CN116874022B - Sewage purification composite material and preparation method thereof - Google Patents
Sewage purification composite material and preparation method thereof Download PDFInfo
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- CN116874022B CN116874022B CN202311141133.6A CN202311141133A CN116874022B CN 116874022 B CN116874022 B CN 116874022B CN 202311141133 A CN202311141133 A CN 202311141133A CN 116874022 B CN116874022 B CN 116874022B
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- 239000010865 sewage Substances 0.000 title claims abstract description 138
- 238000000746 purification Methods 0.000 title claims abstract description 90
- 239000002131 composite material Substances 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000011282 treatment Methods 0.000 claims abstract description 118
- 239000000843 powder Substances 0.000 claims abstract description 38
- 239000000463 material Substances 0.000 claims abstract description 31
- 238000011221 initial treatment Methods 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 66
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 55
- 239000007788 liquid Substances 0.000 claims description 49
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 45
- 239000000126 substance Substances 0.000 claims description 44
- 238000010438 heat treatment Methods 0.000 claims description 41
- 239000008367 deionised water Substances 0.000 claims description 37
- 229910021641 deionized water Inorganic materials 0.000 claims description 37
- 239000007787 solid Substances 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 32
- 238000003756 stirring Methods 0.000 claims description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 25
- 238000000498 ball milling Methods 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 24
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 21
- 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 21
- 239000011248 coating agent Substances 0.000 claims description 21
- 238000000576 coating method Methods 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 20
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 20
- 229960000892 attapulgite Drugs 0.000 claims description 19
- 229910052625 palygorskite Inorganic materials 0.000 claims description 19
- 239000000377 silicon dioxide Substances 0.000 claims description 19
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 16
- 239000005011 phenolic resin Substances 0.000 claims description 16
- 229920001568 phenolic resin Polymers 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 15
- 230000001105 regulatory effect Effects 0.000 claims description 15
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 14
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 12
- 229920000858 Cyclodextrin Polymers 0.000 claims description 12
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 10
- 229920002125 Sokalan® Polymers 0.000 claims description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 10
- 239000007822 coupling agent Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 239000004584 polyacrylic acid Substances 0.000 claims description 10
- 239000001116 FEMA 4028 Substances 0.000 claims description 9
- 229960004853 betadex Drugs 0.000 claims description 9
- 238000004321 preservation Methods 0.000 claims description 8
- 235000012239 silicon dioxide Nutrition 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 238000005286 illumination Methods 0.000 claims description 5
- 238000007789 sealing Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 4
- 230000000630 rising effect Effects 0.000 claims 3
- 238000004519 manufacturing process Methods 0.000 claims 2
- 230000010355 oscillation Effects 0.000 claims 2
- 230000000694 effects Effects 0.000 abstract description 29
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 24
- 238000001179 sorption measurement Methods 0.000 abstract description 21
- 239000003344 environmental pollutant Substances 0.000 abstract description 16
- 231100000719 pollutant Toxicity 0.000 abstract description 16
- 230000008929 regeneration Effects 0.000 abstract description 13
- 238000011069 regeneration method Methods 0.000 abstract description 13
- 239000004408 titanium dioxide Substances 0.000 abstract description 12
- 230000002411 adverse Effects 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 238000012360 testing method Methods 0.000 description 15
- 230000001699 photocatalysis Effects 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 238000004064 recycling Methods 0.000 description 7
- -1 methyl butyl Chemical group 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000004480 active ingredient Substances 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- YZOUYRAONFXZSI-SBHWVFSVSA-N (1S,3R,5R,6R,8R,10R,11R,13R,15R,16R,18R,20R,21R,23R,25R,26R,28R,30R,31S,33R,35R,36R,37S,38R,39S,40R,41S,42R,43S,44R,45S,46R,47S,48R,49S)-5,10,15,20,25,30,35-heptakis(hydroxymethyl)-37,39,40,41,42,43,44,45,46,47,48,49-dodecamethoxy-2,4,7,9,12,14,17,19,22,24,27,29,32,34-tetradecaoxaoctacyclo[31.2.2.23,6.28,11.213,16.218,21.223,26.228,31]nonatetracontane-36,38-diol Chemical compound O([C@@H]([C@H]([C@@H]1OC)OC)O[C@H]2[C@@H](O)[C@@H]([C@@H](O[C@@H]3[C@@H](CO)O[C@@H]([C@H]([C@@H]3O)OC)O[C@@H]3[C@@H](CO)O[C@@H]([C@H]([C@@H]3OC)OC)O[C@@H]3[C@@H](CO)O[C@@H]([C@H]([C@@H]3OC)OC)O[C@@H]3[C@@H](CO)O[C@@H]([C@H]([C@@H]3OC)OC)O3)O[C@@H]2CO)OC)[C@H](CO)[C@H]1O[C@@H]1[C@@H](OC)[C@H](OC)[C@H]3[C@@H](CO)O1 YZOUYRAONFXZSI-SBHWVFSVSA-N 0.000 description 3
- IQUPABOKLQSFBK-UHFFFAOYSA-N 2-nitrophenol Chemical compound OC1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-UHFFFAOYSA-N 0.000 description 3
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 3
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000002159 abnormal effect Effects 0.000 description 3
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- 238000010335 hydrothermal treatment Methods 0.000 description 3
- 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 3
- 229940012189 methyl orange Drugs 0.000 description 3
- 229960000907 methylthioninium chloride Drugs 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- 239000010802 sludge Substances 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000011206 ternary composite Substances 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
- 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
- C02F2101/34—Organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
-
- 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
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention provides a sewage purification composite material and a preparation method thereof, belonging to the field of sewage treatment. The preparation method of the sewage purification composite material comprises the following steps: powder treatment, primary treatment, secondary treatment and tertiary treatment. The preparation method of the sewage purification composite material can effectively reduce the adverse effects of pollutant components, content and pH on the sewage purification composite material and improve the low-temperature activity of the sewage purification composite material; aiming at sewage with the pH value of more than 8.5, the dye content of more than 60mg/L and complex components, the effective sewage purification can be realized; further, the stability of the sewage purifying effect after the titanium dioxide is compounded with the adsorption material is improved; the adverse effect of the regeneration treatment on the sewage purification composite material is reduced, and the long-acting catalytic performance of the composite material is improved.
