CN109603884A - A kind of preparation method and applications of visible light catalyst material - Google Patents
A kind of preparation method and applications of visible light catalyst material Download PDFInfo
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- CN109603884A CN109603884A CN201910004359.9A CN201910004359A CN109603884A CN 109603884 A CN109603884 A CN 109603884A CN 201910004359 A CN201910004359 A CN 201910004359A CN 109603884 A CN109603884 A CN 109603884A
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- visible light
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- 239000003054 catalyst Substances 0.000 title claims abstract description 73
- 239000000463 material Substances 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000010865 sewage Substances 0.000 claims abstract description 41
- UMGDCJDMYOKAJW-UHFFFAOYSA-N aminothiocarboxamide Natural products NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000002243 precursor Substances 0.000 claims abstract description 27
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims abstract description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 22
- 239000010439 graphite Substances 0.000 claims abstract description 22
- XKLJHFLUAHKGGU-UHFFFAOYSA-N nitrous amide Chemical compound ON=N XKLJHFLUAHKGGU-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000005516 engineering process Methods 0.000 claims abstract description 19
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- 239000000273 veterinary drug Substances 0.000 claims abstract description 15
- 230000003647 oxidation Effects 0.000 claims abstract description 11
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 11
- 241000411851 herbal medicine Species 0.000 claims abstract description 10
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims abstract description 9
- 238000002336 sorption--desorption measurement Methods 0.000 claims abstract description 9
- -1 thiourea compound Chemical class 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000003344 environmental pollutant Substances 0.000 claims abstract description 3
- 231100000719 pollutant Toxicity 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 28
- KIPLYOUQVMMOHB-MXWBXKMOSA-L [Ca++].CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O.CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O Chemical group [Ca++].CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O.CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O KIPLYOUQVMMOHB-MXWBXKMOSA-L 0.000 claims description 19
- 229940063650 terramycin Drugs 0.000 claims description 19
- 238000001354 calcination Methods 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 8
- 229910052724 xenon Inorganic materials 0.000 claims description 7
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical group [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000011888 foil Substances 0.000 claims description 5
- 230000000873 masking effect Effects 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 238000005245 sintering Methods 0.000 claims description 3
- 239000013077 target material Substances 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 239000003814 drug Substances 0.000 claims description 2
- 229940079593 drug Drugs 0.000 claims description 2
- 229910052571 earthenware Inorganic materials 0.000 claims description 2
- 239000006071 cream Substances 0.000 claims 1
- 230000000149 penetrating effect Effects 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 239000002351 wastewater Substances 0.000 abstract description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052717 sulfur Inorganic materials 0.000 abstract description 4
- 239000011593 sulfur Substances 0.000 abstract description 4
- 238000012545 processing Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 18
- 230000003115 biocidal effect Effects 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 230000001699 photocatalysis Effects 0.000 description 11
- 230000008569 process Effects 0.000 description 11
- 239000004065 semiconductor Substances 0.000 description 11
- 238000004659 sterilization and disinfection Methods 0.000 description 11
- UMFJAHHVKNCGLG-UHFFFAOYSA-N n-Nitrosodimethylamine Chemical compound CN(C)N=O UMFJAHHVKNCGLG-UHFFFAOYSA-N 0.000 description 9
- 239000006227 byproduct Substances 0.000 description 8
- 150000004005 nitrosamines Chemical class 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 6
- 239000003242 anti bacterial agent Substances 0.000 description 6
- 229940088710 antibiotic agent Drugs 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- 238000007146 photocatalysis Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- RHUYHJGZWVXEHW-UHFFFAOYSA-N 1,1-Dimethyhydrazine Chemical compound CN(C)N RHUYHJGZWVXEHW-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 241001465754 Metazoa Species 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 239000005416 organic matter Substances 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000009303 advanced oxidation process reaction Methods 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000000249 desinfective effect Effects 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- POCJOGNVFHPZNS-ZJUUUORDSA-N (6S,7R)-2-azaspiro[5.5]undecan-7-ol Chemical compound O[C@@H]1CCCC[C@]11CNCCC1 POCJOGNVFHPZNS-ZJUUUORDSA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- JIHQDMXYYFUGFV-UHFFFAOYSA-N 1,3,5-triazine Chemical group C1=NC=NC=N1 JIHQDMXYYFUGFV-UHFFFAOYSA-N 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- 208000005168 Intussusception Diseases 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- 206010058467 Lung neoplasm malignant Diseases 0.000 description 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical class CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- BSPUVYFGURDFHE-UHFFFAOYSA-N Nitramine Natural products CC1C(O)CCC2CCCNC12 BSPUVYFGURDFHE-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229920000289 Polyquaternium Polymers 0.000 description 1
