CN116603514B - Sewage treatment agent for treating groundwater pollution and preparation method thereof - Google Patents
Sewage treatment agent for treating groundwater pollution and preparation method thereof Download PDFInfo
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- CN116603514B CN116603514B CN202310881749.0A CN202310881749A CN116603514B CN 116603514 B CN116603514 B CN 116603514B CN 202310881749 A CN202310881749 A CN 202310881749A CN 116603514 B CN116603514 B CN 116603514B
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- 239000010865 sewage Substances 0.000 title claims abstract description 38
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 27
- 238000003895 groundwater pollution Methods 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000011159 matrix material Substances 0.000 claims abstract description 47
- 239000002131 composite material Substances 0.000 claims abstract description 27
- 239000006260 foam Substances 0.000 claims abstract description 21
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical class O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229920000858 Cyclodextrin Polymers 0.000 claims abstract description 14
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 12
- FZGFBJMPSHGTRQ-UHFFFAOYSA-M trimethyl(2-prop-2-enoyloxyethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCOC(=O)C=C FZGFBJMPSHGTRQ-UHFFFAOYSA-M 0.000 claims abstract description 12
- 239000008367 deionised water Substances 0.000 claims description 37
- 229910021641 deionized water Inorganic materials 0.000 claims description 37
- 239000000758 substrate Substances 0.000 claims description 34
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 27
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 27
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 25
- 239000012065 filter cake Substances 0.000 claims description 21
- 238000001914 filtration Methods 0.000 claims description 20
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 20
- 239000002245 particle Substances 0.000 claims description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 239000000706 filtrate Substances 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 239000001116 FEMA 4028 Substances 0.000 claims description 12
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 claims description 12
- 235000011175 beta-cyclodextrine Nutrition 0.000 claims description 12
- 229960004853 betadex Drugs 0.000 claims description 12
- 229920002678 cellulose Polymers 0.000 claims description 12
- 239000001913 cellulose Substances 0.000 claims description 12
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 12
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 12
- MKIJJIMOAABWGF-UHFFFAOYSA-N methyl 2-sulfanylacetate Chemical compound COC(=O)CS MKIJJIMOAABWGF-UHFFFAOYSA-N 0.000 claims description 12
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 11
- 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 description 11
- 238000000034 method Methods 0.000 claims description 11
- 229920000570 polyether Polymers 0.000 claims description 11
- 229940068918 polyethylene glycol 400 Drugs 0.000 claims description 11
- 229920005862 polyol Polymers 0.000 claims description 11
- 150000003077 polyols Chemical class 0.000 claims description 11
- 229920002545 silicone oil Polymers 0.000 claims description 11
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 125000003277 amino group Chemical group 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 5
- 238000010298 pulverizing process Methods 0.000 claims description 2
- 239000003344 environmental pollutant Substances 0.000 abstract description 11
- 231100000719 pollutant Toxicity 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 7
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 abstract description 5
- 150000001450 anions Chemical class 0.000 abstract description 2
- 125000002091 cationic group Chemical group 0.000 abstract description 2
- 229920000587 hyperbranched polymer Polymers 0.000 abstract description 2
- 230000003647 oxidation Effects 0.000 abstract description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 2
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 2
- 238000005286 illumination Methods 0.000 abstract 1
- 239000002351 wastewater Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 241000196324 Embryophyta Species 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 241000282414 Homo sapiens Species 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 239000003337 fertilizer Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 1
- 244000256297 Euphorbia tirucalli Species 0.000 description 1
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- -1 diphenylmethane dioxycyanate Chemical compound 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 230000002550 fecal effect Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
- B01J20/264—Synthetic macromolecular compounds derived from different types of monomers, e.g. linear or branched copolymers, block copolymers, graft copolymers
-
- 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
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
-
- 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
- B01J20/262—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon to carbon unsaturated bonds, e.g. obtained by polycondensation
-
- 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
- B01J20/28042—Shaped bodies; Monolithic structures
- B01J20/28045—Honeycomb or cellular structures; Solid foams or sponges
-
- 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
- B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
-
- 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
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- 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
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/06—Contaminated groundwater or leachate
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- Water Supply & Treatment (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Water Treatment By Sorption (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The application discloses a sewage treatment agent for treating groundwater pollution and a preparation method thereof, wherein modified cyclodextrin, a modified matrix, acrylamide and acryloyloxyethyl trimethyl ammonium chloride are polymerized to form a hyperbranched structure taking the modified matrix as a central body, the composite matrix is porous foam which can adsorb pollutants in water, and simultaneously promote the pollutants to contact with nano titanium dioxide on the surface, when the nano titanium dioxide surface is subjected to illumination, a large number of holes and electrons are formed, the electrons and the holes with high energy can be regenerated on adjacent water molecules or pollutant molecules, so that free radicals are generated, the free radicals have strong oxidation effect, the adsorbed organic pollutants can be decomposed, and the hyperbranched polymer chain side chain on the surface of the sewage treatment agent contains cationic groups which can adsorb the pollutants with anions in the sewage, and meanwhile, the cyclodextrin-containing cavity on the side chain can cover the pollutants, so that the sewage treatment effect is better.
