CN108176371B - Kaolin composite adsorption material and preparation method and application thereof - Google Patents
Kaolin composite adsorption material and preparation method and application thereof Download PDFInfo
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- CN108176371B CN108176371B CN201711476661.1A CN201711476661A CN108176371B CN 108176371 B CN108176371 B CN 108176371B CN 201711476661 A CN201711476661 A CN 201711476661A CN 108176371 B CN108176371 B CN 108176371B
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- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 239000005995 Aluminium silicate Substances 0.000 title claims abstract description 73
- 235000012211 aluminium silicate Nutrition 0.000 title claims abstract description 73
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 56
- 239000000463 material Substances 0.000 title claims abstract description 49
- 239000002131 composite material Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title description 10
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 72
- 229920001661 Chitosan Polymers 0.000 claims abstract description 39
- 239000011941 photocatalyst Substances 0.000 claims abstract description 33
- 239000011258 core-shell material Substances 0.000 claims abstract description 32
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 36
- 238000002156 mixing Methods 0.000 claims description 16
- 239000002105 nanoparticle Substances 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 11
- 239000000725 suspension Substances 0.000 claims description 9
- COLNVLDHVKWLRT-QMMMGPOBSA-N L-phenylalanine Chemical compound OC(=O)[C@@H](N)CC1=CC=CC=C1 COLNVLDHVKWLRT-QMMMGPOBSA-N 0.000 claims description 8
- COLNVLDHVKWLRT-UHFFFAOYSA-N phenylalanine Natural products OC(=O)C(N)CC1=CC=CC=C1 COLNVLDHVKWLRT-UHFFFAOYSA-N 0.000 claims description 8
- 239000000839 emulsion Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000003763 carbonization Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 238000000151 deposition Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 19
- 230000000694 effects Effects 0.000 abstract description 15
- 239000002351 wastewater Substances 0.000 abstract description 15
- ULGZDMOVFRHVEP-RWJQBGPGSA-N Erythromycin Chemical compound O([C@@H]1[C@@H](C)C(=O)O[C@@H]([C@@]([C@H](O)[C@@H](C)C(=O)[C@H](C)C[C@@](C)(O)[C@H](O[C@H]2[C@@H]([C@H](C[C@@H](C)O2)N(C)C)O)[C@H]1C)(C)O)CC)[C@H]1C[C@@](C)(OC)[C@@H](O)[C@H](C)O1 ULGZDMOVFRHVEP-RWJQBGPGSA-N 0.000 abstract description 6
- 239000003344 environmental pollutant Substances 0.000 abstract description 5
- 231100000719 pollutant Toxicity 0.000 abstract description 5
- 238000011160 research Methods 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 4
- UCSJYZPVAKXKNQ-HZYVHMACSA-N streptomycin Chemical compound CN[C@H]1[C@H](O)[C@@H](O)[C@H](CO)O[C@H]1O[C@@H]1[C@](C=O)(O)[C@H](C)O[C@H]1O[C@@H]1[C@@H](NC(N)=N)[C@H](O)[C@@H](NC(N)=N)[C@H](O)[C@H]1O UCSJYZPVAKXKNQ-HZYVHMACSA-N 0.000 abstract description 4
- 229960003276 erythromycin Drugs 0.000 abstract description 3
- HEFNNWSXXWATRW-UHFFFAOYSA-N Ibuprofen Chemical compound CC(C)CC1=CC=C(C(C)C(O)=O)C=C1 HEFNNWSXXWATRW-UHFFFAOYSA-N 0.000 abstract description 2
- 229930182555 Penicillin Natural products 0.000 abstract description 2
- JGSARLDLIJGVTE-MBNYWOFBSA-N Penicillin G Chemical compound N([C@H]1[C@H]2SC([C@@H](N2C1=O)C(O)=O)(C)C)C(=O)CC1=CC=CC=C1 JGSARLDLIJGVTE-MBNYWOFBSA-N 0.000 abstract description 2
- 108010059993 Vancomycin Proteins 0.000 abstract description 2
- 229960005091 chloramphenicol Drugs 0.000 abstract description 2
- WIIZWVCIJKGZOK-RKDXNWHRSA-N chloramphenicol Chemical compound ClC(Cl)C(=O)N[C@H](CO)[C@H](O)C1=CC=C([N+]([O-])=O)C=C1 WIIZWVCIJKGZOK-RKDXNWHRSA-N 0.000 abstract description 2
- 229960001193 diclofenac sodium Drugs 0.000 abstract description 2
- 229960001680 ibuprofen Drugs 0.000 abstract description 2
- 229940049954 penicillin Drugs 0.000 abstract description 2
- 229960001732 pipemidic acid Drugs 0.000 abstract description 2
- JOHZPMXAZQZXHR-UHFFFAOYSA-N pipemidic acid Chemical compound N1=C2N(CC)C=C(C(O)=O)C(=O)C2=CN=C1N1CCNCC1 JOHZPMXAZQZXHR-UHFFFAOYSA-N 0.000 abstract description 2