Description
Technical Field
The invention relates to the field of sewage purification, in particular to a sewage purification composite material and a preparation method thereof.
Background
Water is an important resource in the life process of people, and a large amount of water resource is consumed every day. In this case, it is more important to treat industrial sewage, and the recovery and utilization of industrial sewage are enhanced on the basis of saving water resources and reducing waste. Therefore, the method has important significance in the research and development of industrial sewage treatment means.
In the existing sewage purification methods, such as an adsorption method and a membrane separation method, the pollutants in the sewage are concentrated after being enriched and transferred by the adsorption action of the pollutants, but the pollutants in the sewage are not thoroughly degraded in the adsorption or membrane separation process, and secondary pollution is easy to generate in the transfer and treatment processes of the adsorption materials; the coagulation method is to put coagulant, flocculant, etc. into sewage to coagulate and precipitate pollutants in the sewage, but the addition amount of the coagulation auxiliary agent is large, the treatment cost is high, a large amount of coagulated sludge can be produced, and the sludge needs to be treated for the second time; the biological method adopts activated sludge containing aerobic/anaerobic microorganisms to carry out biochemical treatment on sewage, but has narrow application range, poor treatment effect on sewage with complex components and poor biodegradability (such as sewage in a chemical industry park, and the like), and longer treatment period; the ozone oxidation method adopts ozone with strong oxidability and is matched with electrolysis equipment to treat sewage, but the equipment cost is high, the consumption of electrodes and electric energy is large, and the comprehensive treatment cost is high.
In recent years, titanium dioxide is used as an emerging photocatalytic oxidation material, and has good application prospect in the field of sewage purification due to the characteristics of safety, no toxicity, strong chemical stability, no secondary pollution, high catalytic oxidation activity and the like. However, the inventor has found that the conventional titanium dioxide sewage purification material is not effective in purifying sewage due to the influence of the pollutant components and contents, acid-base property and temperature in sewage. Especially for the sewage with the pH value of more than 8.5 and high dye content (more than 60 mg/L) and complex pollutant components (such as heavy metal components and the like), effective sewage purification cannot be realized. Meanwhile, the low-temperature activity of the titanium dioxide sewage purification material is still to be further improved, and the ideal sewage purification effect can not be obtained under the lower-temperature condition aiming at the sewage, so that the sewage purification efficiency is ensured.
Furthermore, in order to improve the sewage treatment performance of the titanium dioxide in the prior art, the titanium dioxide is combined with the activated carbon adsorption material, and the pollutants in the sewage are enriched on the surface through the adsorption performance of the activated carbon adsorption material, so that the pollutants are catalytically degraded by the titanium dioxide. The inventor finds that the purifying effect on sewage is unstable after the titanium dioxide is compounded with the adsorption material; and after the adsorption material reaches adsorption equilibrium, the long-acting catalytic performance of the titanium dioxide can be influenced in the regeneration treatment process of the adsorption material, so that the effective service life of the titanium dioxide is reduced.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention provides the sewage purification composite material and the preparation method thereof, which can effectively reduce the adverse effects of pollutant components, content and pH on the sewage purification composite material and improve the low-temperature activity of the sewage purification composite material; aiming at sewage with the pH value of more than 8.5, the dye content of more than 60mg/L and complex components, the effective sewage purification can be realized; further, the stability of the sewage purifying effect after the titanium dioxide is compounded with the adsorption material is improved; the adverse effect of the regeneration treatment on the sewage purification composite material is reduced, and the long-acting catalytic performance of the composite material is improved.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
the preparation method of the sewage purification composite material comprises the following steps: powder treatment, primary treatment, secondary treatment and tertiary treatment.
The powder treatment method comprises the steps of putting macroporous silica, diatomite, attapulgite and sodium dodecyl sulfate into a ball mill, controlling the ball material water ratio to be 6-7:1:0.35-0.4, ball milling at 200-300rpm, ball milling for 30-50min, and drying to obtain ball milling materials; putting ball-milled substances and deionized water into a high-pressure reaction kettle, adopting nitrogen to replace air in the high-pressure reaction kettle completely, regulating the pressure in the high-pressure reaction kettle to be 1-1.2MPa, sealing the high-pressure reaction kettle, heating to 180-190 ℃ at the heating rate of 0.4-0.5 ℃/min, preserving heat for 10-12h, naturally cooling to normal temperature, decompressing to normal pressure, separating out solid substances in the high-pressure reaction kettle, drying the solid substances to constant weight, putting the solid substances into 2-3 times of volume of modified liquid, stirring and heating to 40-50 ℃, preserving heat and stirring for 4-5h, centrifugally separating to obtain centrifugate, washing the centrifugate for 1-2 times by adopting 6-8 times of volume of deionized water, and drying to constant weight to obtain modified powder.
In the powder treatment, the weight ratio of macroporous silicon dioxide to diatomite to attapulgite to sodium dodecyl sulfate is 3-4:7-8:7-8:0.06-0.07;
the weight ratio of the ball milling material to the deionized water is 1:1.5-1.8;
the modifying liquid is ethanol solution of the titanate coupling agent 102; the concentration of the titanate coupling agent 102 in the modified liquid is 2.5-3wt%; the volume concentration of the ethanol solution is 92-95%.
In the powder treatment, the particle size of macroporous silica is 150-180 meshes; the particle size of the diatomite is 150-200 meshes; the particle size of the attapulgite is 120-150 meshes.
