CN105964270B - A kind of photochemical catalyst and preparation method thereof for sewage disposal - Google Patents
A kind of photochemical catalyst and preparation method thereof for sewage disposal Download PDFInfo
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- CN105964270B CN105964270B CN201610267895.4A CN201610267895A CN105964270B CN 105964270 B CN105964270 B CN 105964270B CN 201610267895 A CN201610267895 A CN 201610267895A CN 105964270 B CN105964270 B CN 105964270B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000010865 sewage Substances 0.000 title claims abstract description 16
- 150000001875 compounds Chemical class 0.000 claims abstract description 44
- 238000000034 method Methods 0.000 claims abstract description 25
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims abstract description 19
- OQFRENMCLHGPRB-UHFFFAOYSA-N copper;dioxido(dioxo)tungsten Chemical compound [Cu+2].[O-][W]([O-])(=O)=O OQFRENMCLHGPRB-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- 230000001376 precipitating effect Effects 0.000 claims abstract description 8
- 239000011259 mixed solution Substances 0.000 claims description 39
- 239000010949 copper Substances 0.000 claims description 20
- 229910052802 copper Inorganic materials 0.000 claims description 19
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 16
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 15
- 229910052721 tungsten Inorganic materials 0.000 claims description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 14
- -1 ethyl-3-methylimidazole hexafluorophosphate Chemical compound 0.000 claims description 14
- 239000002002 slurry Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 229910052797 bismuth Inorganic materials 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 229910052720 vanadium Inorganic materials 0.000 claims description 12
- 239000010937 tungsten Substances 0.000 claims description 10
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 9
- 238000000748 compression moulding Methods 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 8
- 239000002131 composite material Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 238000012545 processing Methods 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 6
- 235000006408 oxalic acid Nutrition 0.000 claims description 6
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 5
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 5
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 5
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 claims description 5
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 5
- 230000001699 photocatalysis Effects 0.000 claims description 5
- QYIGOGBGVKONDY-UHFFFAOYSA-N 1-(2-bromo-5-chlorophenyl)-3-methylpyrazole Chemical compound N1=C(C)C=CN1C1=CC(Cl)=CC=C1Br QYIGOGBGVKONDY-UHFFFAOYSA-N 0.000 claims description 4
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000007146 photocatalysis Methods 0.000 claims description 3
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims 1
- 150000001412 amines Chemical class 0.000 claims 1
- XTKDAFGWCDAMPY-UHFFFAOYSA-N azaperone Chemical group C1=CC(F)=CC=C1C(=O)CCCN1CCN(C=2N=CC=CC=2)CC1 XTKDAFGWCDAMPY-UHFFFAOYSA-N 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 6
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 4
- 238000001556 precipitation Methods 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 230000002153 concerted effect Effects 0.000 abstract description 3
- 230000007812 deficiency Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 230000009257 reactivity Effects 0.000 abstract description 3
- 239000006104 solid solution Substances 0.000 abstract description 3
- 230000007704 transition Effects 0.000 abstract description 3
- 239000006185 dispersion Substances 0.000 abstract description 2
- 230000015556 catabolic process Effects 0.000 description 6
- 238000006731 degradation reaction Methods 0.000 description 6
- 229910001868 water Inorganic materials 0.000 description 5
- 239000003643 water by type Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 3
- 229910002915 BiVO4 Inorganic materials 0.000 description 3
- 241001062009 Indigofera Species 0.000 description 3
- 235000000177 Indigofera tinctoria Nutrition 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 229940097275 indigo Drugs 0.000 description 3
- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 description 3
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 3
- 229960000907 methylthioninium chloride Drugs 0.000 description 3
- 239000011941 photocatalyst Substances 0.000 description 3
- 239000010908 plant waste Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052724 xenon Inorganic materials 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- IBZJNLWLRUHZIX-UHFFFAOYSA-N 1-ethyl-3-methyl-2h-imidazole Chemical group CCN1CN(C)C=C1 IBZJNLWLRUHZIX-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 230000032683 aging Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- PPNKDDZCLDMRHS-UHFFFAOYSA-N dinitrooxybismuthanyl nitrate Chemical class [Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PPNKDDZCLDMRHS-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- WKLWZEWIYUTZNJ-UHFFFAOYSA-K diacetyloxybismuthanyl acetate Chemical class [Bi+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WKLWZEWIYUTZNJ-UHFFFAOYSA-K 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 238000006263 metalation reaction Methods 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000003911 water pollution 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- 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
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
The present invention provides a kind of photochemical catalyst and preparation method thereof for sewage disposal, copper tungstate and pucherite is carried out compound, is conducive to the transition of light induced electron, improves its separative efficiency and avoids compound, and then improves catalytic efficiency；Secondly, raw material is sufficiently mixed by the alkalinity using tetraethylenepentamine and the complex performance to different metal, forms precipitation, so that active component is obtained evenly dispersed, overcomes the deficiency of active component dispersion inhomogeneities existing for conventional precipitating reagent.Again, catalyst is post-processed using the method for hydro-thermal process, is conducive to active component and forms corresponding solid solution, given full play to concerted catalysis effect, effectively increase the reactivity of catalyst.The experimental results showed that the photochemical catalyst for sewage disposal prepared by the present invention has higher catalytic efficiency.
