triolein mixed liquor.
The composite material obtained by regeneration is utilized to remove pollutants in wastewater, and specifically, a water purification filter material is added into water containing odor substances, bromate and nitrate (300 ng/L of geosmin, 100ng/L of 2-methylisoborneol, 1 microgram/L of bromate and 5mg/L of nitrate) according to the proportion of 1.5% (mass ratio), the removal rate of the odor substances is more than 95%, and the removal rate of the bromate and the nitrate is more than 90%.
Example 3
Dissolving cellulose acetate by using acetone, then adding a dimethyl silicone oil dispersing agent, uniformly mixing to ensure that the final concentration of the dispersing agent in the dissolved solution is 0.1% by mass, adding additives, namely magnesium perchlorate, anhydrous sodium sulfate and triolein, after uniformly mixing, and fully mixing for 24 hours at 40 ℃ to obtain a composite membrane liquid for later use. Wherein, cellulose acetate: acetone: magnesium perchlorate: anhydrous sodium sulfate: triolein ═ 2: 35: 0.2: 0.1: 0.2 (mass ratio);
soaking the purchased ceramsite filter material in 1% calcium lignosulfonate aqueous solution by mass concentration for 4h, washing with water until the water body is clear, drying, adding the ceramsite filter material into the composite membrane liquid according to the addition of 800g/L, stirring uniformly, and collecting solid substances; then adding the mixture into a 10wt% chitosan dilute acid (1.5% hydrochloric acid) aqueous solution containing sodium gluconate and PEG1000, wherein the weight ratio of sodium gluconate: PEG 1000: the mass ratio of the chitosan is 1: 1: 10, the mass ratio of the chitosan to the composite membrane-loaded liquid filter material is 1: and 30, stirring and mixing for 20min, collecting the solid modified filter material, and drying to obtain the water purification filter material.
The composite material prepared by the method is used for removing pollutants in wastewater, and specifically, a water purification filter material is added into wastewater (PAHs 10 microgram/L, copper 4mg/L, cadmium 0.3mg/L, lead 1mg/L and zinc 2mg/L) containing Polycyclic Aromatic Hydrocarbons (PAHs) and heavy metals according to the proportion of 1% (mass ratio), wherein the removal rate of the PAHs and the heavy metals exceeds 90%.
Mixing the water purification filter material after wastewater treatment with methanol, and shaking for 20min at 30 ℃ to elute pollutants; then soaking the water purification filter material in a regeneration liquid for 5min, and then drying to obtain a regenerated water purification filter material; the regeneration liquid is a mixed solution which is fully mixed for 48 hours at the temperature of 35 ℃, and the mixed solution is prepared from the following components in percentage by mass: 35: 3.5: 0.2: 0.2 cellulose acetate: 90% acetic acid aqueous solution: and (3) chitosan: magnesium chloride: and (3) triolein mixed liquor.
The composite material obtained by regeneration is utilized to remove pollutants in wastewater, specifically, a water purification filter material is added into wastewater (PAHs 10 microgram/L, copper 4mg/L, cadmium 0.3mg/L, lead 1mg/L and zinc 2mg/L) containing Polycyclic Aromatic Hydrocarbon (PAHs) and heavy metals according to the proportion of 1% (mass ratio), and the removal rate of the PAHs and the heavy metals exceeds 90%.
Claims (6)
1. A preparation method of a filter material for purifying organic-inorganic composite polluted water is characterized by comprising the following steps:
1) dissolving cellulose acetate with acetone, adding a dimethyl silicone oil dispersant, mixing uniformly, adding a mixed additive, mixing fully for 6-48h at 30-40 ℃ to obtain a composite membrane liquid, adding a treated filter material carrier according to the addition of 500 plus materials of 1000g/L, and stirring uniformly to obtain a filter material loaded with the composite membrane liquid; the mixed additive is magnesium perchlorate, anhydrous sodium sulfate and triolein, wherein the ratio of cellulose acetate: acetone: magnesium perchlorate: anhydrous sodium sulfate: the mass ratio of the triolein is 1-2: 10-35: 0.2-0.5: 0.1-0.2: 0.2 to 4;
2) adding the filter material loaded with the composite membrane liquid into a chitosan dilute acid aqueous solution containing sodium gluconate and PEG1000, and uniformly mixing to obtain a purification filter material; wherein the mass ratio of the filter material loaded with the composite membrane liquid to the chitosan in the dilute acid aqueous solution is 30-60: 1;
the treated filter material carrier is prepared by soaking the filter material carrier in calcium lignosulfonate aqueous solution for 4-24h, washing with water until the water body is in a clear state, and drying for later use;
the chitosan concentration in the chitosan diluted acid water solution containing sodium gluconate and PEG1000 is 1-10 wt%; wherein the dilute acid is hydrochloric acid or acetic acid with concentration of 1-2%; wherein, sodium gluconate: PEG 1000: the mass ratio of the chitosan is 1: 1: 10.
2. the method for preparing the filter material for purifying organic-inorganic composite polluted water according to claim 1, which is characterized in that: the filter material carrier is ceramsite, gravel, iron ore filter material or zeolite.
3. A filter material for purifying organic-inorganic composite polluted water is characterized in that: the filter material for purifying organic-inorganic composite polluted water, which is prepared by the method of claim 1.
4. The use of the organic-inorganic composite polluted water purification filter material of claim 3, which is characterized in that: the purifying filter material is applied to water purification.
5. The use of the organic-inorganic composite polluted water purification filter material according to claim 4, wherein: the purifying filter material is applied to the adsorption removal of organic pollutants and heavy metals in water.
6. A method for regenerating a filter material for purifying organic-inorganic composite polluted water according to claim 3, characterized in that: mixing the purification filter material saturated with adsorbed pollutants with a regeneration cleaning agent, and shaking at 20-40 deg.C for 20-120min to elute the pollutants; soaking in the regeneration liquid for 5-20min after elution, and drying to obtain a purified filter material after regeneration treatment;
the regeneration liquid is fully mixed for 6-48h at the temperature of 30-40 ℃ to obtain the regeneration liquid with the mass ratio of 1-2: 10-35: 0.1-3.5: 0.2-0.5: 0.2-4 cellulose acetate: 80-90% acetic acid aqueous solution: and (3) chitosan: magnesium chloride: triolein mixed liquor; the regenerated cleaning agent is dilute acid water solution and/or alcohol.
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