The one-time treatment method comprises the steps of adding methylation-beta-cyclodextrin into methanol, dispersing uniformly, adding butyl methacrylate and tetrabutyl titanate, oscillating at 100-200rpm for 10-12h, evaporating at 65-70 ℃ to remove methanol, placing the steaming residue in an environment with the vacuum degree of 0.06-0.08MPa, and keeping the temperature at 40-50 ℃ for 8-10h to obtain a coating; and (3) adding polyacrylic acid, acrylamide and a coating into deionized water, regulating the pH to 5.5-6.0, stirring and heating to 30-35 ℃ in a nitrogen atmosphere environment, adding tetramethyl ethylenediamine and azobisisobutyronitrile hydrochloride at a constant temperature, and carrying out heat preservation for 4-6 hours under an illumination condition to obtain the primary treatment liquid.
In the one-time treatment, the weight ratio of the methylation-beta-cyclodextrin to the butyl methacrylate to the tetrabutyl titanate to the methanol is 50-55:1.3-1.5:8-9:120-130;
the weight ratio of polyacrylic acid, acrylamide, coating, tetramethyl ethylenediamine, azo diisobutylamidine hydrochloride and deionized water is 0.8-0.9:35-40:14-15:0.15-0.2:0.08-0.1:300-350.
The secondary treatment method comprises the steps of adding water-soluble phenolic resin, modified powder, primary treatment liquid and resorcinol into deionized water, stirring and heating to 37-40 ℃, preserving heat, and stirring at 300-400rpm for 40-60 min; transferring into a constant temperature box, standing for 14-16h at 60-70deg.C, and separating out solid; transferring the solid into a calciner, heating to 700-750 ℃ at a heating rate of 2-3 ℃/min in a nitrogen atmosphere environment, preserving heat for 2-3h, and naturally cooling; and (3) when the mixture is cooled to 110-120 ℃, regulating the pressure to 0.2-0.4MPa by adopting nitrogen, continuously introducing water vapor for 30-40min at an introducing rate of 3-5L/min, drying and grinding uniformly to obtain a secondary treated product.
In the secondary treatment, the weight ratio of the water-soluble phenolic resin to the modified powder to the primary treatment liquid to the resorcinol to the deionized water is 8-10:15-16:28-30:0.02-0.03:200-250;
the pressure of the water vapor is 0.2-0.4MPa, and the temperature is 120.5-144 ℃.
The method for the tertiary treatment comprises the steps of putting the secondary treatment substance into tertiary treatment liquid with the volume of 4-5 times, stirring for 2-3 hours, and filtering out solid substances; transferring the solid into a calciner, heating to 400-420 ℃ at a heating rate of 0.8-1.2 ℃/min, preserving heat for 3-4h, and naturally cooling to obtain the sewage purification composite material.
In the three treatments, the three treatment solutions are absolute ethanol solutions in which tetrabutyl titanate is dissolved; the concentration of tetrabutyl titanate in the tertiary treatment liquid is 2-2.5wt%.
The sewage purifying composite material is prepared through the preparation process.
Compared with the prior art, the invention has the beneficial effects that:
(1) The preparation method of the sewage purification composite material comprises the steps of mixing and ball milling macroporous silicon dioxide, diatomite, attapulgite and sodium dodecyl sulfate in the powder treatment process, and then carrying out high-temperature and high-pressure hydrothermal treatment and modification liquid treatment on ball milling substances to prepare modified powder; after preparing a coating by adopting the matching of the methylation-beta-cyclodextrin and the butyl methacrylate and the tetrabutyl titanate, the coating is used in the polymerization process of acrylamide to prepare primary treatment liquid; then, the water-soluble phenolic resin, the modified powder and the primary treatment liquid are crosslinked and combined, and the inorganic porous adsorption material, the phenolic resin-based carbon material and the photocatalytic active ingredient ternary composite secondary treatment substance is prepared through the processes of gel, aging, carbonization and high-temperature steam treatment; the secondary treatment substance is treated for three times by adopting a tertiary treatment liquid containing tetrabutyl titanate, and then the sewage purification composite material is prepared by calcining; the adverse effects of pollutant components, content and pH on the sewage purification composite material can be effectively reduced, and the low-temperature activity of the sewage purification composite material is improved; aiming at sewage with the pH value of more than 8.5, the dye content of more than 60mg/L and complex components, the effective sewage purification can be realized; further, the stability of the sewage purifying effect after the titanium dioxide is compounded with the adsorption material is improved; the adverse effect of the regeneration treatment on the sewage purification composite material is reduced, and the long-acting catalytic performance of the composite material is improved.
(2) Through experiments, the sewage purification composite material provided by the invention has the advantages that under the condition that the addition amount is 15g/L, after the sewage purification treatment is carried out on simulated sewage with the temperature of 12 ℃ and the pH value of 9.5 for 16 hours, the removal rate of nitrophenol in the sewage is 97.1-97.4%, the removal rate of methyl orange is 99.0-99.1%, the removal rate of Congo red is 98.0-98.3%, the removal rate of methylene blue is 98.5-98.9%, and Cu is removed 2+ The removal rate is 98.9-99.2%, zn 2+ The removal rate is 98.9-99.1%, the methyl tertiary butyl ether removal rate is 98.3-98.7%, and the decoloring rate is 98.3-98.6%.
(3) Through experiments, the sewage purification composite material of the invention has the initial COD at the temperature of 12 ℃ under the condition that the addition amount is 15g/L cr After the chemical industrial park comprehensive sewage (secondary sedimentation tank supernatant) with the value of 164mg/L is subjected to sewage purification treatment, COD (chemical oxygen demand) cr The value is 17.5-18.4mg/L, COD cr The removal rate is 88.8-89.3%, and the decoloring rate is 98.3-98.8%.
