CN108187706A - A kind of indium doping containing phosphatization is modified TiO2Catalysis material catalytic degradation antibiotic waste water method - Google Patents
A kind of indium doping containing phosphatization is modified TiO2Catalysis material catalytic degradation antibiotic waste water method Download PDFInfo
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- CN108187706A CN108187706A CN201810015831.4A CN201810015831A CN108187706A CN 108187706 A CN108187706 A CN 108187706A CN 201810015831 A CN201810015831 A CN 201810015831A CN 108187706 A CN108187706 A CN 108187706A
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- catalysis material
- waste water
- indium doping
- sulphadiazine
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- 239000000463 material Substances 0.000 title claims abstract description 62
- 239000002351 wastewater Substances 0.000 title claims abstract description 41
- 229910052738 indium Inorganic materials 0.000 title claims abstract description 34
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 29
- 238000006731 degradation reaction Methods 0.000 title claims description 60
- 230000015556 catabolic process Effects 0.000 title claims description 58
- 230000003197 catalytic effect Effects 0.000 title claims description 17
- 230000003115 biocidal effect Effects 0.000 title abstract description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 77
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 45
- SEEPANYCNGTZFQ-UHFFFAOYSA-N sulfadiazine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)NC1=NC=CC=N1 SEEPANYCNGTZFQ-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229960004306 sulfadiazine Drugs 0.000 claims abstract description 43
- GPXJNWSHGFTCBW-UHFFFAOYSA-N Indium phosphide Chemical compound [In]#P GPXJNWSHGFTCBW-UHFFFAOYSA-N 0.000 claims abstract description 34
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 13
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000002360 preparation method Methods 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 45
- 235000019441 ethanol Nutrition 0.000 claims description 18
- 239000005725 8-Hydroxyquinoline Substances 0.000 claims description 16
- 229960003540 oxyquinoline Drugs 0.000 claims description 16
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 238000001354 calcination Methods 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- 238000001994 activation Methods 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical compound NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 claims description 10
- 229940124530 sulfonamide Drugs 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 238000012986 modification Methods 0.000 claims description 9
- 230000004048 modification Effects 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- 230000004913 activation Effects 0.000 claims description 8
- 239000000706 filtrate Substances 0.000 claims description 8
- 238000003837 high-temperature calcination Methods 0.000 claims description 8
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 8
- 238000007146 photocatalysis Methods 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 7
- 239000000084 colloidal system Substances 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 238000010525 oxidative degradation reaction Methods 0.000 claims description 6
- 239000013618 particulate matter Substances 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 4
- 238000009298 carbon filtering Methods 0.000 claims description 4
- 239000003292 glue Substances 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 150000004325 8-hydroxyquinolines Chemical class 0.000 claims description 3
- 230000032683 aging Effects 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 3
- 239000012065 filter cake Substances 0.000 claims description 3
- 239000012982 microporous membrane Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000002336 sorption--desorption measurement Methods 0.000 claims description 3
- 238000002604 ultrasonography Methods 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 230000000593 degrading effect Effects 0.000 abstract description 8
- 230000001590 oxidative effect Effects 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 5
- 239000010865 sewage Substances 0.000 abstract description 5
- 239000003795 chemical substances by application Substances 0.000 abstract description 4
- 230000002265 prevention Effects 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 description 29
- 238000007254 oxidation reaction Methods 0.000 description 17
- 239000000243 solution Substances 0.000 description 16
- 230000003647 oxidation Effects 0.000 description 15
- 230000000694 effects Effects 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 230000001699 photocatalysis Effects 0.000 description 6
- 238000005554 pickling Methods 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000004408 titanium dioxide Substances 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000004438 BET method Methods 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000001413 cellular effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 239000008239 natural water Substances 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- PHELOKYCCWVWFE-UHFFFAOYSA-N 2,2-dimethoxyacetic acid Chemical class COC(OC)C(O)=O PHELOKYCCWVWFE-UHFFFAOYSA-N 0.000 description 1
- DAOMIIZPTXDAKO-UHFFFAOYSA-N COCOC.CN(CC=C)C Chemical compound COCOC.CN(CC=C)C DAOMIIZPTXDAKO-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 206010034133 Pathogen resistance Diseases 0.000 description 1
- 241000233805 Phoenix Species 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000009360 aquaculture Methods 0.000 description 1
- 244000144974 aquaculture Species 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000005446 dissolved organic matter Substances 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 239000002552 dosage form Substances 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010812 external standard method Methods 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000036039 immunity Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000008238 pharmaceutical water Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 230000001443 photoexcitation Effects 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000013097 stability assessment Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
- B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
-
- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
- B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
- B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
- B01J27/1811—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates with gallium, indium or thallium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/06—Washing
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/12—Oxidising
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
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- 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
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- 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
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- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- 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
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- 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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Abstract
The invention belongs to organic sewage Prevention Technique fields, and in particular to a kind of indium doping containing phosphatization is modified TiO2Catalysis material catalyzing oxidizing degrading antibiotic waste water method.The present invention provides a kind of indium doping containing phosphatization and is modified TiO2Catalysis material, the present invention using butyl titanate as TiO2Presoma, double modified TiO are obtained using sol-gal process preparation using indium phosphide and 8 oxyquinolines as modifying agent2Catalysis material；Catalysis material prepared by the present invention can under ultraviolet light and/or sunlight catalyzing oxidizing degrading sulphadiazine, and catalysis material recoverable, can be used in high concentration COD waste water.
