CN110479293A - A kind of photochemical catalyst preparation method - Google Patents
A kind of photochemical catalyst preparation method Download PDFInfo
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- CN110479293A CN110479293A CN201910844003.6A CN201910844003A CN110479293A CN 110479293 A CN110479293 A CN 110479293A CN 201910844003 A CN201910844003 A CN 201910844003A CN 110479293 A CN110479293 A CN 110479293A
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- catalyst
- water
- phenol
- solution
- citric acid
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- 239000003054 catalyst Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 56
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 54
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000002131 composite material Substances 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000011941 photocatalyst Substances 0.000 claims abstract description 27
- 229910002518 CoFe2O4 Inorganic materials 0.000 claims abstract description 25
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 43
- 239000011259 mixed solution Substances 0.000 claims description 22
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 15
- -1 is stirred evenly Substances 0.000 claims description 5
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- 239000007863 gel particle Substances 0.000 claims description 2
- 239000008236 heating water Substances 0.000 claims description 2
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 48
- 230000015556 catabolic process Effects 0.000 abstract description 19
- 238000006731 degradation reaction Methods 0.000 abstract description 19
- 239000002351 wastewater Substances 0.000 abstract description 14
- 238000000034 method Methods 0.000 abstract description 13
- 238000002156 mixing Methods 0.000 abstract description 6
- 238000006555 catalytic reaction Methods 0.000 abstract description 5
- 230000001699 photocatalysis Effects 0.000 abstract description 5
- 238000007146 photocatalysis Methods 0.000 abstract description 4
- 150000001868 cobalt Chemical class 0.000 abstract description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 abstract description 3
- 150000002603 lanthanum Chemical class 0.000 abstract description 3
- 229960004756 ethanol Drugs 0.000 description 18
- 235000019441 ethanol Nutrition 0.000 description 18
- 238000002835 absorbance Methods 0.000 description 10
- 230000000593 degrading effect Effects 0.000 description 10
- 239000002253 acid Substances 0.000 description 9
- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 description 8
- 238000013019 agitation Methods 0.000 description 7
- RLFWWDJHLFCNIJ-UHFFFAOYSA-N Aminoantipyrine Natural products CN1C(C)=C(N)C(=O)N1C1=CC=CC=C1 RLFWWDJHLFCNIJ-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- OQUOOEBLAKQCOP-UHFFFAOYSA-N nitric acid;hexahydrate Chemical compound O.O.O.O.O.O.O[N+]([O-])=O OQUOOEBLAKQCOP-UHFFFAOYSA-N 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 230000001476 alcoholic effect Effects 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 239000006249 magnetic particle Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- VEQOALNAAJBPNY-UHFFFAOYSA-N antipyrine Chemical compound CN1C(C)=CC(=O)N1C1=CC=CC=C1 VEQOALNAAJBPNY-UHFFFAOYSA-N 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 239000007853 buffer solution Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229960000935 dehydrated alcohol Drugs 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000007667 floating Methods 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229960005222 phenazone Drugs 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- IQUPABOKLQSFBK-UHFFFAOYSA-N 2-nitrophenol Chemical compound OC1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 208000031320 Teratogenesis Diseases 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- RRTCFFFUTAGOSG-UHFFFAOYSA-N benzene;phenol Chemical compound C1=CC=CC=C1.OC1=CC=CC=C1 RRTCFFFUTAGOSG-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 231100000734 genotoxic potential Toxicity 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003471 mutagenic agent Substances 0.000 description 1
- 231100000707 mutagenic chemical Toxicity 0.000 description 1
- 229910000159 nickel phosphate Inorganic materials 0.000 description 1
- JOCJYBPHESYFOK-UHFFFAOYSA-K nickel(3+);phosphate Chemical compound [Ni+3].[O-]P([O-])([O-])=O JOCJYBPHESYFOK-UHFFFAOYSA-K 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- QXDYIBHUQHUJJI-UHFFFAOYSA-N nitrobenzene phenol Chemical compound OC1=CC=CC=C1.[O-][N+](=O)C1=CC=CC=C1 QXDYIBHUQHUJJI-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000003918 potentiometric titration Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J23/83—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 rare earths or actinides
-
- 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
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- 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
Abstract
The invention discloses a kind of photochemical catalyst preparation methods for handling phenolic waste water.This method is by cobalt salt, molysite, lanthanum salt, it sequentially adds in water, citric acid is added after mixing again with the ethanol solution of butyl titanate, gel is formed under water bath condition, it is calcined after drying, obtain La doping CoFe2O4/TiO2 composite photo-catalyst, wherein Co:Ti:La: water: the molar ratio of citric acid is (0.5-0.8): 1:(0.10-0.18): (120-200): the ratio of (7-10) is matched, and wherein Fe mole is 2 times of Co mole.Photoresponse wavelength is extended to visible region from ultraviolet region by the photochemical catalyst that this method is prepared, photocatalysis performance is significantly improved simultaneously, the catalysis degradation modulus of phenol can achieve 73.59%-84.27% in 1.5h, and the composite photo-catalyst is easily recycled.