- 239000004098 Tetracycline Substances 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 239000003957 anion exchange resin Substances 0.000 description 1
- 239000012984 antibiotic solution Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- POCJOGNVFHPZNS-UHFFFAOYSA-N isonitramine Natural products OC1CCCCC11CNCCC1 POCJOGNVFHPZNS-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 201000007270 liver cancer Diseases 0.000 description 1
- 208000014018 liver neoplasm Diseases 0.000 description 1
- 201000005202 lung cancer Diseases 0.000 description 1
- 208000020816 lung neoplasm Diseases 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 239000002207 metabolite Substances 0.000 description 1
- 230000007886 mutagenicity Effects 0.000 description 1
- 231100000299 mutagenicity Toxicity 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 210000000653 nervous system Anatomy 0.000 description 1
- 238000007034 nitrosation reaction Methods 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 244000144977 poultry Species 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
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- 238000000197 pyrolysis Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
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- 230000001954 sterilising effect Effects 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 229960002180 tetracycline Drugs 0.000 description 1
- 229930101283 tetracycline Natural products 0.000 description 1
- 235000019364 tetracycline Nutrition 0.000 description 1
- 150000003522 tetracyclines Chemical class 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 210000002700 urine Anatomy 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/39—
-
- 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
- C02F2101/306—Pesticides
-
- 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
Abstract
A kind of preparation method and applications of visible light catalyst material are calcined using thiourea compound as presoma through program mode heating step, and the class graphite phase carbon nitride g-C for setting and obtaining sulfur doping by gas phase is stacked by size container set3N4Visible light catalyst material；The visible light catalyst material is used for the visible light photocatalytic degradation of sewage herbal medicine class nitrosamine precursor；The catalyst material is added into the solution containing veterinary drug class nitrosamine precursor；Solution of the catalyst after adsorption-desorption balances is placed under simulated solar visible light environment and is irradiated, the veterinary drug class nitrosamine precursor in oxidation removal sewage.The technology is suitble to handle the sewage and other similar pharmacy waste water difficult to degrade of the nitrosamine precursor of class containing veterinary drug, raw materials required for the reaction is wide, it is at low cost, condition is simple and easy, short processing time, pollutants removal rate is high, and without secondary pollution, be conducive to the resource utilization of sewage, industrial applications have a extensive future.
Description
Technical field
The invention belongs to water-treatment technology fields, are related to the preparation method and applications of visible light catalyst material, especially
It is the application in removal water body herbal medicine class nitrosamine precursor.
Background technique
During the regeneration of sewage, the public health security of recycled water is always the problem of being concerned, and disappears
Poison is to ensure the essential link of water quality safety as last barrier.In current numerous sterilization process, chlorination according to
Its advantage economic, efficiently, easy, is widely used in the disinfection treatment of water and sewage.But meanwhile using Cl2Disinfection can produce
Raw a large amount of disinfection by-products, such as haloform, halogen acetic acid, halogen acetonitrile and halogenated aldehyde, and it is continuous with analysis means
Progress is gradually attracted attention with the nitrosamines disinfection by-products that N-Nitrosodimethylamine (NDMA) is representative in recent years, and at
For current one of research hotspot.The reason is that, the nitrosamines disinfection by-products such as NDMA is a kind of strong carcinogenicity substance, can draw
The damage of liver cancer, lung cancer and nervous system is played, carcinogenic risk and mutagenicity are the several of traditional halogenated disinfection by-products
Ten times, so having to control its generation in disinfecting process, increase generation and removal to nitrosamines disinfection by-products
The research of principle.It is now recognized that discharge and people of the nitrosamines substance in sewage in addition to raw material production (or use) enterprise
Except body metabolism, the precursor in sewage passes through (reinforcing) nitrosation reaction and (modified) 1,1- Dimethylhydrazine
(UDMH) approach generates.In order to control the generation of nitrosamines disinfection by-products in disinfecting process, main path is exactly to strengthen it
Removal of the precursor in sewage disposal system.