(4) Through experiments, after the sewage purification composite material is repeatedly regenerated and recycled for 10 times, the temperature is 12 ℃ and the initial COD is obtained cr After the chemical industrial park comprehensive sewage (secondary sedimentation tank supernatant) with the value of 164mg/L is subjected to sewage purification treatment, COD (chemical oxygen demand) cr The value is 28.5-29.4mg/L, COD cr The removal rate is 82.1-82.6%, and the decoloring rate is 93.9-94.4%; meanwhile, in the sewage purification process of 10 times, the sewage purification performance is stable, and no COD exists cr Abnormal fluctuation of the removal rate and the decoloring rate occurs.
Detailed Description
Specific embodiments of the present invention will now be described in order to provide a clearer understanding of the technical features, objects and effects of the present invention.
Example 1
A preparation method of a sewage purification composite material specifically comprises the following steps:
1. powder treatment
Adding macroporous silica, diatomite, attapulgite and sodium dodecyl sulfate into a ball mill, controlling the ball material water ratio to be 6:1:0.35, ball milling at 200rpm, ball milling for 30min, and drying to obtain a ball-milled material; putting ball-milled substances and deionized water into a high-pressure reaction kettle, adopting nitrogen to replace air in the high-pressure reaction kettle completely, regulating the pressure in the high-pressure reaction kettle to be 1MPa, sealing the high-pressure reaction kettle, heating to 180 ℃ at a heating rate of 0.4 ℃/min, preserving heat for 10 hours, naturally cooling to normal temperature, decompressing to normal pressure, separating out solid substances in the high-pressure reaction kettle, drying the solid substances to constant weight, putting the solid substances into a 2-time volume modified liquid, stirring and heating to 40 ℃, preserving heat and stirring for 4 hours, centrifugally separating to obtain a centrifugate, washing the centrifugate for 1 time by adopting 6-time volume deionized water, and drying to constant weight to obtain modified powder.
Wherein the weight ratio of macroporous silicon dioxide to diatomite to attapulgite to sodium dodecyl sulfate is 3:7:7:0.06.
The particle size of the macroporous silica is 150 meshes; the particle size of the diatomite is 150 meshes; the particle size of the attapulgite is 120 meshes.
The weight ratio of the ball-milling material to the deionized water is 1:1.5.
The modifying liquid is an ethanol solution of the titanate coupling agent 102. The concentration of titanate coupling agent 102 in the modified liquid was 2.5wt%. The volume concentration of the ethanol solution was 92%.
2. One-time treatment
Adding methyl-beta-cyclodextrin into methanol, dispersing uniformly, adding butyl methacrylate and tetrabutyl titanate, oscillating at 100rpm for 10 hours, evaporating at 65 ℃ to remove the methanol, placing the residue in an environment with the vacuum degree of 0.06MPa, and keeping the temperature at 40 ℃ for 8 hours to prepare a coating; and (3) adding polyacrylic acid, acrylamide and a coating into deionized water, regulating the pH to 5.5, stirring and heating to 30 ℃ in a nitrogen atmosphere, adding tetramethyl ethylenediamine and azobisisobutylamin hydrochloride in a heat preservation manner, and carrying out heat preservation for 4 hours under an illumination condition to obtain the primary treatment liquid.
Wherein the weight ratio of the methylated-beta-cyclodextrin to the methyl butyl methacrylate to the methyl tetrabutyl titanate to the methyl alcohol is 50:1.3:8:120.
The weight ratio of polyacrylic acid, acrylamide, coating, tetramethyl ethylenediamine, azo diisobutylamidine hydrochloride and deionized water is 0.8:35:14:0.15:0.08:300.
3. Secondary treatment
Adding water-soluble phenolic resin, modified powder, primary treatment liquid and resorcinol into deionized water, stirring and heating to 37 ℃, preserving heat, and stirring at 300rpm for 40 min; transferring into a constant temperature box, standing for 14h at 60 ℃ and separating out solid matters; transferring the solid into a calciner, heating to 700 ℃ at a heating rate of 2 ℃/min in a nitrogen atmosphere environment, preserving heat for 2 hours, and naturally cooling; and (3) when the mixture is cooled to 110 ℃, regulating the pressure to 0.2MPa by adopting nitrogen, continuously introducing water vapor for 30min at an introducing rate of 3L/min, drying and grinding uniformly to obtain a secondary treatment product.
Wherein the weight ratio of the water-soluble phenolic resin to the modified powder to the primary treatment liquid to the resorcinol to the deionized water is 8:15:28:0.02:200.
The pressure of the water vapor was 0.2MPa and the temperature was 120.5 ℃.
4. Three treatments
Adding the secondary treatment substance into the tertiary treatment liquid with the volume of 4 times, stirring for 2 hours, and filtering out solid substances; transferring the solid into a calciner, heating to 400 ℃ at a heating rate of 0.8 ℃/min, preserving heat for 3 hours, and naturally cooling to obtain the sewage purification composite material.
In the three treatments, the three treatment solutions are absolute ethanol solutions in which tetrabutyl titanate is dissolved. The concentration of tetrabutyl titanate in the tertiary treatment solution was 2wt%.
Example 2
A preparation method of a sewage purification composite material specifically comprises the following steps:
1. powder treatment
Adding macroporous silica, diatomite, attapulgite and sodium dodecyl sulfate into a ball mill, controlling the ball material water ratio to be 6.5:1:0.37, ball milling at a speed of 250rpm, ball milling for 40min, and drying to obtain a ball-milled material; putting ball-milled substances and deionized water into a high-pressure reaction kettle, adopting nitrogen to replace air in the high-pressure reaction kettle completely, regulating the pressure in the high-pressure reaction kettle to be 1.1MPa, sealing the high-pressure reaction kettle, heating to 185 ℃ at a heating rate of 0.45 ℃/min, preserving heat for 11 hours, naturally cooling to normal temperature, decompressing to normal pressure, separating out solid substances in the high-pressure reaction kettle, drying the solid substances to constant weight, putting the solid substances into a modified liquid with 2.5 times of volume, stirring and heating to 45 ℃, preserving heat and stirring for 4.5 hours, centrifugally separating to obtain a centrifugate, washing the centrifugate with deionized water with 7 times of volume for 2 times, and drying to constant weight to obtain modified powder.