Description
Technical field
The invention belongs to organic sewage Prevention Technique fields, and in particular to a kind of indium doping containing phosphatization is modified TiO2Light urge
Change the method for material catalytic degradation antibiotic waste water.
Background technology
In recent years, being widely used due to antibiotic causes the pollution and harm that can not be ignored to environment.According to document report
Road, many countries including China detect remaining antibiotic, source in natural water and give up for industrial pharmaceutical
Water, hospital sewage etc..Not only aquatile can be caused to poison into these micro antibiotic in water body, can also stimulate cause of disease
Microorganism develops immunity to drugs or even enters human body by food chain, so as to cause tremendous influence to the entire ecosystem.
Sulphadiazine (Sulfadiazine, SD) is widely used fungicide, belongs to noxious material difficult to degrade, main next
Derived from pharmaceuticals industry and aquaculture waste water.After SD and its toxic derivative enter soil and water body environment, inducible resistance bacterial strain
It generates without easily biological-degradable so that such drug is enriched in water body and bed mud, and the final safe drinking water for threatening the mankind has
Numerous studies confirm the harm of such substance in natural water.This kind of waste water is handled at present mainly uses biochemical degradation method, due to
Sulphadiazine class antibiotic has bioprocess strong inhibition effect, and conventional treatment method is extremely difficult to ideal removal effect.
After sewage treatment plant's biodegradation, separation and photolysis, original 60%~90% is still remained in the sewage of discharge
The antibiotic such as sulphadiazine.
Zhang Jia et al.（Safety and environment journal, 2014,14,（6）：143-147, sulfanilamide (SN) is phonetic in Electro-catalytic Oxidation Process water
The research of pyridine）Using the sulphadiazine in the method degradation water of Electro-catalytic Oxidation Process, but it is phonetic to the sulfanilamide (SN) of high concentration 50mg/L
Pyridine waste water solution degradation rate is low, and does not account for the influence of remaining organic matter in waste water；TiO2Having property of photochemical catalytic oxidation
The advantages that matter is stable, nontoxic, catalytic activity is high, non-secondary pollution, Ji'nan University's beam phoenix face et al.（Ecological environment journal 2009,
18(4): 1227-1230）Report is using TiO2Photocatalytic oxidation degradation sulphadiazine, but must be in the ultraviolet of below 400nm
It is carried out under light, and it is only 2mg/L, and do not consider practical sulphadiazine that its sulphadiazine concentration that can degrade is lower
The complexity of ingredient in waste water, such as contain other intermediate glyoxylic dimethyl acetals, 3-（Dimethylamino）Propylene methylal
Or remaining substance in waste water can influence the practical catalytic effect of catalyst to varying degrees.
How by TiO2Material be modified and obtain the catalyst that can be responded in visible region, and can actually answer
It is the research and development focus of research staff instantly for catalyzing oxidizing degrading sulphadiazine waste water.