Existing research shows amine (including tertiary amine and quaternary amine etc.) and its polymer containing dimethylamine (DMA) functional group
(such as polyquaternium), dimethylformamide class, anion exchange resin, the functional group containing DMA drug and personal-care supplies
(PPCPs), Insecticides (tech) & Herbicides (tech), natural organic matter (NOM) in sewage etc. are important NDMA precursors.With grinding
That studies carefully gradually gos deep into, and more and more NDMA precursors are found to have very high formation potential, but still have nearly 80% still to locate
In unknown state.In recent years, using tetracycline as the antibiotics of representative because biodegradability is poor, in sewage treatment system
It cannot be removed well in system, and it largely contains functional group containing DMA, has higher NDMA formation potential, gradually
It attracts attention.Currently, the research about antibiotics nitrosamine precursor is also relatively fewer, and more attention is people's antibiosis
Element, seldom concern veterinary antibiotic.However, from the point of view of the service condition of current global antibiotic, the usage amount of veterinary antibiotic
Much higher than people's antibiotic, main reason is that veterinary antibiotic is made an addition in animal feed with low dosage concentration for a long time, use
In the growth for promoting domestic animal, poultry and fish.And be only absorbed and utilized on a small quantity by animal in used veterinary antibiotic,
It is most of still to enter municipal sewage plant (or soil environment) in the form of parent or metabolite urine and excrement.Into
Enter the veterinary antibiotic of municipal sewage, wherein hydrophobic part passes through the discharge of excess sludge after sewage treatment plant is handled
It is removed, however major part still has in water outlet, this will certainly generate potential risk to the regeneration of tail water.Cause
This, it is necessary to be carried out to the veterinary antibiotic removal technology that can generate one of nitrosamines disinfection by-products formation potential in sewage
Research and development are explored.
After sewage plant biological treatment, remaining veterinary drug class antibiotic has that toxicity is big, complicated component, processing in water body
The features such as difficulty is larger.Therefore, advanced oxidation processes have wide answer in the such antibiotic waste water process field difficult to degrade of processing
Use prospect.Advanced oxidation processes are to utilize oxidizing species (hydroxyl radical free radical, ozone, superoxide radical etc.) and dissolve in waste water
Pollutant reacted, thus by the wastewater treatment method of contaminant degradation.It, can according to the difference of oxide species producing method
To be divided into Fenton oxidation method, photocatalytic oxidation, electrochemical oxidation process, Electrocatalytic Oxidation, low temperature plasma method etc..And its
In photocatalytic oxidation by its handle the reaction condition that has of antibiotic waste water is mild, degradation thoroughly, strong applicability, without two
The advantages that secondary pollution, gets more and more people's extensive concerning.It is generally believed that the principle of photocatalytic oxidation is suspended in light source irradiation
Photochemical catalyst in antibiotic solution, when incident laser energy is greater than the band gap of photochemical catalyst, light energy is absorbed by catalyst, is produced
Raw hole-electron pair, the substances such as the water and oxygen that are adsorbed on catalyst surface and these electron hole pairs act on, and can produce tool
There are hydroxyl radical free radical and the superoxide anion etc. of strong oxidizing property, achievees the effect that oxidative degradation organic matter.But at present about light
The light source that catalysis technique uses focuses primarily upon ultraviolet light level of the wavelength less than 380 nanometers for only accounting for sunlight wavelength 3-5%
On, about using the visible light for occupying sunlight 45% as photocatalysis technology light source come veterinary drug class antibiotic waste water of degrading
It studies also rather seldom.And compared to ultraviolet light, use visible light as light source, also there is energy conservation and environmental protection, at low cost, stability
Well, the advantages that Yi Shixian.
In recent years, with the update of efficient visible light catalyst and development, but also visible light goes to remove water as light source
Hardly degraded organic substance has a good application prospect in body.Although photocatalytic oxidation has centainly in terms of handling antibiotic waste water
Advantage, but be also primarily present certain technical bottleneck at present, be concentrated mainly on that catalyst preparation is at high cost, catalyst material light
Responding ability is weak, the efficiency of light energy utilization is low, there may be the bigger intermediate products of toxicity, catalyst recycling difficulty etc..Wherein,
The preparation of class graphite phase carbon nitride about one of catalyst material, conventional method there is blocky-shaped particles larger, specific surface
The problems such as product is less than normal, crystallinity is lower, polymerization is incomplete, limits the application prospect of carbon nitride material, and preparation method can be to
It is further improved.