Description
Technical field
The invention belongs to environmentally conscious materials preparation field fields, and in particular to a kind of La for wastewater containing phenol of degrading mixes
Miscellaneous CoFe2O4/TiO2 composite photo-catalyst preparation method.
Background technique
Phenol is a kind of common industrial chemicals, is difficult to degrade, and the genotoxic potential with carcinogenic, teratogenesis, mutagens, thus is contained
Phenol wastewater source is very extensive, comes human health with extremely serious harm.Phenol is pollutant common in phenol wastewater,
It has been an important topic in terms of environmental protection that phenolic waste water, which is effectively treated, and photocatalytic oxidation degradation phenol has efficient, stable
A kind of and the features such as without secondary pollution, it has also become novel pollutant abatement technology of environment protection field in recent years.
Using semiconductor and composite semiconductor photocatalysis degradable organic pollutant, obtained in environmental pollution improvement in recent years
Preferable research effect.TiO2 as photochemical catalyst there is good chemical stability, low cost, nontoxic, raw material easily to obtain,
And catalysis oxidation directly can be carried out as excitation light source using the visible light in sunlight, it is without secondary pollution.But TiO2 light
Catalyst quantum low efficiency, and spectral response range visible light part in ultraviolet region, solar spectrum cannot efficiently use, limit
Its industrial application is made.For deficiency existing for TiO2 photocatalysis oxidation technique, domestic and international pertinent literature is mainly to TiO2 at present
Photochemical catalyst carries out the study on the modification of two aspects: first is that passing through doping vario-property；Second is that developmental research loaded photocatalyst, makes
It is preferably utilized in practical applications.
Existing patent 201410286125.5 " a kind of float type CoFe2O4/TiO2/ floating bead composite photo-catalyst and its system
Preparation Method " disclose a kind of floating bead as carrier, first back loading TiO2 and CoFe2O4 on it, but this method preparation process
Complexity, and need to calcine intermediate material and final product respectively, and calcination condition is identical, and to guarantee intermediate production simultaneously
The property of object and final product, therefore in the case of the two is taken into account, it largely will affect the property of final product, and to benzene
The degradation rate of phenol is well below the degradation rate to methylene blue, degradation rate not more than 80% in 3h.
Patent 200410089201.X " photochemical catalyst and preparation method thereof for wastewater containing phenol processing " disclose by
Micropore nickel phosphate VSB-1 is carrier, and active component TiO2 is assembled in duct, formation composite catalyst, but the drop of Pyrogentisinic Acid
Solution rate highest also only only has 64.51%.
Patent 201410764458.4 " a kind of preparation method of the photochemical catalyst for the treatment of of Nitrobenzene phenol waste water, a kind of nitro
The processing method of phenolic waste water " disclose by sol-gel method synthesis nano TiO 2 be supported on modified secondary mesopore molecule
It sieves (ZSM5), the lower potentiometric titrations collaboration OH that generates of UV (ultraviolet light) excitation, which can be improved, can play stronger energy of oxidation
Power, although degradation rate is high, obtained composite catalyst needs on the basis of ferrous sulfate, sodium peroxydisulfate provide sulfate radical,
It could significant catalysis oxidation nitrophenol under 170W ultraviolet high-pressure mercury lamps irradiation condition.