Description
Technical Field
The application relates to the field of sewage treatment, in particular to a sewage treatment agent for treating groundwater pollution and a preparation method thereof.
Background
As the activities of human production and living are more and more abundant, the pollution of water is also more and more serious. Any discharge of the out-of-standard wastewater is a main cause of water body pollution, the wastewater is divided into three categories of agriculture, industry and domestic sewage, and due to weak agricultural knowledge and environmental awareness of farmers, in the process of planting crops, excessive application of chemical fertilizer and pesticide is carried out for grain yield increase, and the crops can not be completely absorbed, so that pollutants such as nitrogen and phosphorus in the chemical fertilizer enter surface water or permeate into underground water to cause out-of-standard nitrogen and phosphorus in the water body, and a large amount of agricultural wastewater is generated; industrial wastewater mainly comprises wastewater discharged by chemical plants, petroleum plants, dye plants and the like, while each enterprise plant is built or provided with sewage treatment facilities according to requirements, the wastewater discharge of some enterprises still does not reach the standard, the daily domestic sewage discharge amount of human beings is huge, the urban resident discharged sewage types mainly comprise restaurant wastewater, laundry wastewater, fecal wastewater and the like, and the traditional water treatment process is an adsorption and precipitation process, so that the method is simple to operate and convenient to use, has wide application in water and wastewater treatment, and receives importance of people. However, a large amount of agents are added, the cost is high, and the formed sludge can cause secondary pollution of the water body, which is a main reason for restricting the application of the water body. Therefore, there is a need to find a cheaper recyclable sewage purification material to reduce the sewage treatment cost and improve the purification efficiency.
Disclosure of Invention
The application aims to provide a sewage treatment agent for treating groundwater pollution and a preparation method thereof, which solve the problems of large use amount and general treatment effect of the sewage treatment agent at the present stage.
The aim of the application can be achieved by the following technical scheme:
the preparation method of the sewage treatment agent for treating groundwater pollution specifically comprises the following steps:
step A1: dispersing the composite matrix in toluene, adding DCC and acrylic acid, reacting for 2-3 hours at the rotation speed of 200-300r/min and the temperature of 25-30 ℃, filtering to remove filtrate, dispersing the filter cake in deionized water, adding methyl thioglycolate, reacting for 30-40 minutes at the rotation speed of 60-80r/min and the temperature of 20-25 ℃ under the irradiation of 365nm ultraviolet lamp, and preparing the pretreated matrix;
step A2: mixing a pretreated substrate, diethanolamine and methanol, stirring for 20-25 hours at the rotating speed of 150-200r/min and the temperature of 20-25 ℃ and the pH value of 9-10, filtering to remove filtrate, dispersing a filter cake in toluene, adding acrylic acid and p-toluenesulfonic acid, and reacting for 6-8 hours at the rotating speed of 60-80r/min and the temperature of 110-120 ℃ to obtain a modified substrate;
step A3: dissolving beta-cyclodextrin in acetic acid solution, stirring and adding maleic anhydride at the rotation speed of 120-150r/min and the temperature of 75-80 ℃ for reaction for 3-5 hours to obtain modified cyclodextrin, dispersing a modified matrix, modified cyclodextrin, acrylamide and acryloyloxyethyl trimethyl ammonium chloride in deionized water, introducing nitrogen for protection, stirring and adding potassium persulfate at the rotation speed of 150-200r/min and the temperature of 50-70 ℃ and the pH value of 7-8, reacting for 6-8 hours, filtering to remove filtrate, crushing a substrate, and obtaining the sewage treatment agent for treating groundwater pollution.
