CN112473733B - Mo-Eu co-doped titanium dioxide/aluminum phosphate molecular sieve composite photocatalyst and application thereof - Google Patents
Mo-Eu co-doped titanium dioxide/aluminum phosphate molecular sieve composite photocatalyst and application thereof Download PDFInfo
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- CN112473733B CN112473733B CN202011382376.5A CN202011382376A CN112473733B CN 112473733 B CN112473733 B CN 112473733B CN 202011382376 A CN202011382376 A CN 202011382376A CN 112473733 B CN112473733 B CN 112473733B
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- titanium dioxide
- doped titanium
- molecular sieve
- aluminum phosphate
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 153
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 73
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 39
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 title claims abstract description 38
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 38
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 35
- 239000002131 composite material Substances 0.000 title claims abstract description 31
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 34
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000004005 microsphere Substances 0.000 claims abstract description 32
- 239000011259 mixed solution Substances 0.000 claims abstract description 31
- 239000002351 wastewater Substances 0.000 claims abstract description 25
- 150000001412 amines Chemical class 0.000 claims abstract description 23
- 239000002608 ionic liquid Substances 0.000 claims abstract description 23
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 21
- 238000004043 dyeing Methods 0.000 claims abstract description 20
- 238000007639 printing Methods 0.000 claims abstract description 20
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 238000000926 separation method Methods 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- 238000002360 preparation method Methods 0.000 claims abstract description 5
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 18
- 235000015393 sodium molybdate Nutrition 0.000 claims description 18
- 239000011684 sodium molybdate Substances 0.000 claims description 18
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- IAZSXUOKBPGUMV-UHFFFAOYSA-N 1-butyl-3-methyl-1,2-dihydroimidazol-1-ium;chloride Chemical compound [Cl-].CCCC[NH+]1CN(C)C=C1 IAZSXUOKBPGUMV-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 6
- WLYAEQLCCOGBPV-UHFFFAOYSA-N europium;sulfuric acid Chemical compound [Eu].OS(O)(=O)=O WLYAEQLCCOGBPV-UHFFFAOYSA-N 0.000 claims description 6
- 239000002105 nanoparticle Substances 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- 239000004480 active ingredient Substances 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 abstract description 11
- 239000003344 environmental pollutant Substances 0.000 abstract description 4
- 231100000719 pollutant Toxicity 0.000 abstract description 4
- 230000009471 action Effects 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 26
- 229910052693 Europium Inorganic materials 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- 229910052750 molybdenum Inorganic materials 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 230000007547 defect Effects 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000002957 persistent organic pollutant Substances 0.000 description 5
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical group [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000005374 membrane filtration Methods 0.000 description 4
- 239000000969 carrier Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 230000001699 photocatalysis Effects 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 230000006798 recombination Effects 0.000 description 3
- 238000005215 recombination Methods 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 239000012028 Fenton's reagent Substances 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000010170 biological method Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- 238000004042 decolorization Methods 0.000 description 2
- 239000010919 dye waste Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000004043 responsiveness Effects 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 238000009279 wet oxidation reaction Methods 0.000 description 2
- 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 1
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000003933 environmental pollution control Methods 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000013385 inorganic framework Substances 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
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/83—Aluminophosphates [APO compounds]
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- B01J37/03—Precipitation; Co-precipitation
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Abstract
The invention discloses a Mo-Eu co-doped titanium dioxide/aluminum phosphate molecular sieve composite photocatalyst, which takes an aluminum phosphate molecular sieve as a carrier and takes Mo-Eu co-doped titanium dioxide nano microspheres as an active component, and the preparation method comprises the following steps: preparing a nano microsphere active component of the Mo-Eu co-doped titanium dioxide; uniformly mixing the ionic liquid, phosphoric acid, an aluminum source, organic amine and hydrofluoric acid; adding the Mo-Eu co-doped titanium dioxide nano microsphere active component prepared in the step S1 into the mixed solution in the step S2, wherein the mixture comprises the following substances in parts by mass: ionic liquid: phosphoric acid, aluminum source: organic amine: hydrofluoric acid: the Mo-Eu co-doped titanium dioxide nano microsphere active component is 10-12:2-3:1:5-6: 0.5-0.8: 0.3-0.5; crystallizing the mixture at the temperature of 350-400 ℃ for 30-50 min; centrifugal separation, washing, drying and roasting. The Mo-Eu co-doped titanium dioxide/aluminum phosphate molecular sieve composite photocatalyst provided by the invention can efficiently degrade pollutants in printing and dyeing wastewater under the action of visible light, and the usage amount of the catalyst is small.