- JGMJQSFLQWGYMQ-UHFFFAOYSA-M sodium;2,6-dichloro-n-phenylaniline;acetate Chemical compound [Na+].CC([O-])=O.ClC1=CC=CC(Cl)=C1NC1=CC=CC=C1 JGMJQSFLQWGYMQ-UHFFFAOYSA-M 0.000 abstract description 2
- 229960005322 streptomycin Drugs 0.000 abstract description 2
- 229960003165 vancomycin Drugs 0.000 abstract description 2
- MYPYJXKWCTUITO-LYRMYLQWSA-N vancomycin Chemical compound O([C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1OC1=C2C=C3C=C1OC1=CC=C(C=C1Cl)[C@@H](O)[C@H](C(N[C@@H](CC(N)=O)C(=O)N[C@H]3C(=O)N[C@H]1C(=O)N[C@H](C(N[C@@H](C3=CC(O)=CC(O)=C3C=3C(O)=CC=C1C=3)C(O)=O)=O)[C@H](O)C1=CC=C(C(=C1)Cl)O2)=O)NC(=O)[C@@H](CC(C)C)NC)[C@H]1C[C@](C)(N)[C@H](O)[C@H](C)O1 MYPYJXKWCTUITO-LYRMYLQWSA-N 0.000 abstract description 2
- MYPYJXKWCTUITO-UHFFFAOYSA-N vancomycin Natural products O1C(C(=C2)Cl)=CC=C2C(O)C(C(NC(C2=CC(O)=CC(O)=C2C=2C(O)=CC=C3C=2)C(O)=O)=O)NC(=O)C3NC(=O)C2NC(=O)C(CC(N)=O)NC(=O)C(NC(=O)C(CC(C)C)NC)C(O)C(C=C3Cl)=CC=C3OC3=CC2=CC1=C3OC1OC(CO)C(O)C(O)C1OC1CC(C)(N)C(O)C(C)O1 MYPYJXKWCTUITO-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000013508 migration Methods 0.000 description 6
- 230000005012 migration Effects 0.000 description 6
- 238000007711 solidification Methods 0.000 description 6
- 230000008023 solidification Effects 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- 238000009830 intercalation Methods 0.000 description 5
- 230000002687 intercalation Effects 0.000 description 5
- 229940079593 drug Drugs 0.000 description 4
- 239000003814 drug Substances 0.000 description 4
- 229940035676 analgesics Drugs 0.000 description 3
- 239000000730 antalgic agent Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000002734 clay mineral Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 2
- 239000003242 anti bacterial agent Substances 0.000 description 2
- 229940088710 antibiotic agent Drugs 0.000 description 2
- RYYVLZVUVIJVGH-UHFFFAOYSA-N caffeine Chemical compound CN1C(=O)N(C)C(=O)C2=C1N=CN2C RYYVLZVUVIJVGH-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- IPUUGQUFDIWIMW-QRPNPIFTSA-N (2S)-2-amino-3-phenylpropanoic acid ethanol Chemical compound CCO.N[C@@H](Cc1ccccc1)C(O)=O IPUUGQUFDIWIMW-QRPNPIFTSA-N 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- LPHGQDQBBGAPDZ-UHFFFAOYSA-N Isocaffeine Natural products CN1C(=O)N(C)C(=O)C2=C1N(C)C=N2 LPHGQDQBBGAPDZ-UHFFFAOYSA-N 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229960001948 caffeine Drugs 0.000 description 1
- VJEONQKOZGKCAK-UHFFFAOYSA-N caffeine Natural products CN1C(=O)N(C)C(=O)C2=C1C=CN2C VJEONQKOZGKCAK-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000002934 diuretic Substances 0.000 description 1
- 229940030606 diuretics Drugs 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000003676 hair preparation Substances 0.000 description 1
- 239000008266 hair spray Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229940088597 hormone Drugs 0.000 description 1
- 239000005556 hormone Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 150000003431 steroids Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
-
- 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
- C02F2101/30—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—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
- C02F2101/38—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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Catalysts (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
本发明提供了一种高岭土复合吸附材料，其中，它包括高岭土和与该高岭土形成插层结构的壳聚糖，该壳聚糖上负载有核壳结构光催化剂。所述核壳结构光催化剂包括二氧化锡纳米核和包覆在该二氧化锡纳米核表面的多孔碳壳。本发明提供还一种由上述方法制备的高岭土复合吸附材料及其应用。上述高岭土复合吸附材料可以用来处理废水中的氯霉素、青霉素、红霉素、链霉素、万古霉素、吡哌酸、布洛芬、双氯芬酸钠等PPCPs污染物，而且处理效果比较好。本专利技术受高等学校重点科研项目（15A610008）和华北水利水电大学博士科研启动金（201610009）资助。The present invention provides a kaolin composite adsorption material, which comprises kaolin and chitosan forming an intercalated structure with the kaolin, and the chitosan is loaded with a core-shell structure photocatalyst. The core-shell structure photocatalyst includes a tin dioxide nano-core and a porous carbon shell coated on the surface of the tin dioxide nano-core. The present invention also provides a kaolin composite adsorption material prepared by the above method and its application. The above-mentioned kaolin composite adsorption materials can be used to treat PPCPs pollutants such as chloramphenicol, penicillin, erythromycin, streptomycin, vancomycin, pipemidic acid, ibuprofen, and diclofenac sodium in wastewater, and the treatment effect is relatively good. . This patented technology is funded by the key scientific research projects of colleges and universities (15A610008) and the doctoral research start-up fund of North China University of Water Conservancy and Hydropower (201610009).