Wherein the weight ratio of macroporous silicon dioxide to diatomite to attapulgite to sodium dodecyl sulfate is 3.5:7.5:7.5:0.065.
The particle size of the macroporous silica is 160 meshes; the particle size of the diatomite is 180 meshes; the particle size of the attapulgite is 130 meshes.
The weight ratio of the ball-milling material to the deionized water is 1:1.7.
The modifying liquid is an ethanol solution of the titanate coupling agent 102. The concentration of titanate coupling agent 102 in the modified liquid was 2.8wt%. The volume concentration of the ethanol solution was 94%.
2. One-time treatment
Adding methyl-beta-cyclodextrin into methanol, dispersing uniformly, adding butyl methacrylate and tetrabutyl titanate, vibrating at 150rpm for 11 hours, evaporating at 68.5 ℃ to remove methanol, placing the residue in an environment with the vacuum degree of 0.07MPa, and keeping the temperature at 45 ℃ for 9 hours to prepare a coating; and (3) adding polyacrylic acid, acrylamide and a coating into deionized water, regulating the pH to 5.8, stirring and heating to 33 ℃ in a nitrogen atmosphere, adding tetramethyl ethylenediamine and azobisisobutylamin hydrochloride in a heat preservation manner, and carrying out heat preservation for 5 hours under an illumination condition to obtain the primary treatment liquid.
Wherein the weight ratio of the methylated-beta-cyclodextrin to the methyl butyl methacrylate to the butyl titanate to the methanol is 52:1.4:8.5:125.
The weight ratio of polyacrylic acid, acrylamide, coating, tetramethyl ethylenediamine, azo diisobutylamidine hydrochloride and deionized water is 0.85:38:14.5:0.17:0.09:325.
3. Secondary treatment
Adding water-soluble phenolic resin, modified powder, primary treatment liquid and resorcinol into deionized water, stirring and heating to 39 ℃, preserving heat, and stirring at 350rpm for 50min; transferring into a constant temperature box, standing for 15h at 65 ℃ and separating out solid matters; transferring the solid into a calciner, heating to 725 ℃ at a heating rate of 2.5 ℃/min in a nitrogen atmosphere environment, preserving heat for 2.5h, and naturally cooling; and (3) when the mixture is cooled to 115 ℃, regulating the pressure to 0.3MPa by adopting nitrogen, continuously introducing water vapor for 35min at an introducing rate of 4L/min, drying and grinding uniformly to obtain a secondary treatment product.
Wherein the weight ratio of the water-soluble phenolic resin to the modified powder to the primary treatment liquid to the resorcinol to the deionized water is 9:15.5:29:0.025:220.
The pressure of the water vapor was 0.3MPa and the temperature was 133.5 ℃.
4. Three treatments
Adding the secondary treatment substance into the tertiary treatment liquid with the volume of 4.5 times, stirring for 2.5 hours, and filtering out solid substances; transferring the solid into a calciner, heating to 410 ℃ at a heating rate of 1 ℃/min, preserving heat for 3.5h, and naturally cooling to obtain the sewage purification composite material.
In the three treatments, the three treatment solutions are absolute ethanol solutions in which tetrabutyl titanate is dissolved. The concentration of tetrabutyl titanate in the tertiary treatment solution was 2.3wt%.
Example 3
A preparation method of a sewage purification composite material specifically comprises the following steps:
1. powder treatment
Adding macroporous silica, diatomite, attapulgite and sodium dodecyl sulfate into a ball mill, controlling the ball material water ratio to be 7:1:0.4, ball milling at 300rpm, ball milling for 50min, and drying to obtain a ball-milled material; putting ball-milled substances and deionized water into a high-pressure reaction kettle, adopting nitrogen to replace air in the high-pressure reaction kettle completely, regulating the pressure in the high-pressure reaction kettle to be 1.2MPa, sealing the high-pressure reaction kettle, heating to 190 ℃ at a heating rate of 0.5 ℃/min, preserving heat for 12 hours, naturally cooling to normal temperature, decompressing to normal pressure, separating out solid substances in the high-pressure reaction kettle, drying the solid substances to constant weight, putting the solid substances into a 3-time volume of modified liquid, stirring and heating to 50 ℃, preserving heat and stirring for 5 hours, centrifugally separating to obtain a centrifugate, washing the centrifugate for 2 times by adopting 8-time volume of deionized water, and drying to constant weight to obtain modified powder.
Wherein the weight ratio of macroporous silicon dioxide to diatomite to attapulgite to sodium dodecyl sulfate is 4:8:8:0.07.
The particle size of the macroporous silica is 180 meshes; the particle size of the diatomite is 200 meshes; the particle size of the attapulgite is 150 meshes.
The weight ratio of the ball milling material to the deionized water is 1:1.8.
The modifying liquid is an ethanol solution of the titanate coupling agent 102. The concentration of the titanate coupling agent 102 in the modified liquid was 3wt%. The volume concentration of the ethanol solution was 95%.
2. One-time treatment
Adding methyl-beta-cyclodextrin into methanol, dispersing uniformly, adding butyl methacrylate and tetrabutyl titanate, oscillating at 200rpm for 12 hours, evaporating at 70 ℃ to remove methanol, placing the residue in an environment with the vacuum degree of 0.08MPa, and keeping the temperature at 50 ℃ for 10 hours to prepare a coating; and (3) adding polyacrylic acid, acrylamide and a coating into deionized water, regulating the pH to 6.0, stirring and heating to 35 ℃ in a nitrogen atmosphere environment, adding tetramethyl ethylenediamine and azobisisobutylamin hydrochloride in a heat preservation manner, and carrying out heat preservation for 6 hours under an illumination condition to obtain the primary treatment liquid.