Description
Technical Field
The invention relates to the technical field of catalysts, and particularly relates to a Mo-Eu co-doped titanium dioxide/aluminum phosphate molecular sieve composite photocatalyst and application thereof.
Background
China is the first country of dye production and consumption in the world, and the printing and dyeing wastewater pollution amount is large and the treatment difficulty is high. According to incomplete statistics, the daily wastewater discharge amount of printing and dyeing enterprises in China reaches 300-400 ten thousand tons, the loss amount of dye reaches 10-20 percent in the printing and dyeing processing process, at least half of the dye waste water flows into the environment, the treatment rate of the current dye waste water is less than 30 percent, and the qualification rate is less than 60 percent. Because the printing and dyeing wastewater has the characteristics of high chromaticity, high concentration of organic pollutants (especially refractory organic pollutants), large alkalinity, high water quantity, large water quality change, complex components, high Chemical Oxygen Demand (COD) and Biochemical Oxygen Demand (BOD), high toxicity and the like, toxic and harmful substances in the printing and dyeing wastewater also have an accumulation effect in animals and plants and are not easy to discharge, so that the toxicity is increased violently, carcinogenicity is generated, and the living environment of human beings is harmed. Therefore, the printing and dyeing wastewater is directly discharged into rivers and lakes without being treated, and the consequences and the damage of the printing and dyeing wastewater are conceivable. Therefore, the treatment of the printing and dyeing wastewater is enhanced, the problem of water resource shortage in China can be solved, the environmental pollution is reduced, the social hazard is reduced, and the method plays an important role in protecting the human environment, particularly the water environment.
At present, the research on the treatment technology of printing and dyeing wastewater at home and abroad mainly focuses on an adsorption method, a membrane filtration method, a coagulation method, a biological method and an oxidation method. The adsorption method is to utilize an adsorbent to adsorb impurities in the printing and dyeing wastewater to achieve the purposes of decoloring and purifying the wastewater, but the adsorbent has the defects of selective adsorption, difficult regeneration, high operation cost, secondary environmental problem and the like; the membrane filtration is to purify water by using water-insoluble impurities in the membrane filtration water, but the membrane filtration has no effect on soluble pollutants, and has large investment, difficult regeneration and high operation cost; the coagulation method is to utilize a flocculating agent to adsorb, flocculate and settle organic pollutants, separate impurities in a sludge form and purify waste water, but has the defects of changing feeding conditions according to the change of water quality, low processing flexibility, poor hydrophilic pollutant decoloring effect, low COD removal rate, difficult sludge dewatering, field occupation and the like; the biological method mainly utilizes microbial enzymes to degrade organic pollutants, thereby realizing the purpose of sewage purification; the oxidation method comprises an ozone oxidation method, a Fenton reagent oxidation method, a wet oxidation method, a catalytic oxidation method and the like, and is mainly a research hotspot because the oxidation method can completely eliminate the harmful degradation organic pollutants in a short time and does not generate secondary pollution, wherein the ozone method mainly has the defects of high treatment cost, unsuitability for treating large-flow wastewater and the like, the Fenton reagent method mainly has the defects of harsh reaction conditions, high acid consumption, high corrosion possibility of equipment and the like, the wet oxidation method needs to be carried out under the high-temperature and high-pressure conditions, the traditional catalytic oxidation method uses an active mercury lamp of an ultraviolet light excitation catalyst to purify the wastewater, and most of the prior catalytic oxidation methods use an industrial light source, an ultraviolet light excitation catalyst and the like as a light source and have low catalytic efficiency.
In the prior art, TiO2The photocatalyst has the characteristics of stable chemical property, strong oxidation-reduction capability, environmental friendliness and the like, and is widely applied to the field of environmental pollution control as a photocatalyst. However, TiO2High recombination rate of photon-generated carriers, narrow spectral response range and poor adsorption capacity which restrict TiO2The major bottleneck for photocatalyst activity.
In view of the above, the present invention aims to provide a composite catalyst with strong photocatalytic activity to solve the above technical problems.