Description
Technical field
The present invention relates to technical field of sewage more particularly to a kind of photochemical catalysts and its preparation for sewage disposal
Method.
Background technology
With China's rapid development of economy, the consumption of fossil energy is growing day by day, the environmental pollution in the whole country
Also the presence of toxic organic pollutant in getting worse, especially water not only causes environmental pollution, ecological disruption, but also serious
It is detrimental to health.The method of conventional process water pollution mainly has physical absorption, chemical oxidative decomposition, microbial degradation etc.,
Although the above method can play pollutant certain treatment effect, there is also inevitable defects, such as：It is dirty decomposing
It is be easy to cause secondary pollution while contaminating object, organic matter can not be fully converted to nontoxic small molecule.
In recent years, solving problem of environmental pollution using solar energy using photocatalysis technology has huge application prospect and skill
Art advantage.BiVO4Gradually it is widely used in visible light catalytic field with the physical and chemical properties that its is special, in visible light
Under irradiation, BiVO4Electronics on catalyst, which is excited, to be transitted on conduction band and generates hole, photoinduced electron and photo-induced hole difference
With very strong oxidation and reducing property, O can be generated in catalyst surface in the presence of oxygen and moisture content2-、O3-, OOH and
The organic matter complete catalysts oxidation being adsorbed in photocatalytic surfaces can be CO by OH isoreactivity species, these active species2And H2O。
Although BiVO4Catalyst has higher photocatalytic activity, and still, as single low-gap semiconductor, there are surface suctions
The defects of attached ability is weak, light induced electron and photohole are difficult to detach, the recombination rate of light induced electron and hole on surface compared with
Soon so that light induced electron and hole have little time to form enough OH, photo-quantum efficiency are reduced, so as to cause catalyst degradation
Performance reduces rapidly, and catalytic efficiency is relatively low.
It is considered as desirable by the inventor to provide a kind of photochemical catalyst and preparation method thereof for sewage disposal, have higher urge
Change efficiency.
Invention content
The photochemical catalyst and preparation method thereof that the main purpose of the present invention is to provide a kind of for sewage disposal, the light are urged
Agent has higher catalytic efficiency.
To achieve the above objectives, the present invention provides a kind of preparation method of the photochemical catalyst for sewage disposal, including with
Lower step：Tetraethylenepentamine and copper source compound are dissolved in deionized water, stirred with the speed of 400~800rpm, copper is formed
Ammonium complex compound, Cu2+A concentration of 0.05~0.3mol/L；Tungsten source compound and oxalic acid are dissolved in deionized water, with 300~
The speed of 500rpm stirs, and obtains the first mixed solution；First mixed solution is added dropwise in the cuprammonium complex, is obtained
To the second mixed solution；Vanadium source compound, bismuth source compound and template are added into second mixed solution, with 300~
The speed of 500rpm stirs, and addition tetraethylenepentamine adjustment pH value is 8~10, and third mixed solution is obtained after burin-in process；It will
The third mixed solution is placed in hydrothermal reaction kettle handles 6~12h in 120~180 DEG C, and slurries are obtained after cooling；It will be described
Slurries are filtered, washed, dry, roast, and photochemical catalyst is obtained after compression molding.
Preferably, in the step of forming cuprammonium complex, the molar ratio of the tetraethylenepentamine and copper source compound is 1:
(1~2).