Summary of the invention
It is simple the purpose of the present invention is in view of the foregoing drawbacks, providing a kind of preparation process, the high light of phenol catalysis degradation modulus
Method for preparing catalyst.
In order to achieve the object of the present invention, by a large number of experiments research and unremitting effort, following technical solution is finally obtained:
A kind of photochemical catalyst preparation method handling phenolic waste water, includes the following steps:
(1) cobalt salt, molysite, lanthanum salt are taken, is sequentially added in water, is stirred evenly, mixed solution A is obtained；
(2) mixed solution A is added in the ethanol solution of butyl titanate, adds citric acid, obtains mixed solution B；
(3) heating water bath, stirring to formation gel at 70-90 DEG C by mixed solution B；
(4) it is ground after gel drying, obtained dry gel particle roasts 2-3h at 150-220 DEG C, then forges at 380-500 DEG C
10-14h is burnt, La doping CoFe2O4/TiO2 composite photo-catalyst is obtained；
According to Co:Ti:La in above-mentioned steps: water: the molar ratio of citric acid is (0.5-0.8): 1:(0.10-0.18): (120-
200): the ratio of (7-10) is sampled, and wherein Fe mole is 2 times of Co mole.
Preferably, handle the photochemical catalyst preparation method of phenolic waste water as described above, wherein Co:Ti:La: citric acid rubs
You are than being 0.6:1:0.12:9.
Preferably, the lanthanum salt is lanthanum nitrate or lanthanum chloride.
Preferably, the cobalt salt is cobalt nitrate or cobalt chloride.
Preferably, the molysite is any one in ferric nitrate, iron chloride and ferric sulfate.
The water is distilled water or deionized water.
Further, the present invention also provides the La being prepared using the above method to adulterate CoFe2O4/TiO2 composite photocatalyst
Agent handle wastewater containing phenol method, by the La doping CoFe2O4/TiO2 composite photo-catalyst be suspended in phenolic waste water into
Row processing.
The method of processing wastewater containing phenol as described above, it is preferable that added in the ratio of 0.5-5g/L into waste water described
La adulterates CoFe2O4/TiO2 composite photo-catalyst, and then stirring at normal temperature handles 1.5-2.5h.
The present invention compared with the existing technology, has the following technical effect that
Preparation method is simple for La of the present invention doping CoFe2O4/TiO2 composite photo-catalyst, by the compound of many kinds of substance,
Not only make photoresponse wavelength be extended to visible region from ultraviolet region, improves the utilization rate of light；And catalyst activity component
For Co, Fe, Ti, and appropriate La is adulterated, whole photocatalysis performance is significantly improved, and the catalysis degradation modulus of phenol can be in 1.5h
Reach 73.59%-84.27%；CoFe2O4 serves not only as catalyst active component in the present invention, and has magnetism, and what is obtained answers
Light combination catalyst is easily recycled.
Specific embodiment
Specific embodiments of the present invention will be further explained below.
Embodiment 1
The preparation of composite photo-catalyst:
Step 1: weighing 4.26g cabaltous nitrate hexahydrate, nine water ferric nitrate of 11.82g, 1.27g lanthanum nitrate hexahydrate 433, sequentially add
It into 63.3g water, stirs evenly, obtains mixed solution A；
Step 2: 10ml butyl titanate (2.927 × 10-2mol) being dissolved in 35ml ethyl alcohol, magnetic agitation obtains four fourth of metatitanic acid
The ethanol solution of ester；
Step 3: mixed solution A being added in the ethanol solution of butyl titanate, then 39.4g citric acid is added thereto, obtained
Mixed solution；
Step 4: mixed solution being heated under 70 DEG C of water bath conditions, stirring carries out gel until formation gel at 40 DEG C
It is dry, it after xerogel is ground into particle, puts it into Muffle furnace, roasts 2h at 150 DEG C first, then be brought rapidly up to 380
DEG C, 11h is calcined, La doping CoFe2O4/TiO2 composite photo-catalyst is obtained.