Disclosure of Invention
The invention aims to overcome the technical defects and provide the Mo-Eu co-doped titanium dioxide/aluminum phosphate molecular sieve composite photocatalyst which can efficiently degrade pollutants in printing and dyeing wastewater under the action of visible light and has small usage amount.
In order to solve the technical problems, the technical scheme of the invention is as follows:
the Mo-Eu co-doped titanium dioxide/aluminum phosphate molecular sieve composite photocatalyst is characterized in that an aluminum phosphate molecular sieve is taken as a carrier, nanometer microspheres of Mo-Eu co-doped titanium dioxide are taken as active ingredients, and the preparation method comprises the following steps:
step S1, preparing the Mo-Eu co-doped titanium dioxide nano microsphere active component, which comprises the following steps:
step S11, mixing 10-20 parts of tetrabutyl orthotitanate and 20-30 parts of absolute ethyl alcohol to obtain a mixed solution A;
step S12, dissolving 5-8 parts of sodium molybdate in water to obtain a sodium molybdate solution;
step S13, adding a sodium molybdate solution into the mixed solution A, and dropwise adding 2-3 parts of europium sulfate under the ultrasonic stirring condition to obtain a mixed solution B;
step S14, carrying out centrifugal separation on the mixed solution B, and carrying out vacuum drying on the obtained slurry for 2-3h at the temperature of 50-60 ℃;
step S15, calcining the dried material, raising the temperature to 400-500 ℃ at the temperature raising speed of 8-10 ℃/min, and preserving the temperature for 30-40 min; then heating to 800-900 ℃ at the heating rate of 4-6 ℃/min, and preserving the heat for 50-60min to obtain the active component of the Mo-Eu co-doped titanium dioxide nano microsphere;
step S2, uniformly mixing the ionic liquid, phosphoric acid, an aluminum source, organic amine and hydrofluoric acid;
step S3, adding the Mo-Eu co-doped titanium dioxide nanoparticle active component prepared in step S1 into the mixed solution in step S2, wherein the mass parts of the components in the mixture are as follows:
ionic liquid: phosphoric acid, aluminum source: organic amine: hydrofluoric acid: the Mo-Eu co-doped titanium dioxide nano microsphere active component is 10-12:2-3:1:5-6: 0.5-0.8: 0.3-0.5;
step S4, crystallizing the mixture at the temperature of 350-400 ℃ for 30-50 min;
and step S5, obtaining the Mo-Eu co-doped titanium dioxide/aluminum phosphate molecular sieve composite photocatalyst through centrifugal separation, washing, drying and roasting.
Further, the ionic liquid is 1-butyl-3-methylimidazole chloride.
Further, the organic amine is triethylamine.
Further, in step S3, the mass parts of the substances in the mixture are:
ionic liquid: phosphoric acid, aluminum source: organic amine: hydrofluoric acid: the active components of the Mo-Eu co-doped titanium dioxide nano microsphere are 10:2:1:5: 0.6: 0.4.
further, in step S13, the frequency of ultrasonic agitation is 30-35 Hz.
The invention also provides an application of the Mo-Eu co-doped titanium dioxide/aluminum phosphate molecular sieve composite photocatalyst in printing and dyeing wastewater treatment.
Compared with the prior art, the Mo-Eu co-doped titanium dioxide/aluminum phosphate molecular sieve composite photocatalyst provided by the invention has the beneficial effects that:
according to the Mo-Eu co-doped titanium dioxide/aluminum phosphate molecular sieve composite photocatalyst provided by the invention, the aluminum phosphate molecular sieve is taken as a carrier, so that the particle size of the photocatalyst can be reduced, particle agglomeration is inhibited, a large specific surface area is provided, and the adsorption capacity is enhanced; the Mo-Eu co-doped titanium dioxide nano-microsphere is used as an active component, Mo and Eu doping can block anatase phase-to-rutile phase transformation of titanium dioxide, can obviously inhibit growth of titanium dioxide crystal grains, enables the crystal structure to be regular and the grain size to be uniform under the synergistic inhibition effect of Mo and Eu, and can be well dispersed in an aluminum phosphate molecular sieve structure; meanwhile, Mo can improve the responsiveness of visible light, and Mo and Eu are jointly doped, so that the recombination probability of photon-generated carriers is effectively reduced, the photocatalytic activity is improved, and the catalytic efficiency of the catalyst is improved. The Mo-Eu co-doped titanium dioxide/aluminum phosphate molecular sieve composite photocatalyst provided by the invention has higher treatment efficiency on printing and dyeing wastewater under the irradiation of visible light, the decolorization rate reaches 97%, the COD removal efficiency reaches 95%, and the toluene removal rate reaches 97%.