Summary of the invention
In view of the above-mentioned deficiencies in the prior art, it is an object of the present invention to provide a kind of preparation side of visible light catalyst material
Gained visible light catalyst material is applied to sewage treatment by method, in particular for sewage herbal medicine class nitrosamine precursor
Visible light photocatalytic degradation technology.
To achieve the above object, the present invention adopts the following technical scheme:
A kind of preparation method of visible light catalyst material: using thiourea compound as presoma, through program mode heating step
Calcining takes different two ceramic crucibles of relative size, raw material thiocarbamide is put into small crucible, after small crucible placed into big crucible
In, it covers and so that crucible cover is fixed together with big crucible around masking foil, apparatus for placing is folded by size crucible sleeve and relies on gas
Mutually obtain the visible light catalyst material.
The preparation method of one type graphite phase carbon nitride particle, comprising the following steps:
(1) presoma prepares: weighing 20 grams of thiocarbamides (Thiourea), thiocarbamide is without doing any pre-treatment；
(2) it calcines: preparing 40 milliliters and 100 milliliters of two crucibles, thiocarbamide alleged by step (1) is placed in 40 milliliters of small crucibles
It is interior.40 milliliters of crucibles are placed in 100 milliliters of crucibles afterwards, as shown in Fig. 1.100 milliliters of crucibles are closed the lid afterwards, are used in combination
Masking foil winds crucible and pot cover to be fixed, and is finally putting into Muffle furnace and carries out heating calcining.
(3) program mode heating step is arranged: from room temperature state, being heated up with the heating rate of 2-3 centigrade per minute
Program setting, and it is small in 259 degrees Celsius of holdings 1-1.5 hours, 426 degrees Celsius of heat preservations 1-1.5 hours, 550 degrees Celsius of heat preservation 3-4
Shi Jinhang calcining, and calcination process does not need any inertia protection gas.
(4) after sintering soak, cooled to room temperature.Crucible is opened, on 100 milliliters of crucible pot covers and pot inner wall
The beige material of attachment is target material g-C3N4, it is ground up, sieved by 300 mesh or with upper screen cloth, that is, is successfully prepared one
Kind has porous and class graphite phase carbon nitride catalyst material containing micro sulfur doping；Such as one kind has porous and divides containing quality
The class graphite phase carbon nitride catalyst material of the micro sulfur doping of number 0.1%.
Afterwards in the environment of initial pH is 3-11, Xiang Hanyou mass concentration is 5-20 milligrams per liter of veterinary drug such as terramycin
Solution in add the catalyst material, catalyst material dosage is 0.2-2 gram per liters.Afterwards be protected from light under stirring condition,
After so that catalyst and solution is reached adsorption-desorption balance by 30-40 minutes, solution is placed under 300 watts of xenon lamps and is simulated
Sun radiation of visible light, reaction time 20-40 minute, can veterinary drug class nitrosamine precursor in oxidation removal sewage.
It is that analysis is pure, and is not necessarily to any pretreatment for step (1) the presoma thiocarbamide in the present invention；
It is that thiocarbamide is quickly evaporate into heating process in order to prevent for step (2) aluminium-foil paper sealing in the present invention
In air, the quality and quality of synthetic material are reduced；
It is not same phase transition temperature of the thiocarbamide in pyrolytic process for several temperature described in step (3) in the present invention
Degree；
In the present invention, for catalyst and solution when being protected from light with reaching used in adsorption-desorption balance under stirring condition
Between be 30-40 minutes.
By adopting the above-described technical solution, the invention has the following advantages that
1. using thiocarbamide as presoma, by simple program mode heating temperature control and high-temperature polycondensation method, by gas phase
It is successfully prepared a type graphite phase carbon nitride catalyst material.Using the above method, it can obtain that specific surface area is bigger, light is urged
Change the higher class graphite phase carbon nitride catalyst material of activity.And relative to other methods, the method operating procedure is more simple,
Preparation cost is lower, provides new thinking for the preparation optimization and application of class graphite phase carbon nitride.