Invention content
The purpose of the present invention is overcome TiO in the prior art2Catalyzing oxidizing degrading sulphadiazine only can be in ultraviolet region
The shortcomings that lower implementation of effect, degradation concentration are only 2mg/L；The present invention provides a kind of indium doping containing phosphatization and is modified TiO2Photocatalysis
Material, the present invention is using butyl titanate as TiO2Presoma, be modifying agent using colloidal sol-solidifying using indium phosphide and 8-hydroxyquinoline
The preparation of glue method obtains double modified TiO2Catalysis material；Catalysis material prepared by the present invention can in ultraviolet light and/or too
Catalyzing oxidizing degrading sulphadiazine under sunlight, and catalysis material recoverable can use in high concentration COD waste water.
According to an aspect of the present invention, the present invention provides a kind of indium dopings containing phosphatization to be modified TiO2Catalysis material
Preparation method, include the following steps：
1）34.0g butyl titanates be dissolved in stirred evenly in ethyl alcohol butyl titanate ethanol solution；
2）0.7-1.4g 8-hydroxyquinolines are dissolved in ethyl alcohol, obtain the ethanol solution of 8-hydroxyquinoline, to the ethyl alcohol of 8-hydroxyquinoline
The toluene dispersion liquid of indium phosphide is added dropwise in solution, stirs evenly to obtain the first mixed liquor；
3）First mixeding liquid temperature is warming up to 60-70 DEG C, mixing speed is adjusted to 1000rpm, and butyl titanate is then added dropwise
Ethanol solution, insulated and stirred 1-2h obtains the second mixed liquor after completion of dropwise addition；
4）Acetic acid is added dropwise into the second mixed liquor, adjusts pH to 2-3 and obtains gel-like suspension stirring 4-6h, be cooled to 30-40 DEG C
It stands aging 24-48h and obtains colloid；
5）Colloid at 60-80 DEG C is dried under vacuum to constant weight, is then ground to the particulate matter that grain size is 200-300 mesh；
6）Particulate matter is carried out to high-temperature calcination certain time under nitrogen atmosphere must contain phosphatization indium doping modification TiO2Photocatalysis
Material.
The addition of 8-hydroxyquinoline not only can preferably realize progress photocatalytic degradation organic wastewater under visible light, and
And improve the catalytic activity under ultraviolet region.Preferably, step 2）The weight of middle 8-hydroxyquinoline is 1.1-1.2g；
Photocatalysis oxidation reaction is mainly using the oxidability of the photohole of photochemical catalyst, and photo-generate electron-hole is to dividing
Better from effect, catalytic activity is also higher；The doping of indium phosphide can effectively improve TiO2Surface photoexcitation carrier
Separating effect, activity hydroxy is made largely to generate and participates in oxidation reaction, so as to improve photocatalysis performance；When phosphatization indium doping
When excessive, excessive In can be deposited on TiO2Surface hinders the progress of light-catalyzed reaction；But it is difficult to produce again when doping deficiency
Raw enough photoelectron capturing agents, can not effectively inhibit light induced electron；To adjust catalyst activity, it is preferred that in molar ratio
It calculates, step 2）The addition of middle indium phosphide is the 1-3% of butyl titanate mole.
Calcination temperature has a significant impact to photocatalytic activity, and higher calcination temperature is conducive to TiO2The solid phase of photochemical catalyst
It reacts and forms complete crystal structure, so as to improve its photocatalytic activity；But if calcination temperature is excessively high, so that causing catalysis
Dosage form state changes and catalyst activity is caused to reduce；Preferably, step 6）Described in high-temperature calcination certain time refer to
2-3h is calcined at 260-300 DEG C.
According to another aspect of the present invention, the present invention provides a kind of indium dopings containing phosphatization to be modified TiO2Photocatalysis material
The purposes of material, for catalytic degradation sulphadiazine waste water；The indium doping containing phosphatization is modified TiO2Catalysis material for urging
Change degradation sulphadiazine waste water the specific steps are：
1）1L sulphadiazine waste water is passed sequentially through into activated carbon filtering and filtering with microporous membrane removes its solid suspension and glue
Object obtains sulphadiazine waste water filtrate；The present invention also plays the effect of partial decolorization using activated carbon filtering, conducive to next step part
Photocatalytic oxidation degradation；
2）Sulphadiazine waste water filtrate pH is adjusted to acidity, indium doping containing phosphatization is then added in and is modified TiO2Catalysis material
Adsorption/desorption, which is carried out, after stirring 0.5-1h balances to obtain degraded solutions to be oxidized；
3）Degraded solutions to be oxidized are warming up to 40-50 DEG C, be placed under sunlight and/or ultraviolet light under carry out oxidative degradation, drop
The modification of indium doping containing phosphatization TiO is recovered by filtration to obtain after solution2Catalysis material and cleaning waste water.