Preferably, copper source compound is one or more of copper sulphate, copper nitrate and copper acetate.
Preferably, the tungsten source compound and copper source compound are weighed according to W: Cu 1: 1.
Preferably, in the step of obtaining the first mixed solution, the tungsten source compound is ammonium tungstate, ammonium paratungstate, wolframic acid
It is one or more of in sodium.
Preferably, the vanadium source compound is ammonium metavanadate.
Preferably, the bismuth source compound is one or more of in bismuth acetate, bismuth nitrate.
Preferably, the template is 1- ethyl-3-methylimidazoles hexafluorophosphate, 1- ethyl-3-methylimidazole tetrafluoros
It is one or more of in borate.
Preferably, described the step of obtaining photochemical catalyst, is specially：The slurries are filtered, filter obtain precipitating it is washed after
It is transferred to 5~10h of processing in 105~120 DEG C of drying device, then the product after drying is placed in 300~500 DEG C of air
Under the conditions of 4~6h of calcination process, obtain photochemical catalyst after compression molding.
Correspondingly, the present invention also provides a kind of photochemical catalyst for sewage disposal, it is made of copper tungstate and pucherite
Composite oxide of metal, wherein the molar ratio of W, Cu, V, Bi are 1: 1: 1: 1.
The present invention provides a kind of photochemical catalyst and preparation method thereof for sewage disposal, including：By tetraethylenepentamine and
Copper source compound is dissolved in deionized water, and cuprammonium complex is formed after stirring；Tungsten source compound and oxalic acid are dissolved in deionized water
In, it is stirred with the speed of 300~500rpm, is added dropwise in the cuprammonium complex, obtains the second mixed solution；To described second
Vanadium source compound, bismuth source compound and template are added in mixed solution, stirs, addition tetraethylenepentamine, burin-in process, then
It is placed in hydrothermal reaction kettle and handles 6~12h in 120~180 DEG C, obtain slurries after cooling, be filtered, washed, dry, roast, press
Photochemical catalyst is obtained after sheetmolding.Compared with prior art, first, the present invention carries out copper tungstate and pucherite compound, favorably
In the transition of light induced electron, improve its separative efficiency avoid it is compound, and then improve catalytic efficiency；Secondly, tetraethylenepentamine is utilized
Alkalinity and complex performance to different metal, raw material is sufficiently mixed, precipitation is formed, so that active component is obtained evenly dispersed,
Overcome the deficiency of active component dispersion inhomogeneities existing for conventional precipitating reagent.Again, using the method for hydro-thermal process to urging
Agent is post-processed, and is conducive to active component and is formed corresponding solid solution, is given full play to concerted catalysis effect, is effectively increased
The reactivity of catalyst.The experimental results showed that the photochemical catalyst for sewage disposal prepared by the present invention has higher urge
Change efficiency.
Specific implementation mode
It is described below for disclosing the present invention so that those skilled in the art can realize the present invention.It is excellent in being described below
Embodiment is selected to be only used as illustrating, it may occur to persons skilled in the art that other obvious modifications.
The present invention provides a kind of photochemical catalyst for sewage disposal, and the catalyst is made of copper tungstate and pucherite
Composite oxide of metal, wherein the molar ratio of W, Cu, V, Bi be 1: 1: 1: 1.
Correspondingly, the present invention also provides a kind of preparation method of the photochemical catalyst for sewage disposal, using co-precipitation and
The method of hydro-thermal Combined Treatment, includes the following steps：Tetraethylenepentamine and copper source compound are dissolved in deionized water, with 400
The speed of~800rpm stirs, and forms cuprammonium complex, Cu2+A concentration of 0.05~0.3mol/L；By tungsten source compound and grass
Acid is dissolved in deionized water, is stirred with the speed of 300~500rpm, is obtained the first mixed solution；By first mixed solution
It is added dropwise in the cuprammonium complex, obtains the second mixed solution；Vanadium source compound, bismuth are added into second mixed solution
Source compound and template are stirred with the speed of 300~500rpm, and addition tetraethylenepentamine adjustment pH value is 8~10, at aging
Third mixed solution is obtained after reason；By the third mixed solution be placed in hydrothermal reaction kettle in 120~180 DEG C handle 6~
12h obtains slurries after cooling；The slurries are filtered, washed, dry, are roasted, photochemical catalyst is obtained after compression molding.