Description
Technical Field
The invention relates to a water treatment agent and a preparation method thereof, in particular to a kaolin composite adsorption material for adsorbing PPCPs pollutants and a preparation method thereof.
Background
PPCPs are short for drugs and personal protective products, and are widely applied to human beings, livestock and fishes. The chemical components that make up PCCPs are about 3000 or more, and mainly include two major groups: one class is drugs, including antibiotics, analgesics, hormones, diuretics, analgesics, steroids, caffeine, etc.; another class is personal protection products including perfumes, hair sprays, cosmetics, and the like. Different types of PPCPs remained in the global environment at present mainly take antibiotics and pyrolytic analgesic drugs as the main components, and most of the PPCPs have low volatility or are not easy to degrade, so most of the PPCPs remain in the water environment and have large detection amount, and the PPCPs already pose threats to the health and ecological environment of human beings. China is the biggest active drug producing country in the world and is also the consuming country of the top 3 active drugs in the world. According to statistics, Chinese recovered 0.69 x 10 in 2007 year8m3The waste water is re-filled into the underground water,this is especially the case in northern regions where water is in short supply, however, large numbers of PPCPs are detected in these recovered waters.
The current PCCPs treatment technology mainly comprises a migration method, an adsorption method, a degradation method and the like. Wherein, the migration method mainly refers to the migration, filtration and solidification effects of natural environment and natural soil on PPCPs. However, the migration method has problems of limited migration and filtration effects through natural environments, low soil solidification efficiency, and the like. The degradation method mainly refers to advanced oxidation (H)2O2UV), adopts a material with stronger oxidation activity, and realizes the gradual decomposition and even complete degradation of the PPCPs under the high-energy radiation or excitation. The adoption of the advanced oxidation method for degrading PPCPs has important significance on the cyclic development of the ecological environment, however, the current research process is complex, and compared with the traditional solid phase adsorption method, the method has the characteristics of high energy consumption, high cost and the like, and the complete degradation of the PPCPs is difficult to realize, so that the application of the method is limited.
The adsorption method mainly means that natural clay minerals and some artificially synthesized functional adsorption materials are adopted to perform adsorption and solidification on PPCPs, and also can perform functional modification on some clay minerals with stronger adsorption performance so as to realize the effect of efficient solidification. Compared with a migration method, the solid-phase adsorption method has the advantage of high-efficiency solidification due to the adoption of a special adsorption structure and a functional adsorption group. In addition, advanced oxidative degradation technology is immature in research and development, high in cost and poor in applicability, solidification is an important premise for realizing complete degradation, and the solid phase adsorption method is still the most common PPCPs pollution treatment method at present. However, in various clay minerals, the treatment of PPCPs wastewater by kaolin still needs to be improved.
Disclosure of Invention
In view of the above, it is necessary to provide a kaolin composite adsorption material and a preparation method thereof, so as to improve the treatment effect of kaolin on PPCPs wastewater.