2, applied widely, reaction condition is simple and easy.The present invention is to containing veterinary drug antibiotics nitrosamine precursor
Waste water in add the class graphite phase carbon nitride semiconductor catalyst material of preparation, under simulated solar irradiation irradiation, reaction temperature
It is unlimited, it can reach good removal effect under normal temperature and pressure.
3. environmental-friendly.It is of the present invention that waste water herbal medicine antibiotics are handled using visible light photocatalytic degradation technology
Nitrosamine precursor is formed by photocatalysis technology and catalyst elements, not will cause in concentration range used to environment
Secondary pollution is generally acknowledged green new catalyst.It is substantially free of harmful organic matter in treated sewage, is conducive to sewage
Resource utilization.
4. applicable object range is wide.The technology of the present invention is in addition to illustrating that antibiotics containing veterinary drug are sub- embodiment suitable for this
The terramycin sewage of one of nitramine precursor applies also for the sewage containing other veterinary drug antibiotics nitrosamine precursors.
Detailed description of the invention
Earthenware size crucible intussusception placement schematic when Fig. 1 is class graphite phase carbon nitride material preparation in the present invention.
Fig. 2 is the positions of materials schematic diagram generated in crucible after program mode heats up pyrolysis step.
Fig. 3 is prepared semiconductor catalyst class graphite phase carbon nitride material figure in the present invention.
Fig. 4 is prepared semiconductor catalyst class graphite phase carbon nitride material XRD spectra in the present invention.
Fig. 5 is prepared semiconductor catalyst class graphite phase carbon nitride material FT-IR spectrogram in the present invention.
Fig. 6 is prepared semiconductor catalyst class graphite phase carbon nitride material SEM scanning electron microscope phenogram in the present invention.
Fig. 7 is prepared semiconductor catalyst class graphite phase carbon nitride material EDX power spectrum Elemental analysis data in the present invention
Table figure.
Fig. 8 is the removal rate figure of light degradation and photocatalytic degradation terramycin.
Fig. 9 is removal rate of the photocatalysis technology to it under the conditions of terramycin (OTC) initial concentration is 5-20 milligrams per liter
Figure.
Figure 10 is removal rate figure of the photocatalysis technology to terramycin under the conditions of initial pH is 3-11.
Figure 11 is removal rate figure of the photocatalysis technology to terramycin under the conditions of catalyst concn is 0.2-2 gram per liters.
Specific embodiment
The present invention is a kind of method using visible light catalytic technology removal water body herbal medicine class nitrosamine precursor.The party
Method can quickly and efficiently remove the veterinary drug class nitrosamine precursor in sewage, reduce nitrosamines precursor content and nitrosamines
Disinfection by-products formation potential is conducive to safe and healthy, the resource utilization of subsequent sewage.
Below in conjunction with attached drawing, the present invention is further illustrated.
Embodiment 1
It is first the preparation of catalyst material class graphite phase carbon nitride particle, specific steps are as follows:
(1) presoma prepares: weighing 20 grams of thiocarbamides, thiocarbamide is without doing any pre-treatment；
(2) it calcines: preparing 40 milliliters and 100 milliliters of two crucibles, the weighed thiocarbamide of step (1) institute is placed in 40 milliliters small
In crucible, after 40 milliliters of crucibles are placed in 100 milliliters of crucibles, as shown in Fig. 1.100 milliliters of crucibles are closed the lid afterwards,
And crucible and pot cover are wound with masking foil (as shown in Figure 1) is fixed, it is finally putting into Muffle furnace and carries out heating calcining.
(3) program mode heating step is arranged: from room temperature state, carrying out heating journey with the heating rate of 2 centigrade per minutes
Sequence setting, and keep the temperature 4 hours within heat preservation 1 hour, 550 degrees Celsius within holding 1 hour, 426 degrees Celsius at 259 degrees Celsius and calcined,
And calcination process does not need any inertia protection gas.
(4) after sintering soak, cooled to room temperature.Crucible is opened, on 100 milliliters of crucible pot covers and pot inner wall
The beige material of attachment is target material g-C3N4(position is as shown in Figure 2), such as Fig. 3 after 300 mesh screens are ground up, sieved
It is shown.