Preferably, in the step of forming cuprammonium complex, mole of the tetraethylenepentamine and copper source compound
Than being preferably 1: (1~2), more preferably 1: 1；Copper source compound is preferably one in copper sulphate, copper nitrate and copper acetate
Kind is several；Mixing speed is preferably 500~800rpm, more preferably 600~700rpm；Mixing time be preferably 20min~
40min, more preferably 25min~40min, more preferably 30min~40min.
In the step of obtaining the first mixed solution, mixing speed is preferably 350~500rpm, more preferably 400~
500rpm；Mixing time is preferably 10min~20min, more preferably 12min~40min, more preferably 14min~40min.
The tungsten source compound is preferably one or more of in ammonium tungstate, ammonium paratungstate and sodium tungstate.The tungsten source compound and copper source
Compound is preferably weighed according to the molar ratio of W and Cu for 1: 1.
In the step of obtaining the second mixed solution, time for adding is preferably 10~40min, more preferably 20~30min.
Raw material are sufficiently mixed by the present invention using the alkalinity of tetraethylenepentamine and the complex performance to different metal, and
Precipitation is formed under corresponding conditions, active component can be made to obtain evenly dispersed, is overcome active existing for conventional precipitating reagent
Component disperses the deficiency of inhomogeneities.
In the step of obtaining third mixed solution, the vanadium source compound is preferably ammonium metavanadate；The bismuth source compound
It is one or more of preferably in bismuth acetate, bismuth nitrate；Mixing speed is preferably 350~500rpm, more preferably 400~
500rpm；Mixing time is preferably 20~40min, more preferably 25~40min, more preferably 30~40min；Burin-in process
Time is preferably 30min~2h, more preferably 1~2h.Preferably, the template is preferably 1- ethyl -3- methyl
It is one or more of in limidazolium hexafluorophosphate, 1- ethyl-3-methylimidazole tetrafluoroborates；The template and metal precursor
The ratio of total weight is 1~3%, and the metal precursor is copper source compound, tungsten source compound, bismuth source compound and vanadium source chemical combination
Object.
The present invention is preferably in 1- ethyl-3-methylimidazoles hexafluorophosphate, 1- ethyl-3-methylimidazole tetrafluoroborates
One or more are used as template, so that prepared catalyst is formed uniform meso-hole structure, are conducive to active specy
With reactant in the contact of catalyst surface, further strengthen the progress of reaction process；On the other hand ionic liquid itself is utilized
N, P, the F contained is doped catalyst, expands the utilization scope to sunlight, and then the reaction for enhancing catalyst is lived
Property.
The present invention post-processes catalyst using the method for hydro-thermal process, is conducive to active component and forms corresponding solid
Solution gives full play to concerted catalysis effect, effectively increases the reactivity of catalyst.
In the step of obtaining slurries, treatment temperature is preferably 130~180 DEG C, more preferably 140~180 DEG C；Processing time
Preferably 7~12h, more preferably 8~12h.
Preferably, described the step of obtaining photochemical catalyst, is specially：The slurries are filtered, filter obtains precipitation warp
It is transferred to 5~10h of processing in 105~120 DEG C of drying device after washing, the product after drying is then placed in 300~500 DEG C
Air conditions under 4~6h of calcination process, obtain photochemical catalyst after compression molding.
For pucherite as single low-gap semiconductor, the recombination rate of light induced electron and hole on surface is very fast, makes
It obtains light induced electron and hole has little time to form enough OH, reduce photo-quantum efficiency, thereby reduce light-catalysed experiment
Effect.The present invention is compound by copper tungstate and pucherite progress, is conducive to the transition of light induced electron, prevents answering for electron hole pair
It closes, improve its separative efficiency, and then improve photocatalysis effect.
For a further understanding of the present invention, technical solution provided by the invention is carried out specifically with reference to embodiment
Bright, protection scope of the present invention is not limited by the following examples.
Copper sulphate, copper nitrate, copper acetate, ammonium tungstate, ammonium paratungstate, wolframic acid in chemical reagent used in the embodiment of the present invention
Sodium, bismuth acetate, bismuth nitrate, ammonium metavanadate, bismuth nitrate are purchased from Sinopharm Chemical Reagent Co., Ltd..