Further, the molar ratio of the amino group, the DCC and the acrylic acid on the surface of the composite matrix in the step A1 is 1:1.2:1.1, and the molar ratio of the double bond on the surface of the filter cake to the methyl thioglycolate is 1:1.
Further, the molar ratio of carboxyl to diethanolamine on the pretreated substrate in the step A2 is 1:1, the molar ratio of hydroxyl on the surface of the filter cake to acrylic acid is 1:1, and the dosage of p-toluenesulfonic acid is 3-5% of the mass of acrylic acid.
Further, the mass ratio of the beta-cyclodextrin to the maleic anhydride in the step A3 is 1:3, the mass fraction of the acetic acid solution is 3%, and the mass ratio of the modified matrix, the modified cyclodextrin, the acrylamide and the acryloyloxyethyl trimethyl ammonium chloride is 1:5:12.5:6.32.
Further, the composite matrix is prepared by the following steps:
step B1: dispersing cellulose in DMF, adding polyethylene glycol 400, silicone oil L580, polyether polyol 330N and deionized water, mixing uniformly, stirring at a rotation speed of 150-200r/min and a temperature of 25-30 ℃, adding diphenylmethane diisocyanate, reacting for 10-15min, injecting into a mold, standing at a temperature of 20-25 ℃ for 20-25h, pulverizing and grinding to 15-20mm to obtain foam particles;
step B2: dispersing foam particles in deionized water, adding ethanol and tetrabutyl titanate, stirring at a rotation speed of 600-800r/min, a temperature of 90-100 ℃ and a pH value of 1-2 for 7-9h, filtering and drying, dispersing a substrate in ethanol, adding KH550 and deionized water, and reacting at a rotation speed of 200-300r/min and a temperature of 25-30 ℃ for 3-5h to obtain a composite matrix.
Further, the mass ratio of cellulose, polyethylene glycol 400, silicone oil L580, polyether polyol 330N, deionized water and diphenylmethane diisocyanate described in step B1 is 5:15:0.3:35:1.5:23.
Further, the dosage ratio of the foam particles, deionized water, ethanol and tetrabutyl titanate in the step B2 is 1g to 80mL to 25mL to 3mL, and the dosage of KH550 is 3-5% of the mass of the substrate.
The application has the beneficial effects that: the application provides a sewage treatment agent for treating groundwater pollution, which is prepared by dehydrating and condensing amino groups on the surface of a composite substrate and carboxyl groups on acrylic acid under the action of DCC, adding methyl thioglycolate, grafting mercapto groups on the methyl thioglycolate with double bonds on the surface of a filter cake under the irradiation of ultraviolet light to prepare a pretreatment substrate, treating the pretreatment substrate with diethanolamine to react ester groups on the surface of the pretreatment substrate with secondary amines on the diethanolamine, adding acrylation to graft a large number of double bonds on the surface to prepare a modified substrate, treating beta-cyclodextrin with maleic anhydride to react maleic anhydride ring-opening with hydroxyl groups on the beta-cyclodextrin to prepare modified cyclodextrin, polymerizing the modified cyclodextrin, the modified substrate, acrylamide and acryloyloxyethyl trimethyl ammonium chloride, forming a hyperbranched structure taking a modified matrix as a central body, taking cellulose, polyethylene glycol 400, silicone oil L580, polyether polyol 330N and diphenylmethane dioxycyanate as raw materials for the composite matrix, forming polyurethane foam on the surface of the cellulose to prepare foam particles, dispersing the foam particles in deionized water, adding tetrabutyl titanate for hydrolysis, loading nano titanium dioxide on the surface of the foam particles, finally treating with KH550 to enable the surface to be grafted with a large amount of active amino groups to prepare the composite matrix, wherein the composite matrix is porous foam which can absorb pollutants in water, simultaneously promote the pollutants to contact the nano titanium dioxide on the surface, the nano titanium dioxide surface is activated by light when being irradiated by light to form a large amount of holes and electrons, and the electrons and the holes with high energy can be regenerated on adjacent water molecules or pollutant molecules, thereby generating free radicals, the free radical has strong oxidation effect, can decompose the organic pollutant adsorbed, and the hyperbranched polymer chain side chain on the surface of the sewage treatment agent contains a cationic group, so that the pollutant with anions in the sewage can be adsorbed, and meanwhile, the cyclodextrin-containing cavity on the side chain can coat the pollutant, so that the sewage treatment effect is better.