Detailed Description
The following detailed description of the present invention is provided to enable those skilled in the art to better understand the technical solutions in the embodiments of the present invention and to make the above objects, features and advantages of the present invention more comprehensible.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For numerical ranges, combinations of values between the endpoints of each of the ranges, between the endpoints of each of the ranges and individual values, and between individual values can result in one or more new numerical ranges, and such numerical ranges should be considered as being specifically disclosed herein.
A Mo-Eu co-doped titanium dioxide/aluminum phosphate molecular sieve composite photocatalyst takes an aluminum phosphate molecular sieve as a carrier and takes Mo-Eu co-doped titanium dioxide nano microspheres as an active component, and the preparation method comprises the following steps:
step S1, preparing the Mo-Eu co-doped titanium dioxide nano microsphere active component, which comprises the following steps:
step S11, mixing 10-20 parts of tetrabutyl orthotitanate and 20-30 parts of absolute ethyl alcohol to obtain a mixed solution A;
step S12, dissolving 5-8 parts of sodium molybdate in water to obtain a sodium molybdate solution;
step S13, adding the sodium molybdate solution into the mixed solution A, and dropwise adding 2-3 parts of europium sulfate under the condition of ultrasonic stirring to obtain a mixed solution B; wherein the frequency of ultrasonic stirring is 30-35 Hz;
step S14, performing centrifugal separation on the mixed solution B, and performing vacuum drying on the obtained slurry for 2-3h at the temperature of 50-60 ℃;
step S15, calcining the dried material, raising the temperature to 400-500 ℃ at the temperature raising speed of 8-10 ℃/min, and preserving the heat for 30-40 min; then heating to 800-900 ℃ at the heating rate of 4-6 ℃/min, and preserving the heat for 50-60min to obtain the active component of the Mo-Eu co-doped titanium dioxide nano microsphere;
step S2, uniformly mixing the ionic liquid, phosphoric acid, an aluminum source, organic amine and hydrofluoric acid;
wherein the ionic liquid is 1-butyl-3-methylimidazole chloride; organic amine is used as a template agent, and specifically is triethylamine; the aluminum source is pseudo-boehmite;
step S3, adding the Mo-Eu co-doped titanium dioxide nanoparticle active ingredient prepared in step S1 into the mixed solution in step S2, wherein the mass parts of the materials in the mixture are as follows:
ionic liquid: phosphoric acid, aluminum source: organic amine: hydrofluoric acid: the Mo-Eu co-doped titanium dioxide nano microsphere active components are (wt%) 10-12:2-3:1:5-6: 0.5-0.8: 0.3-0.5;
step S4, crystallizing the mixture at the temperature of 350-400 ℃ for 30-50 min;
step S5, carrying out centrifugal separation, washing, drying and roasting to obtain the Mo-Eu co-doped titanium dioxide/aluminum phosphate molecular sieve composite photocatalyst;
in the step, the drying also adopts vacuum drying, the vacuum drying temperature is 45-50 ℃, the roasting temperature is 280-350 ℃, and the roasting time is 2-3 h.
The Mo-Eu co-doped titanium dioxide/aluminum phosphate molecular sieve composite photocatalyst of the present invention is described in detail by specific examples.