1- ethyl-3-methylimidazoles hexafluorophosphate, 1- ethyl-3-methylimidazole tetrafluoroborates are purchased from Shanghai flute cypressization
Xue Pin Technology Co., Ltd..
Embodiment 1
1) ratio for being 1: 1 according to molar ratio weighs 2.65g tetraethylenepentamine respectively and 2.23g cupric sulfate pentahydrates are dissolved in
In 200mL deionized waters, cuprammonium complex is formed it into 800rpm stir process 20min at room temperature；
2) ammonium tungstate of 3.55g is weighed respectively and oxalic acid is dissolved in 30mL deionized waters, is stirred at room temperature with 400rpm
20min makes it be sufficiently mixed；
3) mixed solution formed in step 2) is added drop-wise in 20min in the cuprammonium complex prepared by step 1)；
4) 1.64g ammonium metavanadates, 6.79g bismuth nitrates and 0.14g1- ethyl -3- methyl are added into above-mentioned mixed solution
Limidazolium hexafluorophosphate continues to form mixed solution with 300rpm stirrings 40min, and tetraethylenepentamine tune is added into mixed solution
Its whole pH value is 8, and burin-in process 2h at room temperature；
5) mixed solution obtained by step 4) is transferred in hydrothermal reaction kettle and handles 6h in 180 DEG C, then naturally cooled to
Room temperature；
6) slurries that step 5) obtains are filtered, filter obtain precipitating it is washed after be transferred to 105 DEG C of drying device
Then product after drying is placed in calcination process 4h under 500 DEG C of air conditions and carries out compression molding by middle processing 10h.
The composite photo-catalyst of copper tungstate/pucherite made from 50mg is added to the methylene of a concentration of 30mg/L of 100mL
In base indigo plant waste water, 45min is handled under the xenon lamp irradiation of 500w, remaining methylene blue is detected with uv-visible absorption spectra
Degradation rate is 96.8%.The degradation rate of the pucherite of phase homogenous quantities under the same conditions is only 81.3%.
Embodiment 2
3) ratio for being 1: 2 according to molar ratio weighs 1.33g tetraethylenepentamine respectively and 2.64g copper nitrates are dissolved in 300mL
In deionized water, cuprammonium complex is formed it into 400rpm stir process 40min at room temperature；
4) ammonium paratungstate of 3.99g is weighed respectively and oxalic acid is dissolved in 50mL deionized waters, is stirred at room temperature with 450rpm
20min is mixed, it is made to be sufficiently mixed；
3) mixed solution formed in step 2) is added drop-wise in 40min in the cuprammonium complex prepared by step 1)；
4) 1.64g ammonium metavanadates, 5.43g bismuth acetates bismuth and 0.4g1- ethyl -3- first are added into above-mentioned mixed solution
Base tetrafluoroborate continues to form mixed solution with 500rpm stirrings 30min, and tetraethylenepentamine is added into mixed solution
Its pH value is adjusted 10, and burin-in process 1h at room temperature；
5) mixed solution obtained by step 4) is transferred in hydrothermal reaction kettle and handles 12h in 120 DEG C, then naturally cooled to
Room temperature；
6) slurries that step 5) obtains are filtered, filter obtain precipitating it is washed after be transferred to 120 DEG C of drying device
Then product after drying is placed in calcination process 6h under 300 DEG C of air conditions and carries out compression molding by middle processing 5h.
The composite photo-catalyst of copper tungstate/pucherite made from 50mg is added to the methylene of a concentration of 30mg/L of 100mL
In base indigo plant waste water, 45min is handled under the xenon lamp irradiation of 500w, remaining methylene blue is detected with uv-visible absorption spectra
Degradation rate is 97.4%.