Wherein the weight ratio of the methylated-beta-cyclodextrin to the methyl butyl methacrylate to the methyl tetrabutyl titanate to the methyl alcohol is 55:1.5:9:130.
The weight ratio of polyacrylic acid, acrylamide, coating, tetramethyl ethylenediamine, azo diisobutylamidine hydrochloride and deionized water is 0.9:40:15:0.2:0.1:350.
3. Secondary treatment
Adding water-soluble phenolic resin, modified powder, primary treatment liquid and resorcinol into deionized water, stirring and heating to 40 ℃, preserving heat, and stirring at 400rpm for 60 min; transferring into a constant temperature box, standing for 16h at 70 ℃, and separating out solid matters; transferring the solid into a calciner, heating to 750 ℃ at a heating rate of 3 ℃/min in a nitrogen atmosphere environment, preserving heat for 3 hours, and naturally cooling; and (3) when the mixture is cooled to 120 ℃, regulating the pressure to 0.4MPa by adopting nitrogen, continuously introducing water vapor for 40min at an introducing rate of 5L/min, drying and grinding uniformly to obtain a secondary treatment product.
Wherein the weight ratio of the water-soluble phenolic resin to the modified powder to the primary treatment liquid to the resorcinol to the deionized water is 10:16:30:0.03:250.
The pressure of the water vapor was 0.4MPa and the temperature was 144 ℃.
4. Three treatments
Adding the secondary treatment substance into the tertiary treatment liquid with the volume of 4.5 times, stirring for 3 hours, and filtering out solid substances; transferring the solid into a calciner, heating to 420 ℃ at a heating rate of 1.2 ℃/min, preserving heat for 4 hours, and naturally cooling to obtain the sewage purification composite material.
In the three treatments, the three treatment solutions are absolute ethanol solutions in which tetrabutyl titanate is dissolved. The concentration of tetrabutyl titanate in the tertiary treatment solution was 2.5wt%.
Comparative example 1
The technical scheme of the embodiment 2 is adopted, and the difference is that: 1) In powder treatment, high-temperature high-pressure treatment and modified liquid treatment after ball milling are omitted, and ball milling substances are adopted to replace modified powder for subsequent steps. 2) Omitting the three treatment steps and taking the secondary treatment as the final product.
Comparative example 2
The technical scheme of the embodiment 2 is adopted, and the difference is that: 1) In powder treatment, macroporous silica, attapulgite and sodium dodecyl sulfate are omitted, and ball milling is omitted; 2) In one treatment, the preparation and use of the coating is omitted.
The sewage purification performance of the sewage purification composite materials of examples 1 to 3 and comparative examples 1 to 2 was examined, specifically: the nitrophenol, methyl orange, congo red, methylene blue, copper chloride, zinc chloride and methyl tertiary butyl ether are added into deionized water to prepare test simulated sewage, and the test simulated sewage is controlled to have the nitrophenol content of 30mg/L, the methyl orange content of 50mg/L, the Congo red content of 30mg/L, the methylene blue content of 20mg/L, the copper chloride content of 60mg/L, the zinc chloride content of 20mg/L and the methyl tertiary butyl ether content of 200 mu g/L. And the pH value of the simulated sewage of the test is adjusted to 9.5 by adopting 10wt% sodium hydroxide solution.
According to the addition amount of 15g/L, the sewage purification composite materials of the examples 1-3 and the comparative examples 1-2 are respectively put into test simulation sewage with the temperature of 12 ℃, after being uniformly stirred, an ultraviolet light source is kept stirring, the distance between the ultraviolet light source and the sewage liquid level is controlled to be 15cm, the wavelength of the ultraviolet light is 254nm, and the power of the ultraviolet light source is 120W. After the ultraviolet light is continuously irradiated for 16 hours, the ultraviolet light source is turned off, stirring is stopped, and after solid matters are separated, the removal rate of each component in the sewage is detected, and the decolorizing rate of the sewage is simulated by a detection test. The specific results are shown in the following table:
further, the secondary sedimentation tank supernatant of a sewage treatment plant in a chemical industry park of a Shandong Weifang is used as test water (initial COD cr 164 mg/L), the sewage purification composite materials prepared in examples 1-3 and comparative examples 1-2 are respectively added into test water with the temperature of 12 ℃ according to the addition amount of 15g/L, and after being uniformly stirred, an ultraviolet light source is started, the distance between the ultraviolet light source and the sewage liquid level is controlled to be 15cm, the wavelength of the ultraviolet light is 254nm, and the power of the ultraviolet light source is 120W. After the ultraviolet light is continuously irradiated for 2.5 hours, the COD of the test water is detected cr Value and calculate COD cr The removal rate; and detecting the decoloring rate of the test water.