Detailed Description
The following description of the technical solutions in the embodiments of the present application will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present application, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
Example 1
The preparation method of the sewage treatment agent for treating groundwater pollution specifically comprises the following steps:
step A1: dispersing the composite matrix in toluene, adding DCC and acrylic acid, reacting for 2 hours at the rotation speed of 200r/min and the temperature of 25 ℃, filtering to remove filtrate, dispersing the filter cake in deionized water, adding methyl thioglycolate, and reacting for 30 minutes at the rotation speed of 60r/min and the temperature of 20 ℃ and under the irradiation of 365nm ultraviolet lamp to obtain a pretreated matrix;
step A2: mixing a pretreated substrate, diethanolamine and methanol, stirring for 20 hours at a rotating speed of 150r/min and a temperature of 20 ℃ and a pH value of 9, filtering to remove filtrate, dispersing a filter cake in toluene, adding acrylic acid and p-toluenesulfonic acid, and reacting for 6 hours at a rotating speed of 60r/min and a temperature of 110 ℃ to obtain a modified substrate;
step A3: dissolving beta-cyclodextrin in acetic acid solution, stirring and adding maleic anhydride at the rotation speed of 120r/min and the temperature of 75 ℃ for reaction for 3 hours to obtain modified cyclodextrin, dispersing a modified matrix, modified cyclodextrin, acrylamide and acryloyloxyethyl trimethyl ammonium chloride in deionized water, introducing nitrogen for protection, stirring and adding potassium persulfate at the rotation speed of 150r/min and the temperature of 50 ℃ and the pH value of 7, reacting for 6 hours, filtering to remove filtrate, and crushing a substrate to obtain the sewage treatment agent for treating groundwater pollution.
The molar ratio of the amino group to the DCC to the acrylic acid on the surface of the composite matrix in the step A1 is 1:1.2:1.1, and the molar ratio of the double bond on the surface of the filter cake to the methyl thioglycolate is 1:1.
The molar ratio of carboxyl to diethanolamine on the pretreated substrate in the step A2 is 1:1, the molar ratio of hydroxyl on the surface of the filter cake to acrylic acid is 1:1, and the dosage of p-toluenesulfonic acid is 3% of the mass of acrylic acid.
The mass ratio of the beta-cyclodextrin to the maleic anhydride in the step A3 is 1:3, the mass fraction of the acetic acid solution is 3%, and the mass ratio of the modified matrix, the modified cyclodextrin, the acrylamide and the acryloyloxyethyl trimethyl ammonium chloride is 1:5:12.5:6.32.
The composite matrix is prepared by the following steps:
step B1: dispersing cellulose in DMF, adding polyethylene glycol 400, silicone oil L580, polyether polyol 330N and deionized water, mixing uniformly, stirring at a rotation speed of 150r/min and a temperature of 25 ℃, adding diphenylmethane diisocyanate, reacting for 10min, injecting into a mold, standing at a temperature of 20 ℃ for 20h, and grinding to 15mm to obtain foam particles;
step B2: dispersing foam particles in deionized water, adding ethanol and tetrabutyl titanate, stirring for 7 hours at the rotation speed of 600r/min and the temperature of 90 ℃ and the pH value of 1, filtering and drying, dispersing a substrate in ethanol, adding KH550 and deionized water, and reacting for 3 hours at the rotation speed of 200r/min and the temperature of 25 ℃ to obtain a composite matrix.
The mass ratio of the cellulose, the polyethylene glycol 400, the silicone oil L580, the polyether polyol 330N, the deionized water and the diphenylmethane diisocyanate in the step B1 is 5:15:0.3:35:1.5:23.