Example 1
A preparation method of the Mo-Eu co-doped titanium dioxide/aluminum phosphate molecular sieve composite photocatalyst comprises the following steps:
step S1, preparing the Mo-Eu co-doped titanium dioxide nano microsphere active component, which comprises the following steps:
step S11, mixing 10 parts of tetrabutyl orthotitanate and 20 parts of absolute ethyl alcohol to obtain a mixed solution A;
step S12, dissolving 5 parts of sodium molybdate in water to obtain a sodium molybdate solution;
step S13, adding a sodium molybdate solution into the mixed solution A, and dropwise adding 2 parts of europium sulfate under the stirring condition to obtain a mixed solution B;
step S14, carrying out centrifugal separation on the mixed solution B, and carrying out vacuum drying on the obtained slurry for 2-3h at 50 ℃;
step S15, calcining the dried material, heating to 400 ℃ at a heating rate of 8-10 ℃/min, and keeping the temperature for 30-40 min; then heating to 800 ℃ at the heating rate of 4-6 ℃/min, and keeping the temperature for 50-60min to obtain the Mo-Eu co-doped titanium dioxide nano microsphere active component;
step S2, uniformly mixing the ionic liquid, phosphoric acid, an aluminum source, organic amine and hydrofluoric acid;
wherein the ionic liquid is 1-butyl-3-methylimidazole chloride; organic amine is used as a template agent, and specifically is triethylamine; the aluminum source is pseudoboehmite;
step S3, adding the Mo-Eu co-doped titanium dioxide nanoparticle active component prepared in step S1 into the mixed solution in step S2, wherein the mass parts of the components in the mixture are as follows:
ionic liquid: phosphoric acid, aluminum source: organic amine: hydrofluoric acid: the active components of the Mo-Eu co-doped titanium dioxide nano microsphere are as follows (10: 2:1:5: 0.6): 0.4 of the total weight of the mixture;
step S4, crystallizing the mixture at 350 ℃ for 30-50 min;
and step S5, obtaining the Mo-Eu co-doped titanium dioxide/aluminum phosphate molecular sieve composite photocatalyst through centrifugal separation, washing, drying and roasting.
Example 2
A Mo-Eu co-doped titanium dioxide/aluminum phosphate molecular sieve composite photocatalyst comprises the following steps:
step S1, preparing the Mo-Eu co-doped titanium dioxide nano microsphere active component, which comprises the following steps:
step S11, mixing 20 parts of tetrabutyl orthotitanate and 30 parts of absolute ethyl alcohol to obtain a mixed solution A;
step S12, dissolving 8 parts of sodium molybdate in water to obtain a sodium molybdate solution;
step S13, adding a sodium molybdate solution into the mixed solution A, and dropwise adding 3 parts of europium sulfate under the stirring condition to obtain a mixed solution B;
step S14, carrying out centrifugal separation on the mixed solution B, and carrying out vacuum drying on the obtained slurry for 2-3h at the temperature of 60 ℃;
step S15, calcining the dried material, heating to 450 ℃ at a heating rate of 8-10 ℃/min, and preserving heat for 30-40 min; then heating to 900 ℃ at the heating rate of 4-6 ℃/min, and preserving the heat for 50-60min to obtain the Mo-Eu co-doped titanium dioxide nano microsphere active component;
step S2, uniformly mixing the ionic liquid, phosphoric acid, an aluminum source, organic amine and hydrofluoric acid;
wherein the ionic liquid is 1-butyl-3-methylimidazole chloride; organic amine is used as a template agent, and specifically is triethylamine; the aluminum source is pseudo-boehmite;
step S3, adding the Mo-Eu co-doped titanium dioxide nanoparticle active ingredient prepared in step S1 into the mixed solution in step S2, wherein the mass parts of the materials in the mixture are as follows:
ionic liquid: phosphoric acid, aluminum source: organic amine: hydrofluoric acid: the active components of the Mo-Eu co-doped titanium dioxide nano microsphere are as follows (12: 4:1:6: 0.5: 0.5;
step S4, crystallizing the mixture at 400 ℃ for 30-50 min;
and step S5, obtaining the Mo-Eu co-doped titanium dioxide/aluminum phosphate molecular sieve composite photocatalyst through centrifugal separation, washing, drying and roasting.