Wherein, COD cr The method for calculating the removal rate comprises the following steps: [ (initial COD) cr value-COD after treatment cr Value)/initial COD cr Value of]*100%. The specific test results are as follows:
further, the sewage purification composite materials of examples 1 to 3 and comparative examples 1 to 2Material pair test Water (initial COD) cr 164 mg/L), and then, respectively performing regeneration treatment, specifically: putting the sewage purification composite material into deionized water with the volume of 5 times, stirring for 30min at 80 ℃, placing the mixture into a regeneration device, adopting dry air with the temperature of 280 ℃, blowing with hot air for 2h under the pressure condition of 0.1MPa, and naturally cooling to obtain the regenerated sewage purification composite material. The regenerated sewage purification composite material was reused for test water (initial COD cr 164 mg/L) and after each treatment was completed, a regeneration treatment was performed. Repeatedly recycling for 10 times, and observing whether COD is generated in the sewage purification process of the 10 times cr The abnormal fluctuation of the removal rate and the decoloration rate is used for examining the sewage purification stability of the sewage purification composite material; wherein the abnormal fluctuation refers to COD of the sewage purified by two times before and after cr The difference in removal rate or decoloration rate is more than 8%. Meanwhile, when the water was reused for 10 th time, the test water (initial COD cr 164 mg/L), i.e., COD of the test water after purification cr Value, COD cr Removal rate and decoloration rate. The specific results are as follows:
as can be seen from the test results, the preparation method of the sewage purification composite material comprises the steps of mixing and ball-milling macroporous silica, diatomite, attapulgite and sodium dodecyl sulfate in the powder treatment process, and then carrying out high-temperature and high-pressure hydrothermal treatment and modification liquid treatment on the ball-milled material to prepare modified powder; after preparing a coating by adopting the matching of the methylation-beta-cyclodextrin and the butyl methacrylate and the tetrabutyl titanate, the coating is used in the polymerization process of acrylamide to prepare primary treatment liquid; then, the water-soluble phenolic resin, the modified powder and the primary treatment liquid are crosslinked and combined, and the inorganic porous adsorption material, the phenolic resin-based carbon material and the photocatalytic active ingredient ternary composite secondary treatment substance is prepared through the processes of gel, aging, carbonization and high-temperature steam treatment; the secondary treatment substance is treated for three times by adopting a tertiary treatment liquid containing tetrabutyl titanate, and then the sewage purification composite material is prepared by calcining; the adverse effects of pollutant components and contents, acid-base property and temperature in the sewage on the sewage purification composite material are effectively reduced, and the sewage purification effect is improved; especially for the sewage with the pH value of more than 8.5 and higher dye content (more than 60 mg/L), and the pollutant components (such as heavy metal components and the like), the effective sewage purification can be realized, the occurrence of the shielding effect after the heavy metal precipitation suspended matters, the dye components and the organic pollutants form competitive adsorption on the surface of the sewage purification composite material is avoided, and the adverse effect on the sewage purification performance of the sewage purification composite material is avoided. Meanwhile, the low-temperature activity of the sewage purification composite material is further improved, and an ideal sewage purification effect can be obtained while the sewage purification efficiency is ensured under a lower temperature condition; further, the effective composition of each effective component is fully realized, the stability of the sewage purification performance of the sewage purification composite material is improved, the regenerability of the sewage purification composite material is improved, the regeneration loss is reduced, the problems of large photocatalytic performance attenuation and poor recycling performance after regeneration treatment are avoided, and the effective service life is prolonged.
As can be seen from comparative example 1, during the powder treatment, the high-temperature, high-pressure hydrothermal treatment and the modification liquid treatment of the ball-milled material are omitted; and omitting three treatment steps, the adsorption performance and low-temperature activity of the sewage purification composite material on pollutants in the sewage and the combination performance with phenolic resin-based carbon materials and photocatalytic active components are reduced to a certain extent, so that the adsorption performance and photocatalytic performance of the sewage purification composite material are reduced, the adsorption performance and photocatalytic performance of the sewage purification composite material cannot effectively cooperatively purify the sewage, and the sewage purification composite material has obvious purification effect decay aiming at sewage with high alkalinity, high dye content and complex components; meanwhile, the sewage purification composite material has poor sewage purification stability, and the sewage purification effect is abnormally fluctuated in the repeated recycling process; in addition, in the regeneration process of the sewage purification composite material, the regeneration loss is reduced greatly, and the recycling performance is poor.
As can be seen from comparative example 2, in the powder treatment, macroporous silica, attapulgite, sodium dodecyl sulfate and ball milling treatment were omitted; and omitting the preparation of the coating in one treatment, which also results in the enrichment effect of the inorganic porous adsorption material and the phenolic resin-based carbon material on pollutants in sewage and the attenuation of the photocatalytic effect of the photocatalytic active ingredient on the pollutants; meanwhile, in the process of repeated regeneration and recycling of the sewage purification composite material, the regeneration loss of the photocatalytic active ingredients is large, and the recycling performance is poor; the method is characterized in that the sewage purifying effect is reduced, and the sewage purifying effect is obviously declined after repeated recycling.
The percentages used in the present invention are mass percentages unless otherwise indicated.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The preparation method of the sewage purification composite material is characterized by comprising the following steps of: powder treatment, primary treatment, secondary treatment and tertiary treatment;
the powder treatment method comprises the steps of uniformly ball-milling macroporous silicon dioxide, diatomite, attapulgite and sodium dodecyl sulfate, and drying to obtain a ball-milled product; putting ball-milled substances and deionized water into a high-pressure reaction kettle, regulating the pressure in the high-pressure reaction kettle to be 1-1.2MPa in a pure nitrogen atmosphere, sealing the high-pressure reaction kettle, heating to 180-190 ℃, preserving heat for 10-12h, naturally cooling to normal temperature, decompressing to normal pressure, separating out solid substances in the high-pressure reaction kettle, drying the solid substances, putting the solid substances into a modifying solution, heating to 40-50 ℃, preserving heat, stirring, centrifugally separating to obtain a centrifugate, washing and drying the centrifugate by the deionized water, and obtaining modified powder;
the one-time treatment method comprises the steps of adding methylation-beta-cyclodextrin into methanol, dispersing uniformly, adding butyl methacrylate and tetrabutyl titanate, vibrating, evaporating to remove methanol, and keeping the residue at 40-50 ℃ for 8-10h under a vacuum environment to obtain a coating; adding polyacrylic acid, acrylamide and a coating into deionized water, regulating the pH to 5.5-6.0, heating to 30-35 ℃ in a nitrogen atmosphere environment, adding tetramethyl ethylenediamine and azobisisobutyronitrile hydrochloride at a certain temperature, and keeping the temperature for 4-6 hours under an illumination condition to obtain a primary treatment solution;
the secondary treatment method comprises the steps of adding water-soluble phenolic resin, modified powder, primary treatment liquid and resorcinol into deionized water, stirring and heating to 37-40 ℃, preserving heat, stirring, and standing at 60-70 ℃ to separate out solid matters; heating the solid to 700-750 ℃ in a nitrogen atmosphere, preserving heat and naturally cooling; when the temperature is cooled to 110-120 ℃, regulating the pressure to 0.2-0.4MPa, and continuously introducing water vapor; drying and grinding uniformly after the water vapor is introduced, so as to obtain a secondary treatment object;
the method for the tertiary treatment comprises the steps of putting the secondary treatment substance into the tertiary treatment liquid, stirring, and filtering out solid substances; preserving heat at 400-420 ℃ and naturally cooling to prepare the sewage purifying composite material;
in the three treatments, the three treatment solutions are absolute ethanol solutions in which tetrabutyl titanate is dissolved.