The dosage ratio of the foam particles, deionized water, ethanol and tetrabutyl titanate in the step B2 is 1g to 80mL to 25mL to 3mL, and the dosage of KH550 is 3% of the mass of the substrate.
Example 2
The preparation method of the sewage treatment agent for treating groundwater pollution specifically comprises the following steps:
step A1: dispersing the composite matrix in toluene, adding DCC and acrylic acid, reacting for 2.5 hours at the rotation speed of 200r/min and the temperature of 28 ℃, filtering to remove filtrate, dispersing the filter cake in deionized water, adding methyl thioglycolate, and reacting for 35 minutes at the rotation speed of 60r/min and the temperature of 23 ℃ under the irradiation of 365nm ultraviolet lamp to obtain a pretreated matrix;
step A2: mixing a pretreated substrate, diethanolamine and methanol, stirring for 23 hours at the rotating speed of 150r/min and the temperature of 23 ℃ and the pH value of 10, filtering to remove filtrate, dispersing a filter cake in toluene, adding acrylic acid and p-toluenesulfonic acid, and reacting for 7 hours at the rotating speed of 60r/min and the temperature of 115 ℃ to obtain a modified substrate;
step A3: dissolving beta-cyclodextrin in acetic acid solution, stirring and adding maleic anhydride at the rotation speed of 120r/min and the temperature of 78 ℃ for reaction for 4 hours to obtain modified cyclodextrin, dispersing a modified matrix, modified cyclodextrin, acrylamide and acryloyloxyethyl trimethyl ammonium chloride in deionized water, introducing nitrogen for protection, stirring and adding potassium persulfate at the rotation speed of 150r/min and the temperature of 60 ℃ and the pH value of 8, reacting for 7 hours, filtering to remove filtrate, and crushing a substrate to obtain the sewage treatment agent for treating groundwater pollution.
The molar ratio of the amino group to the DCC to the acrylic acid on the surface of the composite matrix in the step A1 is 1:1.2:1.1, and the molar ratio of the double bond on the surface of the filter cake to the methyl thioglycolate is 1:1.
The molar ratio of carboxyl to diethanolamine on the pretreated substrate in the step A2 is 1:1, the molar ratio of hydroxyl on the surface of the filter cake to acrylic acid is 1:1, and the dosage of p-toluenesulfonic acid is 4% of the mass of acrylic acid.
The mass ratio of the beta-cyclodextrin to the maleic anhydride in the step A3 is 1:3, the mass fraction of the acetic acid solution is 3%, and the mass ratio of the modified matrix, the modified cyclodextrin, the acrylamide and the acryloyloxyethyl trimethyl ammonium chloride is 1:5:12.5:6.32.
The composite matrix is prepared by the following steps:
step B1: dispersing cellulose in DMF, adding polyethylene glycol 400, silicone oil L580, polyether polyol 330N and deionized water, mixing uniformly, stirring at a rotation speed of 150r/min and a temperature of 28 ℃, adding diphenylmethane diisocyanate, reacting for 13min, injecting into a mold, standing at a temperature of 23 ℃ for 23h, and grinding to 18mm to obtain foam particles;
step B2: dispersing foam particles in deionized water, adding ethanol and tetrabutyl titanate, stirring at a rotation speed of 600r/min and a temperature of 95 ℃ and a pH value of 2 for 8 hours, filtering and drying, dispersing a substrate in ethanol, adding KH550 and deionized water, and reacting at a rotation speed of 200r/min and a temperature of 30 ℃ for 4 hours to obtain a composite matrix.
The mass ratio of the cellulose, the polyethylene glycol 400, the silicone oil L580, the polyether polyol 330N, the deionized water and the diphenylmethane diisocyanate in the step B1 is 5:15:0.3:35:1.5:23.
The dosage ratio of the foam particles, deionized water, ethanol and tetrabutyl titanate in the step B2 is 1g to 80mL to 25mL to 3mL, and the dosage of KH550 is 4% of the mass of the substrate.