Example 3
A Mo-Eu co-doped titanium dioxide/aluminum phosphate molecular sieve composite photocatalyst comprises the following steps:
step S1, preparing the Mo-Eu co-doped titanium dioxide nano microsphere active component, which comprises the following steps:
step S11, mixing 15 parts of tetrabutyl orthotitanate and 25 parts of absolute ethyl alcohol to obtain a mixed solution A;
step S12, dissolving 6 parts of sodium molybdate in water to obtain a sodium molybdate solution;
step S13, adding a sodium molybdate solution into the mixed solution A, and dropwise adding 3 parts of europium sulfate under the stirring condition to obtain a mixed solution B;
step S14, carrying out centrifugal separation on the mixed solution B, and carrying out vacuum drying on the obtained slurry for 2-3h at the temperature of 58 ℃;
step S15, calcining the dried material, heating to 450 ℃ at a heating rate of 8-10 ℃/min, and keeping the temperature for 30-40 min; then heating to 860 ℃ at the heating rate of 4-6 ℃/min, and keeping the temperature for 50-60min to obtain the Mo-Eu co-doped titanium dioxide nano microsphere active component;
step S2, uniformly mixing the ionic liquid, phosphoric acid, an aluminum source, organic amine and hydrofluoric acid;
wherein the ionic liquid is 1-butyl-3-methylimidazole chloride; organic amine is used as a template agent, and specifically is triethylamine; the aluminum source is pseudoboehmite;
step S3, adding the Mo-Eu co-doped titanium dioxide nanoparticle active component prepared in step S1 into the mixed solution in step S2, wherein the mass parts of the components in the mixture are as follows:
ionic liquid: phosphoric acid, aluminum source: organic amine: hydrofluoric acid: the active components of the Mo-Eu co-doped titanium dioxide nano microsphere are 11:2:1:6: 0.8: 0.3;
step S4, crystallizing the mixture at 380 ℃ for 30-50 min;
and step S5, carrying out centrifugal separation, washing, drying and roasting to obtain the Mo-Eu co-doped titanium dioxide/aluminum phosphate molecular sieve composite photocatalyst.
Comparative example 1
Based on the embodiment 1, the molybdenum element doping is eliminated; the other process steps and parameters were the same as in example 1.
Comparative example 2
Based on the embodiment 1, the doping of rare earth europium element is cancelled, and other process steps and parameters are the same as those of the embodiment 1.
Comparative example 3
Based on the embodiment 1, the doping of molybdenum element and rare earth europium element is cancelled, and other process steps and parameters are the same as those of the embodiment 1.
Comparative example 4
Based on the example 1, the ratio of the active components of the Mo-Eu co-doped titanium dioxide nano microsphere is changed, so that the ionic liquid: phosphoric acid, aluminum source: organic amine: hydrofluoric acid: the active components of the Mo-Eu co-doped titanium dioxide nano microsphere are as follows (10: 2:1:5: 0.6): 0.8; the other process steps and parameters were the same as in example 1.
The catalysts of examples 1 to 3 and comparative examples 1 to 4 were used for the treatment of printing and dyeing wastewater, and performance tests were conducted. The test method is as follows:
taking printing and dyeing wastewater, wherein the content of methylene blue in the wastewater is 90mg/L, the content of toluene in the wastewater is 24mg/L, and the COD concentration is 1280 mg/L;
the catalysts of the examples 1-3 and the comparative examples 1-4 are respectively put into the same amount of printing and dyeing wastewater, stirred for 90-120min under the irradiation of visible light, and then the purified water quality index is detected, wherein the dosage of the catalyst is 3% of the wastewater. The water quality indexes after purification are as follows:
according to the Mo-Eu co-doped titanium dioxide/aluminum phosphate molecular sieve composite photocatalyst provided by the invention, the active component is the nano microsphere particles of Mo-Eu co-doped titanium dioxide, and the Mo and Eu have synergistic effect to improve the catalytic activity of the titanium dioxide, so that the printing and dyeing wastewater purification effect is better;
the Mo-Eu co-doped titanium dioxide/aluminum phosphate molecular sieve composite photocatalyst provided by the invention adopts an ionothermal method to prepare an aluminum phosphate molecular sieve, provides required cations for an inorganic framework structure, and plays a guiding role in the process of combining a carrier and an active component to form an ordered molecular sieve structure; the aluminum phosphate molecular sieve is synthesized by adopting an ionic thermal method, so that hydroxide and amorphous substances can be avoided from being generated, and the catalytic efficiency of the catalyst can be improved.