Embodiment 2
The preparation of composite photo-catalyst:
Step 1: weighing 5.11g cabaltous nitrate hexahydrate, nine water ferric nitrate of 14.19g, 1.52g lanthanum nitrate hexahydrate, be added sequentially to
It in 79.0g water, stirs evenly, obtains mixed solution A；
Step 2: 10ml butyl titanate (2.927 × 10-2mol) being dissolved in 35ml ethyl alcohol, magnetic agitation obtains four fourth of metatitanic acid
The ethanol solution of ester；
Step 3: mixed solution A being added in the ethanol solution of butyl titanate, then 50.61g citric acid is added thereto, obtained
Mixed solution；
Step 4: mixed solution being heated under 80 DEG C of water bath conditions, stirring carries out gel until formation gel at 40 DEG C
It is dry, it after xerogel is ground into particle, puts it into Muffle furnace, roasts 3h at 180 DEG C first, then be brought rapidly up to 450
DEG C, 12h is calcined, La doping CoFe2O4/TiO2 composite photo-catalyst is obtained.
Embodiment 3
The preparation of composite photo-catalyst:
Step 1: weighing 6.81g cabaltous nitrate hexahydrate, nine water ferric nitrate of 18.92g, 2.28g lanthanum nitrate hexahydrate, be added sequentially to
It in 105g water, stirs evenly, obtains mixed solution A；
Step 2: 10ml butyl titanate (2.927 × 10-2mol) being dissolved in 35ml ethyl alcohol, magnetic agitation obtains four fourth of metatitanic acid
The ethanol solution of ester；
Step 3: mixed solution A being added in the ethanol solution of butyl titanate, then 56.2g citric acid is added thereto, is obtained
To mixed solution；
Step 4: mixed solution being heated under 90 DEG C of water bath conditions, stirring carries out gel until formation gel at 40 DEG C
It is dry, it after xerogel is ground into particle, puts it into Muffle furnace, roasts 3h at 220 DEG C first, then be brought rapidly up to 500
DEG C, 14h is calcined, La doping CoFe2O4/TiO2 composite photo-catalyst is obtained.
Embodiment 4
The measuring method of phenol content: using spectrophotometry measurement-phenol solution through 4- ammonium antipyrine colour developing after, with point
Light photometric determination absorbance.Phenol is in pH=10.0 ± 0.2 and solution using the potassium ferricyanide as oxidant, with 4- amino
Antipyrine reacts to form coloured antipyrine dyestuff.The maximum absorption wavelength of this dyestuff is at 510nm, and color is in 30min
Interior stabilization.
The measurement of phenol initial absorbance: it takes the phenol solution 10mL of 1.00g/L in the volumetric flask of 100mL, adds water
It is diluted to 100mL, while adjusting solution PH=7~8, is configured to the phenol solution of 100mg/L.After room temperature 15min, take
The phenol solution of the 100mg/L of 5.0mL adds a small amount of water in the volumetric flask of another 100mL, then plus 2.0mL buffer solution and
4.0mL4- amino-antipyrine solution mixes；Again plus the 4.0mL potassium ferricyanide, mixing are settled to 100mL, in room temperature
After 15min, on spectrophotometer at 510nm wavelength with 1cm cuvette using zero-dose as reference measurement absorbance, measure it
Absorbance A 1=0.992.
The measurement of phenol absorbance in degradation solution: sampling 5.0mL filters out solid on suction filtration machine and is placed on after degradation
In the volumetric flask of 100mL, add a small amount of water, then plus 2.0mL buffer solution and 4.0mL4- amino-antipyrine solution, mix；Again plus
The 4.0mL potassium ferricyanide mixes, 100mL is settled to, after room temperature 15min, on spectrophotometer at 510nm wavelength
With 1cm cuvette using zero-dose as reference measurement absorbance, its degradation rate is calculated.