Example 3
The preparation method of the sewage treatment agent for treating groundwater pollution specifically comprises the following steps:
step A1: dispersing the composite matrix in toluene, adding DCC and acrylic acid, reacting for 3 hours at the rotation speed of 300r/min and the temperature of 30 ℃, filtering to remove filtrate, dispersing the filter cake in deionized water, adding methyl thioglycolate, and reacting for 40 minutes at the rotation speed of 80r/min and the temperature of 25 ℃ and under the irradiation of 365nm ultraviolet lamp to obtain a pretreated matrix;
step A2: mixing a pretreated substrate, diethanolamine and methanol, stirring for 25 hours at the rotation speed of 200r/min and the temperature of 25 ℃ and the pH value of 10, filtering to remove filtrate, dispersing a filter cake in toluene, adding acrylic acid and p-toluenesulfonic acid, and reacting for 8 hours at the rotation speed of 80r/min and the temperature of 120 ℃ to obtain a modified substrate;
step A3: dissolving beta-cyclodextrin in acetic acid solution, stirring and adding maleic anhydride at the rotation speed of 150r/min and the temperature of 80 ℃ for reaction for 5 hours to obtain modified cyclodextrin, dispersing a modified matrix, modified cyclodextrin, acrylamide and acryloyloxyethyl trimethyl ammonium chloride in deionized water, introducing nitrogen for protection, stirring and adding potassium persulfate at the rotation speed of 200r/min and the temperature of 70 ℃ and the pH value of 8 for reaction for 8 hours, filtering to remove filtrate, and crushing a substrate to obtain the sewage treatment agent for treating groundwater pollution.
The molar ratio of the amino group to the DCC to the acrylic acid on the surface of the composite matrix in the step A1 is 1:1.2:1.1, and the molar ratio of the double bond on the surface of the filter cake to the methyl thioglycolate is 1:1.
The molar ratio of carboxyl to diethanolamine on the pretreated substrate in the step A2 is 1:1, the molar ratio of hydroxyl on the surface of the filter cake to acrylic acid is 1:1, and the dosage of p-toluenesulfonic acid is 5% of the mass of acrylic acid.
The mass ratio of the beta-cyclodextrin to the maleic anhydride in the step A3 is 1:3, the mass fraction of the acetic acid solution is 3%, and the mass ratio of the modified matrix, the modified cyclodextrin, the acrylamide and the acryloyloxyethyl trimethyl ammonium chloride is 1:5:12.5:6.32.
The composite matrix is prepared by the following steps:
step B1: dispersing cellulose in DMF, adding polyethylene glycol 400, silicone oil L580, polyether polyol 330N and deionized water, mixing uniformly, stirring at a rotation speed of 200r/min and a temperature of 30 ℃, adding diphenylmethane diisocyanate, reacting for 15min, injecting into a mold, standing at a temperature of 25 ℃ for 25h, and grinding to 20mm to obtain foam particles;
step B2: dispersing foam particles in deionized water, adding ethanol and tetrabutyl titanate, stirring for 9 hours at the rotation speed of 800r/min, the temperature of 100 ℃ and the pH value of 2, filtering and drying, dispersing a substrate in ethanol, adding KH550 and deionized water, and reacting for 5 hours at the rotation speed of 300r/min and the temperature of 30 ℃ to obtain a composite matrix.
The mass ratio of the cellulose, the polyethylene glycol 400, the silicone oil L580, the polyether polyol 330N, the deionized water and the diphenylmethane diisocyanate in the step B1 is 5:15:0.3:35:1.5:23.
The dosage ratio of the foam particles, deionized water, ethanol and tetrabutyl titanate in the step B2 is 1g to 80mL to 25mL to 3mL, and the dosage of KH550 is 5% of the mass of the substrate.
Comparative example 1
In this comparative example, foam particles were dispersed in ethanol, KH550 and deionized water were added, and the reaction was carried out at a rotation speed of 200r/min and a temperature of 30℃for 4 hours, to obtain a product instead of a composite matrix, and the other steps were the same.
Comparative example 2
In this comparative example, the composite matrix was dispersed in toluene, DCC and acrylic acid were added, and the reaction was carried out at a rotation speed of 200r/min and a temperature of 28 ℃ for 2.5 hours, to obtain a product instead of the modified matrix, and the other steps were the same.
Comparative example 3
This comparative example was compared to example 1 without the addition of modified cyclodextrin, the remainder of the procedure being identical.