The dosage of catalysis material can influence the efficiency of wastewater treatment, and generally catalysis material dosage is more, can generate
More reactive hydroxyl radicals are so as to accelerate degradation speed, and it is more thorough to degrade, and intermediates product is fewer；But it is catalyzed
Agent dosage can excessively cause cost to increase, as the preferred embodiment of the present invention, step 2）In indium doping containing phosphatization be modified TiO2's
The addition of catalysis material is 15-25mg；
In order to study influences of the pH to reaction in catalyzing oxidizing degrading reaction, the present invention is adjusted molten using sodium hydroxide or hydrochloric acid
Liquid obtains step 2 into different pH）The acid pH is 5.5-5.8 catalytic efficiency highests.
Indium doping containing phosphatization prepared by the present invention is modified TiO2Catalysis material it is recyclable apply mechanically, but use three times after
Its oxidative degradation ability to sulphadiazine declines, and especially visible region degradation capability declines particularly evident；To overcome this
Defect, the present invention provides a kind of indium dopings containing phosphatization to be modified TiO2Catalysis material activation method, include the following steps：
1）The modification of indium doping containing phosphatization TiO will be recycled to obtain2Catalysis material be impregnated in first in N,N-Dimethylformamide surpass
Sound 1-2h；
2）It is filtered after ultrasound, filter cake, which is impregnated in the mixed liquor of hydrogen peroxide and hydrochloric acid, impregnates 12h；
3）Filtering, the indium doping containing phosphatization of washing, acetone washing after 1-2h is calcined under nitrogen atmosphere and must be activated are modified TiO2
Catalysis material, calcining 1-2h refers to carry out calcining 1-2h at 260-300 DEG C under the preferred nitrogen atmosphere.
In activation process the present invention it is ultrasonically treated using organic solvent DMF first, removal catalysis material surface with
Dissolved organic matter inside aperture releases the active site that organic matter covers, will secondly using the method for oxidation
The substance combined with catalysis material active site is aoxidized the catalysis material that then calcining is activated, if only simple calcining
Then activation effect unobvious.
Compared with prior art, the invention has the advantages that：
1）The invention uses indium phosphide and 8-hydroxyquinoline as dopant, using sol-gal process to TiO2Changed
Property, it obtains material and may be implemented in catalyzing oxidizing degrading organic wastewater in the range of visible region；
2）Indium doping containing phosphatization prepared by the present invention is modified TiO2Catalysis material can be used for catalytic degradation high concentration sulfanilamide (SN) it is phonetic
Pyridine waste water, degradation rate is high, non-secondary pollution；
3）Indium doping containing phosphatization prepared by the present invention is modified TiO2Catalysis material recoverable, and can be in acid item
Oxidation processes activation is carried out under part, reduces production cost to a certain extent；
4）Catalysis material of the present invention can degrade the sulphadiazine in high COD systems, have actual application prospect.
Description of the drawings
Fig. 1 is the InP/8-HQ/TiO that embodiment 1 is prepared2The scanning electron microscope (SEM) photograph of material；
Fig. 2 is the InP/TiO that embodiment 1-A is prepared2The scanning electron microscope (SEM) photograph of material；
Fig. 3 is degradation rate curve of the different catalysts under natural light.
Specific embodiment
Understand to make the object, technical solutions and advantages of the present invention clearer, With reference to embodiment, to this
Invention is further described.It should be understood that these descriptions are merely illustrative, and it is not intended to limit the scope of the present invention.
Sulphadiazine waste water used comes from the pretreated waste water of Zhengzhou Chemical Co., Ltd. in the embodiment of the present invention（It is useless
Water is into brown, CODcr=8940mg/L, pH=7.2-7.5；A concentration of 42-48mg/L of sulphadiazine）, sulphadiazine in waste water
Content is measured using HPLC using external standard method, Detection wavelength 254nm, chromatographic column C18（250mmX4.6mm）, flowing
Phase V（Acetonitrile）：V（0.01wt% phosphate aqueous solutions）=20:80, flow velocity 1ml/min.