2. The method for preparing the sewage purification composite material according to claim 1, wherein in the powder treatment, the ball-milling ball material water ratio is 6-7:1:0.35-0.4, the ball-milling rotating speed is 200-300rpm, and the ball-milling time is 30-50min;
the weight ratio of the ball milling material to the deionized water is 1:1.5-1.8;
the temperature rising rate of the mixture is 0.4 to 0.5 ℃/min when the mixture is heated to 180 to 190 ℃;
the volume ratio of the solid matter to the modifying liquid is 1:2-3.
3. The method for preparing the sewage purification composite material according to claim 1, wherein in the powder treatment, the weight ratio of macroporous silica, diatomite, attapulgite and sodium dodecyl sulfate is 3-4:7-8:7-8:0.06-0.07;
the modifying liquid is ethanol solution of the titanate coupling agent 102; the concentration of the titanate coupling agent 102 in the modified liquid is 2.5-3wt%; the volume concentration of the ethanol solution is 92-95%;
the particle size of the macroporous silica is 150-180 meshes; the particle size of the diatomite is 150-200 meshes; the particle size of the attapulgite is 120-150 meshes.
4. The method for preparing a sewage purification composite material according to claim 1, wherein in the one-time treatment, the oscillation speed is 100-200rpm, and the oscillation time is 10-12h;
the weight ratio of the methylated-beta-cyclodextrin to the butyl methacrylate to the tetrabutyl titanate to the methanol is 50-55:1.3-1.5:8-9:120-130.
5. The method for preparing the sewage purification composite material according to claim 1, wherein in the one-time treatment, the weight ratio of polyacrylic acid, acrylamide, coating, tetramethyl ethylenediamine, azo diisobutylamidine hydrochloride and deionized water is 0.8-0.9:35-40:14-15:0.15-0.2:0.08-0.1:300-350.
6. The method for producing a sewage purification composite material according to claim 1, wherein in the secondary treatment, a temperature rising rate of raising the temperature to 700 to 750 ℃ is 2 to 3 ℃/min;
the water vapor is introduced at a rate of 3-5L/min;
the pressure of the water vapor is 0.2-0.4MPa, and the temperature is 120.5-144 ℃.
7. The method for preparing the sewage purification composite material according to claim 1, wherein in the secondary treatment, the weight ratio of the water-soluble phenolic resin to the modified powder to the primary treatment liquid to the resorcinol to the deionized water is 8-10:15-16:28-30:0.02-0.03:200-250.
8. The method for preparing a sewage purification composite material according to claim 1, wherein in the third treatment, the volume ratio of the secondary treatment substance to the third treatment liquid is 1:4-5;
the temperature rising rate of the mixture is 0.8 to 1.2 ℃/min when the mixture is heated to 400 to 420 ℃;
the heat preservation time at 400-420 ℃ is 3-4h.
9. The method for preparing a sewage purification composite material according to claim 1, wherein the concentration of tetrabutyl titanate in the tertiary treatment liquid is 2-2.5wt%.
10. A composite material for purifying sewage, characterized in that it is produced by the production method according to any one of claims 1 to 9.
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| JP2004305947A (en) * | 2003-04-08 | 2004-11-04 | Shinto V-Cerax Ltd | Anatase-type titanium-dioxide photo-catalyst carrying silica gel and its manufacturing method |
| WO2015131632A1 (en) * | 2014-03-03 | 2015-09-11 | 福州大学 | Catalytic filter filtering material having tio2 thin-film protective layer and preparation method for same |
| CN105817209A (en) * | 2016-05-20 | 2016-08-03 | 张能力 | Active carbon water treatment composite adsorbent and preparing method thereof |
| CN108126663A (en) * | 2018-02-26 | 2018-06-08 | 彭万喜 | A kind of high-efficiency adsorbent |
| CN108774448A (en) * | 2018-06-01 | 2018-11-09 | 宁波帝杨电子科技有限公司 | A kind of purifying formaldehyde water paint and preparation method thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004305947A (en) * | 2003-04-08 | 2004-11-04 | Shinto V-Cerax Ltd | Anatase-type titanium-dioxide photo-catalyst carrying silica gel and its manufacturing method |
| WO2015131632A1 (en) * | 2014-03-03 | 2015-09-11 | 福州大学 | Catalytic filter filtering material having tio2 thin-film protective layer and preparation method for same |
| CN105817209A (en) * | 2016-05-20 | 2016-08-03 | 张能力 | Active carbon water treatment composite adsorbent and preparing method thereof |
| CN108126663A (en) * | 2018-02-26 | 2018-06-08 | 彭万喜 | A kind of high-efficiency adsorbent |
| CN108774448A (en) * | 2018-06-01 | 2018-11-09 | 宁波帝杨电子科技有限公司 | A kind of purifying formaldehyde water paint and preparation method thereof |
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