The invention provides a kaolin composite adsorption material, which comprises kaolin and chitosan forming an intercalation structure with the kaolin, wherein the chitosan is loaded with a photocatalyst with a core-shell structure.
Based on the above, the core-shell structured photocatalyst includes a tin dioxide nano core and a porous carbon shell coated on the surface of the tin dioxide nano core.
Based on the above, the particle size of the tin dioxide nano core is 50-150 nm, and the porous carbon shell comprises a plurality of micropores with the pore diameter of 20-50 nm.
Based on the above, the porosity of the porous carbon shell is 30% to 60%.
Based on the above, the specific surface area of the core-shell structure photocatalyst is 300-400 m2/g。
Based on the above, in the kaolin composite adsorption material, the content of the chitosan is 4-8% of the mass of the kaolin, and the content of the tin dioxide nanoparticles is 40-80% of the mass of the chitosan.
The invention also provides a preparation method of the kaolin composite adsorption material, which comprises the following steps:
firstly, dispersing phenylalanine in an ethanol water solution with the volume concentration of 30-50%, then adding tin dioxide nanoparticles for uniform mixing, carrying out carbonization reaction on the phenylalanine at 150-180 ℃, and depositing and wrapping the phenylalanine on the surfaces of the tin dioxide nanoparticles to obtain a core-shell structured photocatalyst;
uniformly dispersing the core-shell structure photocatalyst in water to form a catalyst suspension, adding acetic acid to enable the mass concentration of the acetic acid to be 1% -5%, adding chitosan to be uniformly mixed, and enabling the core-shell structure photocatalyst to be loaded on the chitosan to obtain a chitosan emulsion;
step three, adding kaolin into water, stirring and mixing uniformly, then heating to 60-80 ℃, and keeping the temperature for 0.5-1 h to obtain a kaolin suspension; adding the chitosan emulsion into the kaolin suspension, and stirring for 24-48 h at normal temperature to obtain a blended solution;
and step four, filtering the blending solution, washing the blending solution to be neutral by water, and drying the blending solution at 80-100 ℃ to obtain the kaolin composite adsorbing material.
The invention also provides application of the kaolin composite adsorption material in the aspect of PPCPs treatment.
Compared with the prior art, in the kaolin composite adsorption material provided by the invention, the chitosan and the kaolin form an intercalation structure, so that the kaolin composite adsorption material has larger specific surface area than a kaolin raw material, the interlayer spacing of the kaolin is improved after the intercalation modification of the chitosan, and the chitosan is loaded with the photocatalyst with the core-shell structure, so that part of PPCPs can be decomposed, and meanwhile, the chitosan also has a certain adsorption effect on pollutants, so that the adsorption capacity of the kaolin composite adsorption material on the PPCPs is improved, the adsorbed PPCPs are solidified in the chitosan, and the treatment effect on the PPCPs pollutants is better.
Furthermore, the core-shell structure photocatalyst loaded on the chitosan comprises a tin dioxide nano core and a porous carbon shell coated on the surface of the tin dioxide nano core, and meanwhile, a plurality of mesopores are uniformly distributed on the porous carbon shell, so that the core-shell structure photocatalyst has a large specific surface area, and the tin dioxide nano core can be directly contacted with the surrounding environment to decompose the PPCPs of macromolecules adsorbed by the kaolin composite adsorption material into carbon dioxide and water, so that the PPCPs are prevented from being accumulated in the kaolin composite adsorption material, the kaolin composite adsorption material loses activity, the adsorption efficiency of the kaolin on the PPCPs is further improved, and the treatment effect of the kaolin on the PPCPs wastewater is improved. Therefore, the composite adsorption material provided by the invention can be used for treating the PPCPs pollutants such as chloramphenicol, penicillin, erythromycin, streptomycin, vancomycin, pipemidic acid, ibuprofen, diclofenac sodium and the like in wastewater, and has a good treatment effect. In addition, the carbon layer and the chitosan are easily degraded, so that the tin dioxide nano-particles are easy to recycle, and the water treatment cost is reduced.
It should be noted that: the patent technology is funded by key scientific research projects (15A610008) of higher schools and scientific research starting gold (201610009) of doctor of North China water conservancy and hydropower university.
Detailed Description
The technical solution of the present invention is further described in detail by the following embodiments.