Embodiment 1
It prepares indium doping containing phosphatization and is modified TiO2Catalysis material, include the following steps：
1）34.0g butyl titanates be dissolved in stirred evenly in 500ml ethyl alcohol butyl titanate ethanol solution；
2）1.1g 8-hydroxyquinolines are dissolved in 30ml ethyl alcohol, obtain the ethanol solution of 8-hydroxyquinoline, to the ethyl alcohol of 8-hydroxyquinoline
The toluene dispersion liquid of 10ml indium phosphides is added dropwise in solution（0.29g containing indium phosphide）, stir evenly to obtain the first mixed liquor；
3）First mixeding liquid temperature is warming up to 60-70 DEG C, mixing speed is adjusted to 1000rpm, and butyl titanate is then added dropwise
Ethanol solution, insulated and stirred 1-2h obtains the second mixed liquor after completion of dropwise addition；
4）Acetic acid is added dropwise into the second mixed liquor, adjusts pH to 2-3 and obtains gel-like suspension stirring 4-6h, be cooled to 30-40 DEG C
It stands aging 24-48h and obtains colloid；
5）Colloid at 60-80 DEG C is dried under vacuum to constant weight, is then ground to the particulate matter that grain size is 200-300 mesh；
6）Particulate matter is calcined to 2-3h at 260-300 DEG C under nitrogen atmosphere must contain phosphatization indium doping modification TiO2Photocatalysis
Material is abbreviated as InP/8-HQ/TiO2。
Catalysis material (the InP/8-HQ/TiO that embodiment 1 is prepared2) scanning electron microscope (SEM) photograph is as shown in Figure 1, by can in figure
To find out the catalysis material pattern of the invention prepared as cellular particle, using specific surface area and pore-size distribution tester
（JW-K types）The specific surface of sample is measured, specific surface area 167.2m2/ g (BET method).
Embodiment 1-A
Using single-factor variable method comparative illustration 8-hydroxyquinoline as organic additive to preparing the catalytic of catalysis material
The influence of energy, compared with Example 1, difference lies in 8-hydroxyquinoline is not added, remaining is completely the same with embodiment 1, prepares
Product be abbreviated as InP/TiO2。
The catalysis material scanning electron microscope (SEM) photograph that embodiment 1-A is prepared is as shown in Fig. 2, the present invention makes as can be seen from Figure
It is cellular particle for the catalysis material pattern gone out, aperture is significantly big compared with sample prepared by embodiment 1；Using specific surface area
And pore-size distribution tester（JW-K types）The specific surface of sample is measured, specific surface area is only 117.1m2/g(BET
Method).
Embodiment 1-B
Using single-factor variable method comparative illustration indium phosphide as additive to preparing the influence of the catalytic performance of catalysis material,
Compared with Example 1, difference lies in indium phosphide is not added, remaining is completely the same with embodiment 1, and the product prepared is abbreviated as 8-
HQ/TiO2。
Take sulphadiazine waste water（Waste water is into brown, CODcr=8940mg/L, pH=7.2-7.5；A concentration of 42- of sulphadiazine
48mg/L）Removal solids and colloid substances are filtered using activated carbon, filtrate salt acid for adjusting pH to 6 carries out catalyzing oxidizing degrading
Experiment：
Take titanium dioxide P25,1 product of embodiment（InP/8-HQ/TiO2）And embodiment 1-A（InP/TiO2）With embodiment 1-
B（8-HQ/TiO2）Each 20mg of product, is respectively placed in the filtrate of 1L pH=6, respectively in experiment respectively in natural light and ultraviolet light
（30W, wavelength 254nm）Photocatalytic oxidation degradation is carried out at lower 40 DEG C, HPLC detects remaining sulphadiazine in reaction solution after 3h
Residual quantity and calculate degradation rate, the results are shown in Table 1：
The different catalysis materials of table 1 are under natural light and ultraviolet light to the degradation rate of sulphadiazine
| Titanium dioxide P25 | InP/8-HQ/TiO2 | InP/TiO2 | 8-HQ/TiO2 | |
| Natural light | 13.2% | 89.3% | 67.2% | 25.3% |
| Ultraviolet light（254nm） | 31.8% | 95.8% | 89.1% | 89.6% |
Result above can obtain：1）Degradation rate under ultraviolet light is significantly larger than the degradation rate under natural light, is removed under ultraviolet light several
Reach simple TiO2Degradation rate for outside 31.8%, remaining catalyst is 90% or so；2）After indium phosphide doping vario-property
The degradation rate under natural light can be improved, degradation rate has been increased to 67.2% by 13.2% under simple natural light；Using 8- hydroxyls
Degradation rate under the modified natural light of base quinoline is also promoted, and degradation rate has been increased to 25.3% by 13.2%；And indium phosphide and
The codope modification of 8-hydroxyquinoline plays synergistic effect；3）In high-COD waste water, simple TiO2It is several under natural light
Can not degrade sulphadiazine, although degradation rate is 13.2%, with Liang Fengyan et al.（Ecological environment journal 2009,18 (4):
1227-1230）Report uses TiO under visible light2The degradation rate that degradation sulphadiazine reaches 50% still has very big difference
Away from；Also illustrate that the sulphadiazine in degradation high-COD waste water will complexity more than simple sulphadiazine from another angle.