Please refer to Fig. 4: by the g-C that the above method is made3N4XRD spectra can be seen that material tool there are two obvious
Diffraction maximum, 2 θ=13.8 ° with 27.3 ° at correspond respectively to standard g-C3N4(100) in (PDF No.87-1526) card
(002) crystal face, the peak at 13.8 ° are structure peaks in the face of s-triazine unit, and the highest peak at 27.3 ° is virtue
Fragrant loop system typical interlayer stacking peak illustrates in synthesized sample with the presence of three-S -5-triazine units, and miscellaneous phase does not spread out
Penetrate peak appearance, it was demonstrated that be the g-C of pure phase using this method products therefrom3N4。
Please refer to Fig. 5: by obtained g-C3N4Known to the FTIR spectrum figure of sample, which has 6 significantly to spread out
Penetrate characteristic peak.812cm-1The absorption peak at place is g-C3N4Triazine ring stretching vibration characteristic peak, 1200-1700cm-1The absorption in section
Peak is due to g-C3N4The characteristic peak that heterocycle stretching vibration generates.And 2900-3500cm-1The broad peak in section is N-H and O-H
The stretching vibration peak of key, the mainly amino and g-C due to the non-polycondensation of thiocarbamide3N4It is infrared caused by the hydrone of adsorption
The characterization of spectrum further demonstrates the g-C that pure phase can be made in above-mentioned this method3N4。
Please refer to Fig. 6: using g- made from the above method it can be seen from the SEM electron-microscope scanning figure of different amplification
C3N4Material is by many relatively small, irregular g-C3N4Lamella stacks, and there are some folds and holes for its lamella
Gap, this is primarily due to caused by the gases such as the ammonia that thiocarbamide generates during thermal polycondensation.To pass through this gas phase shape
At porosity and looseness it is laminar structured so that g-C3N4Specific surface area increase, enhance it in photocatalytic activity.
Please refer to Fig. 7: by the elemental analysis of EDX power spectrum it is found that with common g-C3N4It compares, other than two kinds of elements of C/N,
A small amount of S element is also contained in this material.Show to have also obtained part nonmetalloid sulfur doping by this kind of gas phase process
G-C3N4, by nonmetal doping, the transmitting of semiconductor type catalyst light induced electron can be promoted, reduce light induced electron and sky
Cave recombination rate, this mechanism significantly improve catalyst photocatalytic activity.
It is degraded afterwards using visible light photocatalytic degradation technology to sewage herbal medicine class nitrosamine precursor, is in initial pH
In the environment of 7, above-mentioned prepared semiconductor catalysis is added in the solution for the terramycin that Xiang Hanyou mass concentration is 10 milligrams per liter
Agent material, catalyst material dosage are 1 gram per liter.Maintained 30 minutes under stirring condition being protected from light afterwards, make catalyst with it is molten
After liquid reaches adsorption-desorption balance, solution is placed under 300 watts of xenon lamps, wavelength is isolated out using optical filter and is lower than 380 nanometers
Ultraviolet light, progress simulated visible light irradiation, the reaction time 40 minutes.Before photochemical catalytic oxidation removes the veterinary drug class nitrosamine in sewage
Body object terramycin effect picture is as shown in Figure 1.In reaction 40 minutes, under each primary condition of the present embodiment, terramycin can reach
To completely removing.
Embodiment 2
It is first the preparation of catalyst material class graphite phase carbon nitride particle, the specific steps are the same as those in embodiment 1.
It is degraded afterwards using visible light photocatalytic degradation technology to sewage herbal medicine class nitrosamine precursor, is in initial pH
In the environment of 7, above-mentioned prepared semiconductor is added in the solution for the terramycin that Xiang Hanyou mass concentration is 5-20 milligrams per liter and is urged
Agent material, catalyst material dosage are 1 gram per liter.Maintained 30 minutes under stirring condition being protected from light afterwards, make catalyst with
After solution reaches adsorption-desorption balance, solution is placed under 300 watts of xenon lamps, isolates out wavelength lower than 380 nanometers using optical filter
Ultraviolet light, carry out simulated visible light irradiation, the reaction time 40 minutes.Photochemical catalytic oxidation removes the veterinary drug class nitrosamine in sewage
Precursor terramycin effect picture is as shown in Figure 2.In reaction 40 minutes, under the conditions of initial pH and catalyst concn, moiety concentrations
Terramycin can reach and completely remove.