Adsorption of Phenol effect detection:
La doping each 0.05g of CoFe2O4/TiO2 composite photo-catalyst that embodiment 1-3 is obtained is weighed, 100ml conical flask is put into,
The phenol solution of prepared 50ml100mg/L is added, it is carried out degradation experiment by pH=5 under visible light catalytic reactor,
Solution is filtered after reaction 1.5h, filtrate is then surveyed at wavelength 510nm to its suction with 752 type ultraviolet-visible spectrophotometers
Luminosity is converted into phenol solution concentration when adsorption equilibrium according to absorbance-concentration working curve, and then calculates the drop of phenol
Solution rate η %.
η %={ (A1-A2)/A1 } × 100%, wherein A1-phenol solution initial absorbance value, A2-phenol water
The final states absorbance value of solution.
1 difference La of table adulterates CoFe2O4/TiO2 composite photocatalyst for degrading phenol
As known from Table 1, the present invention is prepared La doping CoFe2O4/TiO2 Pyrogentisinic Acid has a significant degradation effect, and
The degradation rate of Pyrogentisinic Acid is up to 73.59% or more in 1.5h, and highest can achieve 84.27%.
Embodiment 5
The additional amount of the catalyst that Example 1-3 is prepared, catalyst is in the same manner as in Example 4, changes mixing time point
Not Wei 40min, 1.5h, 2.5h, investigate phenol degrading rate, obtain result as shown in table 2.
Phenol degrading rate under the different mixings time of table 2
As known from Table 2, upon agitation between from 40min to 1.5h when, phenol degrading rate increase it is significant, when from 1.5h to 2.5h,
The raising of phenol degrading rate is unobvious, therefore in actual treatment, and mixing time is higher than 40min after phenol is added in selecting catalyst,
Mixing time is no more than 2.5h in 1.5h or so.
Embodiment 6
The catalyst that embodiment 2 obtains is weighed, is added into phenol solution, other steps are identical as embodiment 4, change benzene
Phenol solution concentration is 25mg/L, 50mg/L, 75mg/L, 100mg/L, and degradation rate when investigating its 1h obtains result as shown in table 3.
3 various concentration phenol solution degradation rate (%) of table
From 3 data of table it is found that the La doping CoFe2O4/TiO2 composite photo-catalyst that the present invention obtains is lower than 100mg/L to concentration
Phenolic waste water treatment effect it is significant, degradation rate highest can achieve 87.04% or more.
Embodiment 7
Step 1: weighing 2.55g cabaltous nitrate hexahydrate, nine water ferric nitrate of 7.1g, 0.88g lanthanum nitrate hexahydrate, be added sequentially to
In 63.3g water, stir evenly；
Step 2: 10ml butyl titanate (2.927 × 10-2mol) being dissolved in 35ml ethyl alcohol, magnetic agitation obtains four fourth of metatitanic acid
The ethanol solution of ester；
Step 3: the ethanol solution of butyl titanate being added in the mixed solution of step 1, add 33.7g citric acid；
Remaining step is as described in Example 2, and composite photo-catalyst is prepared, and weighs the composite photo-catalyst that 0.05g is obtained, presses
Treatment process described in embodiment 4 is added in 100mg/L phenol solution, and measuring phenol degrading rate is 68.17%.
Embodiment 8
Step 1: weighing 8.51g cabaltous nitrate hexahydrate, nine water ferric nitrate of 23.65g, 2.53g lanthanum nitrate hexahydrate, be added sequentially to
In 79.0g water, stir evenly；
Step 2: 10ml butyl titanate (2.927 × 10-2mol) being dissolved in 35ml ethyl alcohol, magnetic agitation obtains four fourth of metatitanic acid
The ethanol solution of ester；
Step 3: the ethanol solution of butyl titanate being added in the mixed solution of step 1, add 50.61g citric acid；
Remaining step is as described in Example 2, obtains composite photo-catalyst, weighs the composite photo-catalyst that 0.05g is obtained, by implementation
Treatment process described in example 5 is added in 100mg/L phenol solution, and measuring phenol degrading rate is 74.28%.