Fig. 3 is titanium dioxide P25, InP/8-HQ/TiO2、InP/TiO2、8-HQ/TiO2Four kinds of catalyst system and catalyzings are in visible ray
Under degradation rate table（Using the time as horizontal axis, using degradation rate as the longitudinal axis）, in table it can be seen that before individual titanium dioxide P25 systems
90min occurs almost without the degradation of sulphadiazine, and most degradations is happened between 90-120min；And 8-HQ/TiO2It urges
Change system shifts to an earlier date compared with titanium dioxide P25 systems, and overwhelming majority degradation is happened in 60-90min sections, so 8-hydroxyquinoline
Addition can not only increase degradation rate, but also rates of oxidative degradation can be accelerated；InP/TiO2Degradation in 30-150min
Almost linear degradation reaches degradation balance after 150min；InP/8-HQ/TiO2System degradation occurs mainly in 30-
In 120min sections, compared with InP/TiO2In advance close to degradation balance, so also demonstrating 8-hydroxyquinoline from another angle
Addition can not only increase degradation rate, but also rates of oxidative degradation can be accelerated.
Embodiment 2
InP/8-HQ/TiO under natural light2The optimization of catalyst system and catalyzing：Primary study InP/8-HQ/TiO2The dosage of material is urged
Change the influence that the parameters such as degradation temperature, degradation system pH generate degradation rate, the results are shown in Table 2：
Wherein test procedure is：
1）1L sulphadiazine waste water is passed sequentially through into activated carbon filtering and filtering with microporous membrane removes its solid suspension and glue
Object obtains sulphadiazine waste water filtrate；
2）Sulphadiazine waste water filtrate is adjusted using hydrochloric acid or Strong oxdiative sodium pH to certain pH value, then adds in and is mixed containing indium phosphide
Miscellaneous modified TiO2Catalysis material stirring 0.5-1h after carry out adsorption/desorption balance to obtain degraded solutions to be oxidized；
3）Degraded solutions to be oxidized are warming up to certain temperature, are placed in progress oxidative degradation 3h, mistake after degradation under sunlight
The modification of indium doping containing phosphatization TiO is recycled to obtain in filter2Catalysis material and cleaning waste water, HPLC measure sulphadiazine before and after degradation
Concentration calculates its degradation rate.
InP/8-HQ/TiO under 2 natural light of table2Influence of the catalyst system and catalyzing different parameters to degradation rate
| Test serial number | InP/8-HQ/TiO2Dosage mg/L | System pH | Reaction temperature/DEG C | Degradation rate/% |
| 1 | 5 | 7.3 | 30 | 56.4 |
| 2 | 10 | 7.3 | 30 | 68.2 |
| 3 | 15 | 7.3 | 30 | 73.2 |
| 4 | 20 | 7.3 | 30 | 75.2 |
| 5 | 25 | 7.3 | 30 | 74.3 |
| 6 | 30 | 7.3 | 30 | 74.7 |
| 7 | 20 | 2-3 | 30 | 49.7 |
| 8 | 20 | 3-4 | 30 | 51.7 |
| 9 | 20 | 4-5 | 30 | 71.7 |
| 10 | 20 | 5-6 | 30 | 72.5 |
| 11 | 20 | 5-6 | 30 | 78.5 |
| 12 | 20 | 6-7 | 30 | 72.6 |
| 13 | 20 | 7-8 | 30 | 72.4 |
| 14 | 20 | 8-9 | 30 | 62.3 |
| 15 | 20 | 5-6 | 0 | 73.2 |
| 16 | 20 | 5-6 | 20 | 79.3 |
| 17 | 20 | 5-6 | 40 | 89.3 |
| 18 | 20 | 5-6 | 45 | 92.1 |
| 19 | 20 | 5-6 | 50 | 92.3 |
| 20 | 20 | 5-6 | 60 | 92.2 |
So optimal procedure parameters are：InP/8-HQ/TiO2The dosage 20mg/L waste water of material, 40-50 DEG C of catalytic degradation temperature,
Degradation system pH is 5-6；To experiment serial number 20 treated wastewater test, its CODcr is 930, and oxygen demand substantially reduces.