Embodiment 3
It is first the preparation of catalyst material class graphite phase carbon nitride particle, the specific steps are the same as those in embodiment 1.
It is degraded afterwards using visible light photocatalytic degradation technology to sewage herbal medicine class nitrosamine precursor, at the beginning of adjusting solution
In the environment of beginning pH is 3-11, above-mentioned prepared half is added in the solution for the terramycin that Xiang Hanyou mass concentration is 10 milligrams per liter
Conductor catalyst material, catalyst material dosage are 1 gram per liter.It is maintained 30 minutes under stirring condition being protected from light afterwards, makes to urge
After agent and solution reach adsorption-desorption balance, solution is placed under 300 watts of xenon lamps, wavelength is isolated out using optical filter and is lower than
380 nanometers of ultraviolet light, progress simulated visible light irradiation, the reaction time 40 minutes.The removal of terramycin (OTC) in different time
Rate is shown in Fig. 3.With the difference of the initial pH of initial soln, degrade required reaction time and final removal rate completely are also different.
In reaction 40 minutes, under the conditions of pH is 5,7,9 and 11, terramycin, which can reach, to be completely removed.
Embodiment 4
It is first the preparation of catalyst material class graphite phase carbon nitride particle, the specific steps are the same as those in embodiment 1.
It is degraded afterwards using visible light photocatalytic degradation technology to sewage herbal medicine class nitrosamine precursor, at the beginning of adjusting solution
In the environment of beginning pH is 7, above-mentioned prepared partly lead is added in the solution for the terramycin that Xiang Hanyou mass concentration is 10 milligrams per liter
Body catalyst material, it is 0.2-2 gram per liters that catalyst concn, which is added,.It is maintained 30 minutes under stirring condition being protected from light afterwards, makes to urge
After agent and solution reach adsorption-desorption balance, solution is placed under 300 watts of xenon lamps, wavelength is isolated out using optical filter and is lower than
380 nanometers of ultraviolet light, progress simulated visible light irradiation, the reaction time 40 minutes.The removal rate of terramycin is shown in different time
Fig. 4.With the difference of the catalyst concn of addition, degrade required reaction time and final removal rate completely are also different.?
Reaction 40 minutes in, catalyst add concentration be 1.0,1.5 and 2.0 gram per liters under the conditions of, terramycin, which can reach, to be completely removed.
The visible optical semiconductor catalyst material class graphite phase carbon nitride arrived applied in this technology is amorphous material, is had
Nano-scale particle sizes can be uniformly distributed in aqueous solution and be stabilized.This technology simple process, raw material is wide and cost compared with
It is low, meet needs of production, has in terms of semiconductor catalyst material, solar energy, water process larger
Industrial applications potentiality.
The above-mentioned description to embodiment is that this hair can be understood and applied for the ease of those skilled in the art
It is bright.Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein
General Principle is applied in other embodiments without having to go through creative labor.Therefore, the present invention is not limited to implementations here
Example, those skilled in the art's announcement according to the present invention, the improvement made for the present invention and modification all should be of the invention
Within protection scope.
Claims (11)
1. a kind of preparation method of visible light catalyst material, it is characterised in that: using thiourea compound as presoma, through program mode
Heating step calcining is stacked by size container set and is set by gas phase acquisition class graphite phase carbon nitride g-C3N4Visible light catalyst
Material.
2. the preparation method of visible light catalyst material according to claim 1, it is characterised in that: the container is earthenware
Raw material thiocarbamide is put into small crucible by crucible, after small crucible is placed into big crucible, covering simultaneously makes crucible cover around masking foil
It is fixed together with big crucible.