Compared by the degradation rate of embodiment 2 and embodiment 7,8, it is known that, when the mole ratio of active material in reactant
When outside range disclosed by the invention, the La that the method for the present invention is prepared is far below to the degradation rate of 100mg/L phenol solution
Adulterate CoFe2O4/TiO2 composite photo-catalyst.
Comparative example 1
The preparation of CoFe2O4/TiO2 photochemical catalyst:
Step 1: taking dehydrated alcohol 35ml, acetic acid 4ml, distilled water 10ml and 3.5gCoFe2O4 magnetic particle, stirring forms outstanding
Turbid, CoFe2O4 magnetic particle are the prior art, and specifically using ferric nitrate, cobalt nitrate as raw material, citric acid is complexing agent, is adopted
It is prepared with sol-gel method；
Step 2: taking dehydrated alcohol 35ml, butyl titanate 10ml that another beaker is added, obtain butyl titanate after stirring 10mni
Alcoholic solution, the alcoholic solution of butyl titanate is added drop-wise to CoFe2O4 suspension with 15ml/min, continuing vigorous stirring is suspended
Liquid is stirred for 30min after being added dropwise, and obtains the colloidal sol for being dispersed with CoFe2O4 magnetic particle, by colloidal sol in 40 DEG C of waters bath with thermostatic control
Drying obtains xerogel in 105 DEG C after 2h, xerogel is roasted 3h, then be brought rapidly up to 480 DEG C at 220 DEG C first, forged
12h is burnt, CoFe2O4/TiO2 photochemical catalyst is obtained.
CoFe2O4/TiO2 photochemical catalyst 0.5g is taken, is thrown the phenol solution for being added to 50ml100mg/L, pH value of solution=
It is 0.475 that filtrate absorbance is measured after 5,1.5h, and phenol degrading rate is 52.12%.
Comparative example 2
Step 1: 10ml butyl titanate (2.927 × 10-2mol) being dissolved in 35ml ethyl alcohol, magnetic agitation obtains four fourth of metatitanic acid
The ethanol solution of ester；
Step 2: weighing 1.55g lanthanum nitrate hexahydrate, be dissolved in 30ml water, obtain lanthanum nitrate hexahydrate；
Step 3: lanthanum nitrate hexahydrate being added dropwise in the alcoholic solution of butyl titanate, continues stirring until forming colloidal sol, colloidal sol exists
Water bath with thermostatic control 2h, obtains gel at 60 DEG C, will dry at gel in an oven 80 DEG C, and xerogel grinding is placed on Muffle furnace
In, 3h is first roasted at 200 DEG C, then be brought rapidly up to 480 DEG C, calcine 12h, obtain La doping TiO2 composite photo-catalyst.
The La doping TiO2 composite photo-catalyst for taking 0.5g to be prepared, is added in the phenol solution of 50ml100mg/L,
It is 0.568 that filtrate absorbance is measured after pH value of solution=5,1.5h, and phenol degrading rate is 42.74%.
Claims (2)
1. a kind of photochemical catalyst preparation method, it is characterised in that include the following steps:
(1) cobalt nitrate, ferric nitrate, lanthanum nitrate are taken, is sequentially added in water, is stirred evenly, mixed solution A is obtained；
(2) mixed solution A is added in the ethanol solution of butyl titanate, adds citric acid, obtains mixed solution B；
(3) by mixed solution B at 70-90 DEG C heating water bath, form gel under stirring condition；
(4) it is ground after gel drying, obtained dry gel particle roasts 2-3h at 150-220 DEG C, then forges at 380-500 DEG C
10-14h is burnt, La doping CoFe2O4/TiO2 composite photo-catalyst is obtained；
According to Co:Ti:La in above-mentioned steps: water: the molar ratio of citric acid is (0.5-0.8): 1:(0.10-0.18): (120-
200): the ratio of (7-10) is matched, and wherein Fe mole is 2 times of Co mole.
2. photochemical catalyst preparation method according to claim 1, it is characterised in that: Co:Ti:La: the molar ratio of citric acid
For 0.6:1:0.12:9.
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