1L of wastewater in a certain place is respectively taken, COD3820mg/L, NH3-N638mg/L, TN78.2mg/L, TP85.6mg/L and SS1428mg/L, and under the condition of rotating speed of 200r/min, 2g of sewage treatment agents prepared in examples 1 to 3 and comparative examples 1 to 2 are respectively stirred and added, and are stirred for 120min, standing and sedimentation are carried out, water samples at the position of 2cm below the liquid level are taken for analysis, and the removal rate is calculated, and the results are shown in the following table.
The table shows that the application has good sewage treatment effect.
The foregoing is merely illustrative and explanatory of the principles of the application, as various modifications and additions may be made to the specific embodiments described, or similar thereto, by those skilled in the art, without departing from the principles of the application or beyond the scope of the appended claims.
Claims (7)
1. A preparation method of a sewage treatment agent for treating groundwater pollution is characterized by comprising the following steps: the method specifically comprises the following steps:
step A1: dispersing the composite matrix in toluene, adding DCC and acrylic acid for reaction, filtering to remove filtrate, dispersing filter cake in deionized water, adding methyl thioglycolate for reaction, and preparing a pretreated matrix;
step A2: mixing and stirring a pretreatment matrix, diethanolamine and methanol, filtering to remove filtrate, dispersing a filter cake in toluene, adding acrylic acid and p-toluenesulfonic acid, and reacting to obtain a modified matrix;
step A3: dissolving beta-cyclodextrin in acetic acid solution, stirring and adding maleic anhydride, reacting to obtain modified cyclodextrin, dispersing a modified matrix, modified cyclodextrin, acrylamide and acryloyloxyethyl trimethyl ammonium chloride in deionized water, introducing nitrogen for protection, stirring and adding potassium persulfate, reacting, filtering to remove filtrate, and crushing a substrate to obtain a sewage treatment agent for treating groundwater pollution;
the composite matrix is prepared by the following steps:
step B1: dispersing cellulose in DMF, adding polyethylene glycol 400, silicone oil L580, polyether polyol 330N and deionized water, mixing and stirring, adding diphenylmethane diisocyanate, reacting, injecting into a mold, standing, pulverizing and grinding to obtain foam particles;
step B2: dispersing foam particles in deionized water, adding ethanol and tetrabutyl titanate, stirring, filtering and drying, dispersing a substrate in ethanol, adding KH550 and deionized water, and reacting to obtain the composite matrix.
2. The method for preparing the sewage treatment agent for treating groundwater pollution according to claim 1, wherein: the molar ratio of the amino group to the DCC to the acrylic acid on the surface of the composite matrix in the step A1 is 1:1.2:1.1, and the molar ratio of the double bond on the surface of the filter cake to the methyl thioglycolate is 1:1.
3. The method for preparing the sewage treatment agent for treating groundwater pollution according to claim 1, wherein: the molar ratio of carboxyl to diethanolamine on the pretreated substrate in the step A2 is 1:1, the molar ratio of hydroxyl on the surface of the filter cake to acrylic acid is 1:1, and the dosage of p-toluenesulfonic acid is 3-5% of the mass of acrylic acid.
4. The method for preparing the sewage treatment agent for treating groundwater pollution according to claim 1, wherein: the mass ratio of the beta-cyclodextrin to the maleic anhydride in the step A3 is 1:3, and the mass ratio of the modified matrix, the modified cyclodextrin, the acrylamide and the acryloyloxyethyl trimethyl ammonium chloride is 1:5:12.5:6.32.
5. The method for preparing the sewage treatment agent for treating groundwater pollution according to claim 1, wherein: the mass ratio of the cellulose, the polyethylene glycol 400, the silicone oil L580, the polyether polyol 330N, the deionized water and the diphenylmethane diisocyanate in the step B1 is 5:15:0.3:35:1.5:23.
6. The method for preparing the sewage treatment agent for treating groundwater pollution according to claim 1, wherein: the dosage ratio of the foam particles, deionized water, ethanol and tetrabutyl titanate in the step B2 is 1g to 80mL to 25mL to 3mL, and the dosage of KH550 is 3-5% of the mass of the substrate.
7. A sewage treatment agent for treating groundwater pollution is characterized in that: the preparation method according to any one of claims 1-6.
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