3. the preparation method of visible light catalyst material according to claim 1, it is characterised in that the following steps are included:
(1) presoma prepares: weighing 20 grams of thiocarbamides；
(2) it calcines: preparing 40 milliliters and 100 milliliters of two crucibles, thiocarbamide alleged by step (1) is placed in 40 milliliters of small crucibles；
40 milliliters of crucibles are placed in 100 milliliters of crucibles afterwards；100 milliliters of crucibles are closed the lid afterwards, and wind crucible with masking foil
With pot cover to be fixed, it is finally putting into Muffle furnace and carries out heating calcining；
(3) program mode heating step is arranged: from room temperature state, carrying out temperature program with the heating rate of 2-3 centigrade per minute
Setting, and 259 degrees Celsius of holdings 1-1.5 hours, 426 degrees Celsius of heat preservations 1-1.5 hours, 550 degrees Celsius of heat preservations 3-4 hours into
Row calcining；
(4) after sintering soak, cooled to room temperature, open crucible, on crucible pot cover and pot inner wall attachment cream colour
Color substance is the class graphite phase carbon nitride g-C of target material in this method3N4。
4. the application of visible light catalyst material any one of claims 1 to 3 in sewage treatment.
5. application of the visible light catalyst material according to claim 4 in sewage treatment, it is characterised in that: will be described
Visible light catalyst material is used for the visible light photocatalytic degradation of sewage herbal medicine class nitrosamine precursor.
6. application of the visible light catalyst material according to claim 5 in sewage treatment, it is characterised in that: Xiang Hanyou
The catalyst material is added in the solution of veterinary drug class nitrosamine precursor；By solution of the catalyst after adsorption-desorption balances
It is placed under simulated solar visible light environment and irradiates, the veterinary drug class nitrosamine precursor in oxidation removal sewage.
7. application of the visible light catalyst material according to claim 6 in sewage treatment, it is characterised in that: be used for mould
The light source of quasi- sun visible light is xenon lamp.
8. application of the visible light catalyst material according to claim 6 in sewage treatment, it is characterised in that: the beast
Medicine is terramycin.
9. application of the visible light catalyst material according to claim 6 in sewage treatment, it is characterised in that: the skill
It is 3-11 that initial pH is reacted in art.
10. application of the visible light catalyst material according to claim 6 in sewage treatment, it is characterised in that: described
Catalyst amounts are 0.2-2 gram per liters in technology, and pollutant initial concentration is 5-20 milligrams per liter.
11. application of the visible light catalyst material according to claim 6 in sewage treatment, it is characterised in that: make to urge
It is 30-40 minutes that agent and solution, which reach adsorption-desorption balance,；Solution is placed in 300 watts of xenon lamp Imitating sun visible lights to shine
Penetrating the reaction time is 20-40 minutes.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112958157A (en) * | 2021-02-08 | 2021-06-15 | 华侨大学 | Bimetallic organic framework material catalyst, preparation method and application |
| CN114405404A (en) * | 2022-01-10 | 2022-04-29 | 南京工程学院 | Improved doping reaction device |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103769213A (en) * | 2014-01-07 | 2014-05-07 | 河北科技大学 | Preparation method for phosphor-doped graphite-phase carbon nitride visible-light catalyst |
| CN106040274A (en) * | 2016-05-19 | 2016-10-26 | 中国计量大学 | High-concentration organic pollutant visible-light high-efficiency degradation amorphous carbon nitride catalyst and preparation method thereof |
-
2019
- 2019-01-03 CN CN201910004359.9A patent/CN109603884A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103769213A (en) * | 2014-01-07 | 2014-05-07 | 河北科技大学 | Preparation method for phosphor-doped graphite-phase carbon nitride visible-light catalyst |
| CN106040274A (en) * | 2016-05-19 | 2016-10-26 | 中国计量大学 | High-concentration organic pollutant visible-light high-efficiency degradation amorphous carbon nitride catalyst and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| SHIHAI CAO ET AL.: "Sulfur-doped g-C3N4 nanosheets with carbon vacancies: General synthesis and improved activity for simulated solar-light photocatalytic nitrogen fifixation", 《CHEMICAL ENGINEERING JOURNAL》 * |
| 覃艳蕾: "基于前驱体热化学性质调控g-C3N4的合成", 《武汉工程大学学报》 * |
| 赵萍: "g-C3N¬4光催化降解抗生素及其机理研究", 《万方数据库》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112958157A (en) * | 2021-02-08 | 2021-06-15 | 华侨大学 | Bimetallic organic framework material catalyst, preparation method and application |
| CN112958157B (en) * | 2021-02-08 | 2022-09-30 | 华侨大学 | Bimetallic organic framework material catalyst, preparation method and application |
| CN114405404A (en) * | 2022-01-10 | 2022-04-29 | 南京工程学院 | Improved doping reaction device |
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