Embodiment 3
Assess catalyst（InP/8-HQ/TiO2Material）Recycled performance（After being recovered by filtration, washing, which is dried, carries out weight
It is multiple to use）：It is degraded under natural light sulphadiazine waste water, access times and sulfanilamide (SN) using the optimal procedure parameters of embodiment 2
The degradation rate of pyrimidine the results are shown in Table shown in 3：
3 catalyst performance stability assessment of table
| Access times n/ times | 1 | 2 | 3 | 4 | 5 |
| Sulphadiazine degradation rate/% | 92.5 | 83.4 | 65.3 | 39.2 | 34.6 |
Decline the above result shows that the catalyst increases catalyst performance accumulation with access times, can recycle twice, but
Using the degradation rate for being only afterwards three times 65.3%, follow-up use can not be met.
Embodiment 4
In order to be activated catalyst performance, so as to make catalyst cost reduction, the present invention have studied high-temperature calcination, pickling,
The modes such as alkali cleaning, oxidation activate the catalyst after recycling：
First, high-temperature calcination activates：Fresh catalyst is dried in vacuo using being washed after 1 time to it at 80 DEG C, then
Calcining 2h is carried out at 260-300 DEG C；
2nd, pickling or alkali cleaning：Fresh catalyst is subsequently placed in the hydrochloric acid or 2 of 2 mol/L using being washed after 1 time to it
Soaking at room temperature for 24 hours, wash, be dried in vacuo at 80 DEG C, then at 260-300 DEG C by filtering in the sodium hydrate aqueous solution of mol/L
Under carry out calcining 2h；
3rd, oxidized activating：Fresh catalyst is subsequently placed in soaking at room temperature in 30%wt hydrogen peroxide using being washed after 1 time to it
For 24 hours, it filters, wash, be dried in vacuo at 80 DEG C, calcining 2h is then being carried out at 260-300 DEG C；
4th, pickling/oxidation：Then fresh catalyst is impregnated in N,N-Dimethylformamide using being washed after 1 time to it
Ultrasonic 1-2h；It is filtered after ultrasound, filter cake is impregnated in the mixed liquor of hydrogen peroxide and hydrochloric acid（Concentration of hydrochloric acid 2mol/ in mixed liquor
L, hydrogen peroxide concentration 25-30%wt）Middle dipping 12h；Filtering, washing, acetone washing after under nitrogen atmosphere at 260-300 DEG C
Carry out calcining 2h.
Using the optimal procedure parameters in embodiment 2, performance is carried out to the catalyst that above-mentioned Different Activation Methods obtain and is commented
Estimate, it is as a result as shown in table 4 below：
The catalyst activity that 4 Different Activation Methods of table obtain
| High-temperature calcination | Pickling | Alkali cleaning | Oxidation | Pickling/oxidation | |
| Sulphadiazine degradation rate/% | 82.1 | 83.2 | 79.6 | 86.3 | 93.1 |
The above result shows that merely using two methods of high-temperature calcination, pickling substantially to catalyst without activation, alkali cleaning is instead
Catalyst activity is reduced to a certain extent；And method for oxidation improves amount of activated, the method especially in acidity/oxidation
In its catalytic activity reached highest, sulphadiazine degradation rate has reached 93.1%, high with fresh catalyst 92.5%, it may be possible to by
In in catalyst activation process, catalyst generates substance of the part containing oxidation susceptibility, its oxidisability is caused to enhance, and increases
The degradation rate of sulphadiazine.