Embodiment 3
1) ratio for being 1: 1.5 according to molar ratio weighs 1.33g tetraethylenepentamine respectively and 2.10g copper acetates are dissolved in
In 200mL deionized waters, cuprammonium complex is formed it into 600rpm stir process 30min at room temperature；
2) sodium tungstate of 3.48g is weighed respectively and oxalic acid is dissolved in 50mL deionized waters, is stirred at room temperature with 500rpm
20min makes it be sufficiently mixed；
3) mixed solution formed in step 2) is added drop-wise in 20min in the cuprammonium complex prepared by step 1)；
4) it is 1: 1 that 1.23g ammonium metavanadates, 5.11g bismuth nitrates and 0.25g mass ratioes are added into above-mentioned mixed solution
The mixture of 1- ethyl-3-methylimidazoles hexafluorophosphate and 1- ethyl-3-methylimidazole tetrafluoroborates continues with 400rpm
It stirs 30min and forms mixed solution, tetraethylenepentamine is added into mixed solution and adjusts its pH value 10, and aging at room temperature
Handle 1h；
5) mixed solution obtained by step 4) is transferred in hydrothermal reaction kettle and handles 8h in 150 DEG C, then naturally cooled to
Room temperature；
6) slurries that step 5) obtains are filtered, filter obtain precipitating it is washed after be transferred to 110 DEG C of drying device
Then product after drying is placed in calcination process 5h under 400 DEG C of air conditions and carries out compression molding by middle processing 8h.
The composite photo-catalyst of copper tungstate/pucherite made from 50mg is added to the methylene of a concentration of 30mg/L of 100mL
In base indigo plant waste water, 45min is handled under the xenon lamp irradiation of 500w, remaining methylene blue is detected with uv-visible absorption spectra
Degradation rate is 97.1%
The basic principles, main features and advantages of the present invention have been shown and described above.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and what is described in the above embodiment and the description is only the present invention
Principle, various changes and improvements may be made to the invention without departing from the spirit and scope of the present invention, these variation and
Improvement is both fallen in the range of claimed invention.The present invention claims protection domain by appended claims and its
Equivalent defines.
Claims (8)
1. a kind of preparation method of photochemical catalyst for sewage disposal, which is characterized in that include the following steps：
Tetraethylenepentamine and copper source compound are dissolved in deionized water, stirred with the speed of 400~800rpm, cuprammonium network is formed
Close object, Cu2+A concentration of 0.05~0.3mol/L；
Tungsten source compound and oxalic acid are dissolved in deionized water, is stirred with the speed of 300~500rpm, it is molten to obtain the first mixing
Liquid；
First mixed solution is added dropwise in the cuprammonium complex, the second mixed solution is obtained；
Vanadium source compound, bismuth source compound and template are added into second mixed solution, with the speed of 300~500rpm
Stirring, addition tetraethylenepentamine adjustment pH value is 8~10, and third mixed solution is obtained after burin-in process, and the template is 1-
One or more of ethyl-3-methylimidazole hexafluorophosphate, 1- ethyl-3-methylimidazole tetrafluoroborates；
The third mixed solution is placed in hydrothermal reaction kettle and handles 6~12h in 120~180 DEG C, slurries are obtained after cooling；
The slurries are filtered, washed, dry, are roasted, photochemical catalyst is obtained after compression molding,
The composite oxide of metal that the photochemical catalyst is made of copper tungstate and pucherite, wherein the molar ratio of W, Cu, V, Bi
It is 1:1:1:1.
2. preparation method according to claim 1, which is characterized in that in the step of forming cuprammonium complex, the tetrem
The molar ratio of five amine of alkene and copper source compound is 1:(1~2).
3. preparation method according to claim 1, which is characterized in that copper source compound be copper sulphate, copper nitrate and
One or more of copper acetate.
4. preparation method according to claim 1, which is characterized in that in the step of obtaining the first mixed solution, the tungsten
Source compound is one or more of in ammonium tungstate, ammonium paratungstate and sodium tungstate.
5. preparation method according to claim 1, which is characterized in that the vanadium source compound is ammonium metavanadate.
6. preparation method according to claim 1, which is characterized in that the bismuth source compound is in bismuth acetate, bismuth nitrate
One or more.
7. preparation method according to claim 1, which is characterized in that described the step of obtaining photochemical catalyst is specially：
The slurries are filtered, obtain precipitating it is washed after be transferred to 5~10h of processing in 105~120 DEG C of drying device, so
The product after drying is placed in 4~6h of calcination process under 300~500 DEG C of air conditions afterwards, photocatalysis is obtained after compression molding
Agent.
8. according to a kind of photochemical catalyst for sewage disposal made from claim 1-7 any one method, which is characterized in that
The composite oxide of metal being made of copper tungstate and pucherite, wherein the molar ratio of W, Cu, V, Bi are 1:1:1:1.
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| KR20150139965A (en) * | 2013-04-11 | 2015-12-14 | 메르크 파텐트 게엠베하 | Metal complexes and use thereof in electronic devices |
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