The Mo-Eu co-doped titanium dioxide/aluminum phosphate molecular sieve composite photocatalyst provided by the invention takes the aluminum phosphate molecular sieve as a carrier, can reduce the particle size of the photocatalyst, inhibit particle agglomeration, provide large specific surface area and enhance adsorption capacity; the Mo-Eu co-doped titanium dioxide nano-microsphere is used as an active component, Mo and Eu doping can block anatase phase-to-rutile phase transformation of titanium dioxide, can obviously inhibit growth of titanium dioxide crystal grains, enables the crystal structure to be regular and the grain size to be uniform under the synergistic inhibition effect of Mo and Eu, and can be well dispersed in an aluminum phosphate molecular sieve structure; meanwhile, Mo can improve the responsiveness of visible light, and under the effect of the co-doping of Mo and Eu, the recombination probability of photon-generated carriers is effectively reduced, the photocatalytic activity under the irradiation of visible light is improved, and the catalytic efficiency of the catalyst is improved. The Mo-Eu co-doped titanium dioxide/aluminum phosphate molecular sieve composite photocatalyst provided by the invention has higher treatment efficiency on printing and dyeing wastewater under the irradiation of visible light, the decolorization rate reaches 97%, the COD removal efficiency reaches 95%, and the toluene removal rate reaches 97%.
The embodiments of the present invention have been described in detail, but the present invention is not limited to the described embodiments. Various changes, modifications, substitutions and alterations to these embodiments will occur to those skilled in the art without departing from the spirit and scope of the present invention.
Claims (4)
1. The Mo-Eu co-doped titanium dioxide/aluminum phosphate molecular sieve composite photocatalyst is characterized in that an aluminum phosphate molecular sieve is taken as a carrier, nanometer microspheres of Mo-Eu co-doped titanium dioxide are taken as active ingredients, and the preparation method comprises the following steps:
step S1, preparing the Mo-Eu co-doped titanium dioxide nano microsphere active component, which comprises the following steps:
step S11, mixing 10-20 parts of tetrabutyl orthotitanate and 20-30 parts of absolute ethyl alcohol to obtain a mixed solution A;
step S12, dissolving 5-8 parts of sodium molybdate in water to obtain a sodium molybdate solution;
step S13, adding a sodium molybdate solution into the mixed solution A, and dropwise adding 2-3 parts of europium sulfate under the ultrasonic stirring condition to obtain a mixed solution B;
step S14, performing centrifugal separation on the mixed solution B, and performing vacuum drying on the obtained slurry for 2-3h at the temperature of 50-60 ℃;
step S15, calcining the dried material, raising the temperature to 400-500 ℃ at the temperature raising speed of 8-10 ℃/min, and preserving the temperature for 30-40 min; then heating to 800-900 ℃ at the heating rate of 4-6 ℃/min, and preserving the heat for 50-60min to obtain the active component of the Mo-Eu co-doped titanium dioxide nano microsphere;
step S2, uniformly mixing the ionic liquid, phosphoric acid, an aluminum source, organic amine and hydrofluoric acid; wherein the ionic liquid is 1-butyl-3-methylimidazole chloride; the organic amine is triethylamine;
step S3, adding the Mo-Eu co-doped titanium dioxide nanoparticle active ingredient prepared in step S1 into the mixed solution in step S2, wherein the mass parts of the materials in the mixture are as follows:
ionic liquid: phosphoric acid, aluminum source: organic amine: hydrofluoric acid: the Mo-Eu co-doped titanium dioxide nano microsphere active component is 10-12:2-3:1:5-6: 0.5-0.8: 0.3-0.5;
step S4, crystallizing the mixture at the temperature of 350-400 ℃ for 30-50 min;
and step S5, carrying out centrifugal separation, washing, drying and roasting to obtain the Mo-Eu co-doped titanium dioxide/aluminum phosphate molecular sieve composite photocatalyst.
2. The Mo-Eu co-doped titanium dioxide/aluminum phosphate molecular sieve composite photocatalyst of claim 1, wherein in step S3, the mass part ratio of each substance in the mixture is:
ionic liquid: phosphoric acid, aluminum source: organic amine: hydrofluoric acid: the active components of the Mo-Eu co-doped titanium dioxide nano microsphere are as follows (10: 2:1:5: 0.6): 0.4.
3. the Mo-Eu co-doped titanium dioxide/aluminum phosphate molecular sieve composite photocatalyst of claim 1, wherein in step S13, the frequency of ultrasonic stirring is 30-35 Hz.
4. The application of the Mo-Eu co-doped titanium dioxide/aluminum phosphate molecular sieve composite photocatalyst disclosed by any one of claims 1-3 in treatment of printing and dyeing wastewater.