Although embodiments of the present invention are described in detail, it should be understood that, without departing from the present invention's
In the case of spirit and scope, can embodiments of the present invention be made with various changes, replacement and change.
Claims (10)
1. a kind of indium doping containing phosphatization is modified TiO2Catalysis material preparation method, include the following steps：
1）34.0g butyl titanates be dissolved in stirred evenly in ethyl alcohol butyl titanate ethanol solution；
2）0.7-1.4g 8-hydroxyquinolines are dissolved in ethyl alcohol, obtain the ethanol solution of 8-hydroxyquinoline, to the ethyl alcohol of 8-hydroxyquinoline
The toluene dispersion liquid of indium phosphide is added dropwise in solution, stirs evenly to obtain the first mixed liquor；
3）First mixeding liquid temperature is warming up to 60-70 DEG C, mixing speed is adjusted to 1000rpm, and butyl titanate is then added dropwise
Ethanol solution, insulated and stirred 1-2h obtains the second mixed liquor after completion of dropwise addition；
4）Acetic acid is added dropwise into the second mixed liquor, adjusts pH to 2-3 and obtains gel-like suspension stirring 4-6h, be cooled to 30-40 DEG C
It stands aging 24-48h and obtains colloid；
5）Colloid at 60-80 DEG C is dried under vacuum to constant weight, is then ground to the particulate matter that grain size is 200-300 mesh；
6）Particulate matter is carried out to high-temperature calcination certain time under nitrogen atmosphere must contain phosphatization indium doping modification TiO2Photocatalysis material
Material.
2. preparation method according to claim 1, it is characterised in that：Step 2）The weight of middle 8-hydroxyquinoline is 1.1-
1.2g。
3. preparation method according to claim 1, it is characterised in that：For calculation in the molar ratio, step 2）Middle indium phosphide adds
Enter the 1-3% that amount is butyl titanate mole.
4. preparation method according to claim 1, it is characterised in that：Step 6）Described in high-temperature calcination certain time refer to
2-3h is calcined at 260-300 DEG C.
5. a kind of indium doping containing phosphatization is modified TiO2Catalysis material purposes, it is characterised in that：It is phonetic for catalytic degradation sulfanilamide (SN)
Pyridine waste water.
6. purposes according to claim 5, it is characterised in that：The indium doping containing phosphatization is modified TiO2Catalysis material
For catalytic degradation sulphadiazine waste water the specific steps are：
1）1L sulphadiazine waste water is passed sequentially through into activated carbon filtering and filtering with microporous membrane removes its solid suspension and glue
Object obtains sulphadiazine waste water filtrate；
2）Sulphadiazine waste water filtrate pH is adjusted to acidity, indium doping containing phosphatization is then added in and is modified TiO2Catalysis material
Adsorption/desorption, which is carried out, after stirring 0.5-1h balances to obtain degraded solutions to be oxidized；
3）Degraded solutions to be oxidized are warming up to 40-50 DEG C, be placed under sunlight and/or ultraviolet light under carry out oxidative degradation, drop
The modification of indium doping containing phosphatization TiO is recovered by filtration to obtain after solution2Catalysis material and cleaning waste water.
7. purposes according to claim 6, it is characterised in that：Step 2）In indium doping containing phosphatization be modified TiO2Photocatalysis
The addition of material is 15-25mg.
8. purposes according to claim 6, it is characterised in that：Step 2）The acid pH is 5.5-5.8.
9. indium doping containing phosphatization described in a kind of claim 1 is modified TiO2Catalysis material activation method, it is characterised in that：
Include the following steps：
1）The modification of indium doping containing phosphatization TiO will be recycled to obtain2Catalysis material be impregnated in first in N,N-Dimethylformamide it is ultrasonic
1-2h；
2）It is filtered after ultrasound, filter cake, which is impregnated in the mixed liquor of hydrogen peroxide and hydrochloric acid, impregnates 12h；
3）Filtering, the indium doping containing phosphatization of washing, acetone washing after 1-2h is calcined under nitrogen atmosphere and must be activated are modified TiO2's
Catalysis material.
10. activation method according to claim 9, it is characterised in that：1-2h is calcined under the nitrogen atmosphere to refer to
Calcining 1-2h is carried out at 260-300 DEG C.
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