Example 1
The embodiment provides a kaolin composite adsorption material, which comprises kaolin and chitosan forming an intercalation structure with the kaolin, wherein a core-shell structure photocatalyst is loaded on the chitosan, the core-shell structure photocatalyst comprises a tin dioxide nano core with the particle size of 50-100 nm and a porous carbon shell coated on the surface of the tin dioxide nano core, and the porous carbon shell comprises a plurality of micropores with the pore size of 20-50 nm; the porosity of the porous carbon shell is 30%, and the specific surface area of the core-shell structure photocatalyst is 300m2(ii)/g; in the kaolin composite adsorption material, the content of the chitosan is 4% of the mass of the kaolin, and the content of the tin dioxide nanoparticles is 40% of the mass of the chitosan.
The embodiment also provides a preparation method of the kaolin composite adsorption material, which comprises the following steps:
step one, dispersing phenylalanine in an ethanol water solution with the volume concentration of 30%, adding tin dioxide nanoparticles with the particle size, and uniformly mixing, wherein the tin dioxide nanoparticles are wrapped in the phenylalanine ethanol water solution; then, at the temperature of 150-180 ℃, phenylalanine distributed on the surfaces of the tin dioxide particles is carbonized and deposited on the surfaces of the corresponding tin dioxide particles, and ethanol on the surfaces of the tin dioxide particles is heated to volatilize, so that porous carbon shells are formed on the surfaces of the tin dioxide particles, and the core-shell structured photocatalyst is obtained;
uniformly dispersing the core-shell structure photocatalyst in water to form a catalyst suspension, adding acetic acid to enable the concentration of the acetic acid to be 1%, adding chitosan to be uniformly mixed, and enabling the core-shell structure photocatalyst to be loaded on the chitosan to obtain a chitosan emulsion;
step three, adding kaolin into distilled water, stirring and mixing uniformly, then heating to about 70 ℃, and keeping the temperature for 1h to obtain kaolin suspension; adding the chitosan emulsion into the kaolin suspension, and stirring for 36 hours at normal temperature to enable the chitosan and the kaolin to form an intercalation structure, and the chitosan is loaded with the core-shell structure photocatalyst to obtain a blending solution;
and step four, filtering and washing the blending solution until the blending solution is washed to be neutral by water, and then drying the blending solution at about 90 ℃ to obtain the kaolin composite adsorption material.
Example 2
The present example provides a kaolin composite adsorption material, the structure of which is substantially the same as that of the composite adsorption material provided in example 1, except that: the core-shell structure photocatalyst comprises a tin dioxide nano core with the particle size of 60-90 nm and a porous carbon shell coated on the surface of the tin dioxide nano core; the porosity of the porous carbon shell is 40%, and the specific surface area of the core-shell structure photocatalyst is 320m2(ii)/g; in the kaolin composite adsorption material, the content of the chitosan is 5% of the mass of the kaolin, and the content of the tin dioxide nanoparticles is 50% of the mass of the chitosan.
The preparation method of the kaolin composite adsorption material provided by the embodiment is basically the same as that provided by the embodiment 1, and the main difference is that: in the first step of this example, an ethanol aqueous solution with a volume concentration of 40% is used, and after acetic acid is added in the second step, the mass concentration of acetic acid is 2.5%.
Example 3
The present example provides a kaolin composite adsorption material, the structure of which is substantially the same as that of the composite adsorption material provided in example 1, except that: the core-shell structure photocatalyst comprises a tin dioxide nano core with the particle size of 60-120 nm and a porous carbon shell coated on the surface of the tin dioxide nano core; the porosity of the porous carbon shell is 50%, and the specific surface area of the core-shell structure photocatalyst is 350m2(ii)/g; in the kaolin composite adsorption material, the content of the chitosan is 6% of the mass of the kaolin, and the content of the tin dioxide nanoparticles is 70% of the mass of the chitosan.
The preparation method of the kaolin composite adsorption material provided by the embodiment is basically the same as that provided by the embodiment 1, and the main difference is that: in the first step of this example, an ethanol aqueous solution with a volume concentration of 45% is used, and after acetic acid is added in the second step, the mass concentration of acetic acid is 4%.
Example 4
The present example provides a kaolin composite adsorption material, the structure of which is substantially the same as that of the composite adsorption material provided in example 1, except that: the core-shell structure photocatalyst comprises a tin dioxide nano core with the particle size of 80-150 nm and a porous carbon shell coated on the surface of the tin dioxide nano core; the porosity of the porous carbon shell is 60%, and the specific surface area of the core-shell structure photocatalyst is 380m2(ii)/g; in the kaolin composite adsorption material, the content of the chitosan is 8% of the mass of the kaolin, and the content of the tin dioxide nanoparticles is 80% of the mass of the chitosan.