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Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4207745A1 (en) * | 1992-03-11 | 1993-09-16 | Basf Ag | MOLECULAR SCREENS CONTAINING AZO DYES |
| FR2869897A1 (en) * | 2004-05-10 | 2005-11-11 | Saint Gobain | PHOTOCATALYTIC COATING SUBSTRATE |
| CN101952116A (en) * | 2007-11-16 | 2011-01-19 | 瓦林格光催化股份有限公司 | Photocatalytic boards or panels and a method of manufacturing thereof |
| CN102101681A (en) * | 2009-12-16 | 2011-06-22 | 中国科学院大连化学物理研究所 | Ionothermal synthesis method of microporous aluminum phosphate molecular sieve |
| CN102872774A (en) * | 2011-07-11 | 2013-01-16 | 张�林 | Titanium dioxide (shell)-dopant (core) composite material and preparation method thereof |
| CN103801391A (en) * | 2014-02-19 | 2014-05-21 | 山西大学 | Preparation method for titanium-silicon-aluminum phosphate molecular sieve catalyst |
| CN105142782A (en) * | 2013-04-24 | 2015-12-09 | 沙特基础工业公司 | Catalyst for selective synthesis of lower hydrocarbons from syngas |
| KR20180065493A (en) * | 2016-12-08 | 2018-06-18 | 한국과학기술원 | Gas sensor and member using metal oxide nanotubes including nanoscale heterogeneous catalysts by using metal-organic framework, and manufacturing method thereof |
| KR101876938B1 (en) * | 2017-09-12 | 2018-07-10 | 주식회사 소프스톤 | Manufacturing of titanium dioxide and titanium dioxide manufactured therefrom |
| CN109535305A (en) * | 2018-11-26 | 2019-03-29 | 贵州省化工研究院 | A kind of preparation method of Rhein adsorbent material |
| CN110801827A (en) * | 2019-11-24 | 2020-02-18 | 南京公诚节能新材料研究院有限公司 | Preparation method of photosensitive degradation catalyst |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20160339416A1 (en) * | 2010-12-09 | 2016-11-24 | Sk Innovation Co., Ltd. | Hydroprocessing catalyst and method for preparing same |
-
2020
- 2020-12-01 CN CN202011382376.5A patent/CN112473733B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4207745A1 (en) * | 1992-03-11 | 1993-09-16 | Basf Ag | MOLECULAR SCREENS CONTAINING AZO DYES |
| FR2869897A1 (en) * | 2004-05-10 | 2005-11-11 | Saint Gobain | PHOTOCATALYTIC COATING SUBSTRATE |
| CN101952116A (en) * | 2007-11-16 | 2011-01-19 | 瓦林格光催化股份有限公司 | Photocatalytic boards or panels and a method of manufacturing thereof |
| CN102101681A (en) * | 2009-12-16 | 2011-06-22 | 中国科学院大连化学物理研究所 | Ionothermal synthesis method of microporous aluminum phosphate molecular sieve |
| CN102872774A (en) * | 2011-07-11 | 2013-01-16 | 张�林 | Titanium dioxide (shell)-dopant (core) composite material and preparation method thereof |
| CN105142782A (en) * | 2013-04-24 | 2015-12-09 | 沙特基础工业公司 | Catalyst for selective synthesis of lower hydrocarbons from syngas |
| CN103801391A (en) * | 2014-02-19 | 2014-05-21 | 山西大学 | Preparation method for titanium-silicon-aluminum phosphate molecular sieve catalyst |
| KR20180065493A (en) * | 2016-12-08 | 2018-06-18 | 한국과학기술원 | Gas sensor and member using metal oxide nanotubes including nanoscale heterogeneous catalysts by using metal-organic framework, and manufacturing method thereof |
| KR101876938B1 (en) * | 2017-09-12 | 2018-07-10 | 주식회사 소프스톤 | Manufacturing of titanium dioxide and titanium dioxide manufactured therefrom |
| CN109535305A (en) * | 2018-11-26 | 2019-03-29 | 贵州省化工研究院 | A kind of preparation method of Rhein adsorbent material |
| CN110801827A (en) * | 2019-11-24 | 2020-02-18 | 南京公诚节能新材料研究院有限公司 | Preparation method of photosensitive degradation catalyst |
Non-Patent Citations (1)
| Title |
|---|
| 镧铕共掺TiO_2/复合白土光催化剂的合成及工业废水处理活性;郭莉等;《应用化工》;20110428(第04期);全文 * |
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