The preparation method of the kaolin composite adsorption material provided by the embodiment is basically the same as that provided by the embodiment 1, and the main difference is that: in the first step of this example, an ethanol aqueous solution with a volume concentration of 50% is used, and the mass concentration of acetic acid after adding acetic acid in the second step is 5%.
Performance testing
1. The three columnar reactors with the same specification and the effective volume of 10L are respectively filled with the same amount of kaolin raw material, the core-shell structure photocatalyst and the kaolin composite adsorbing material provided in the embodiment 3, erythromycin simulated wastewater (COD: 150-200 mg/L) is subjected to advanced treatment under the condition of the same operation parameters, and the treatment effect is shown in Table 1, wherein the core-shell structure photocatalyst has the basically same structure as the core-shell structure photocatalyst in the kaolin composite adsorbing material adopted in the embodiment 3. Wherein the process conditions are as follows: the pH value of the wastewater is 7-8, and the HRT is 30 min.
TABLE 1 Water treatment Effect of different adsorbents
As can be seen from table 1, under the same operation conditions, the water treatment effect of the kaolin composite adsorption material provided by the present invention on PPCPs wastewater is much higher than that of a kaolin raw material, and compared with a core-shell structured photocatalyst, the removal rate of the COD of the PPCPs wastewater by the kaolin composite adsorption material provided by the embodiment of the present invention is increased by more than 20%.
2. The kaolin composite adsorption material provided by the embodiment 3 of the invention is respectively filled in four columnar reactors with the same specification and the effective volume of 10L, and the advanced treatment is carried out on the simulation wastewater of several different PPCPs under the condition of the same operation parameters, wherein the process conditions are as follows: the HRT of the wastewater is 30min, and the treatment effect is shown in Table 2.
TABLE 2 effluent treatment effect table for different PPCPs wastewater biochemical pools
As can be seen from Table 2: under certain operating conditions, the COD removal rates of different PPCPs wastewater by the kaolin composite adsorption material provided by the embodiment of the invention are all over 70%, and the treatment performance of the PPCPs wastewater by the kaolin composite adsorption material provided by the embodiment of the invention has broad spectrum.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention and not to limit it; although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art will understand that: modifications to the specific embodiments of the invention or equivalent substitutions for parts of the technical features may be made; without departing from the spirit of the present invention, it is intended to cover all aspects of the invention as defined by the appended claims.
Claims (3)
1. A kaolin composite adsorption material is characterized in that: the photocatalyst comprises a tin dioxide nano core and a porous carbon shell coated on the surface of the tin dioxide nano core, wherein the porosity of the porous carbon shell is 30-60%, the content of the chitosan is 4-8% of the mass of the kaolin, and the content of the tin dioxide nano particles is 40-80% of the mass of the chitosan; the kaolin composite adsorption material is mainly prepared by the following steps:
firstly, dispersing phenylalanine in an ethanol water solution with the volume concentration of 30-50%, then adding tin dioxide nanoparticles for uniform mixing, carrying out carbonization reaction on the phenylalanine at 150-180 ℃, and depositing and wrapping the phenylalanine on the surfaces of the tin dioxide nanoparticles to obtain a core-shell structured photocatalyst;
uniformly dispersing the core-shell structure photocatalyst in water to form a catalyst suspension, adding acetic acid to enable the mass concentration of the acetic acid to be 1% -5%, adding chitosan to be uniformly mixed, and enabling the core-shell structure photocatalyst to be loaded on the chitosan to obtain a chitosan emulsion;
step three, adding kaolin into water, stirring and mixing uniformly, then heating to 60-80 ℃, and keeping the temperature for 0.5-1 h to obtain a kaolin suspension; adding the chitosan emulsion into the kaolin suspension, and stirring for 24-48 h at normal temperature to obtain a blended solution;
and step four, filtering the blending solution, washing the blending solution to be neutral by water, and drying the blending solution at 80-100 ℃ to obtain the kaolin composite adsorbing material.
2. The kaolin composite adsorption material of claim 1, wherein: the particle size of the tin dioxide nano core is 50-150 nm, and the porous carbon shell comprises a plurality of micropores with the pore diameter of 20-50 nm.
3. The kaolin composite adsorption material according to claim 2, wherein: the specific surface area of the core-shell structure photocatalyst is 300-400 m2/g。
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