CN113244950A - Composite carrier photocatalyst and application thereof - Google Patents
Composite carrier photocatalyst and application thereof Download PDFInfo
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- CN113244950A CN113244950A CN202110575387.3A CN202110575387A CN113244950A CN 113244950 A CN113244950 A CN 113244950A CN 202110575387 A CN202110575387 A CN 202110575387A CN 113244950 A CN113244950 A CN 113244950A
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- 239000002131 composite material Substances 0.000 title claims abstract description 136
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 54
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 70
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 claims abstract description 68
- 239000002808 molecular sieve Substances 0.000 claims abstract description 68
- 238000000034 method Methods 0.000 claims abstract description 33
- 239000004005 microsphere Substances 0.000 claims abstract description 33
- 229910010442 TiO2-SnO2 Inorganic materials 0.000 claims abstract description 30
- 229910010257 TiO2—SnO2 Inorganic materials 0.000 claims abstract description 30
- 229940019931 silver phosphate Drugs 0.000 claims abstract description 29
- 229910000161 silver phosphate Inorganic materials 0.000 claims abstract description 29
- FJOLTQXXWSRAIX-UHFFFAOYSA-K silver phosphate Chemical compound [Ag+].[Ag+].[Ag+].[O-]P([O-])([O-])=O FJOLTQXXWSRAIX-UHFFFAOYSA-K 0.000 claims abstract description 27
- 239000002351 wastewater Substances 0.000 claims abstract description 26
- 238000004043 dyeing Methods 0.000 claims abstract description 23
- 230000009471 action Effects 0.000 claims abstract description 14
- 239000004480 active ingredient Substances 0.000 claims abstract description 14
- 238000002360 preparation method Methods 0.000 claims abstract description 11
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 239000000969 carrier Substances 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims description 28
- 239000011259 mixed solution Substances 0.000 claims description 24
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 20
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 18
- 239000002608 ionic liquid Substances 0.000 claims description 13
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 12
- 238000003760 magnetic stirring Methods 0.000 claims description 12
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 12
- 238000000926 separation method Methods 0.000 claims description 10
- 238000001291 vacuum drying Methods 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 9
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 8
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 6
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- 230000031700 light absorption Effects 0.000 claims description 5
- 239000011148 porous material Substances 0.000 claims description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 abstract description 9
- 239000003344 environmental pollutant Substances 0.000 abstract description 4
- 231100000719 pollutant Toxicity 0.000 abstract description 4
- 238000004065 wastewater treatment Methods 0.000 abstract description 3
- 239000002077 nanosphere Substances 0.000 abstract 1
- 230000003197 catalytic effect Effects 0.000 description 11
- 239000013078 crystal Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 230000003647 oxidation Effects 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 6
- 229940012189 methyl orange Drugs 0.000 description 6
- 238000000746 purification Methods 0.000 description 6
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 6
- 229940043267 rhodamine b Drugs 0.000 description 6
- 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 5
- 230000007547 defect Effects 0.000 description 5
- 229960000907 methylthioninium chloride Drugs 0.000 description 5
- 239000002957 persistent organic pollutant Substances 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- KAIPKTYOBMEXRR-UHFFFAOYSA-N 1-butyl-3-methyl-2h-imidazole Chemical class CCCCN1CN(C)C=C1 KAIPKTYOBMEXRR-UHFFFAOYSA-N 0.000 description 4
- 238000003917 TEM image Methods 0.000 description 4
- 238000005374 membrane filtration Methods 0.000 description 4
- 230000001699 photocatalysis Effects 0.000 description 4
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000012028 Fenton's reagent Substances 0.000 description 2
- 241000282414 Homo sapiens Species 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
- 229940001007 aluminium phosphate Drugs 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000010170 biological method Methods 0.000 description 2
- 230000005540 biological transmission Effects 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
- 230000000295 complement effect Effects 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 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
- -1 silver phosphate compound Chemical class 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 238000009279 wet oxidation reaction Methods 0.000 description 2
- 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
- 230000004075 alteration 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
- 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
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 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
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- MCPLVIGCWWTHFH-UHFFFAOYSA-L methyl blue Chemical compound [Na+].[Na+].C1=CC(S(=O)(=O)[O-])=CC=C1NC1=CC=C(C(=C2C=CC(C=C2)=[NH+]C=2C=CC(=CC=2)S([O-])(=O)=O)C=2C=CC(NC=3C=CC(=CC=3)S([O-])(=O)=O)=CC=2)C=C1 MCPLVIGCWWTHFH-UHFFFAOYSA-L 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
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 239000010865 sewage Substances 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
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Images
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/83—Aluminophosphates [APO compounds]
-
- 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
-
- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/32—Hydrocarbons, e.g. oil
- C02F2101/322—Volatile compounds, e.g. benzene
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention discloses a composite carrier photocatalyst, which takes an aluminum phosphate molecular sieve and a silver phosphate composite as carriers and TiO2‑SnO2The composite nano-microsphere is an active component, and the preparation method comprises the following steps: preparation of TiO2‑SnO2A composite nanosphere active ingredient; preparing an aluminum phosphate molecular sieve by an ionic thermal method; preparing an aluminum phosphate molecular sieve and a silver phosphate composite carrier; adding TiO into the mixture2‑SnO2The composite nano-microspheres are loaded on a composite carrier. The composite carrier photocatalyst provided by the invention can efficiently degrade various printing and dyeing wastewater pollutants under the action of visible light,the treatment efficiency of the printing and dyeing wastewater is improved. The invention also provides an application of the composite carrier catalyst in printing and dyeing wastewater treatment.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to a composite carrier photocatalyst and a preparation method and application thereof.
Background
The printing and dyeing wastewater has the characteristics of high chromaticity, high concentration of organic pollutants (especially refractory organic pollutants), high 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, wherein toxic and harmful substances 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 harm 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 utilize the water-insoluble impurities in the membrane filtration water to purify the water, but the membrane filtration has no function on soluble pollutants, the investment is large, the regeneration is difficult, and the operation cost is high; 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 a research hotspot mainly because the oxidation method can completely eliminate the harmful degradation of 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, easy corrosion of equipment and the like, the wet oxidation method needs to be carried out under the conditions of high temperature and high pressure, the traditional catalytic oxidation method is to use an artificial light source ultraviolet light to excite the activity of a mercury lamp of a catalyst to purify wastewater, and most of the prior catalytic oxidation methods use a light source, a xenon lamp and the like as light sources and have low catalytic efficiency.
In view of the above, it is necessary to provide a new process to solve the above technical problems.
Disclosure of Invention
The invention aims to overcome the technical defects and provide the composite carrier photocatalyst which can efficiently degrade various printing and dyeing wastewater pollutants under the action of visible light and improve the treatment efficiency of the printing and dyeing wastewater.
In order to solve the technical problems, the technical scheme of the invention is as follows:
a composite carrier photocatalyst is prepared from aluminium phosphate molecular sieve and silver phosphate compound as carrier and TiO2-SnO2The preparation method of the composite nano microsphere which is used as an active ingredient comprises the following steps:
step S1, preparing TiO2-SnO2The active component of the composite nano microsphere comprises the following steps:
step S11, mixing a certain amount of tetrabutyl orthotitanate and absolute ethyl alcohol to obtain a mixed solution A;
step S12, adding SnCl2Adding the solution into the mixed solution A, and obtaining a mixed solution B under the condition of ultrasonic stirring;
step S13, 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 60-70 ℃;
step S14, calcining the dried material, raising the temperature to 200 ℃ and 230 ℃ at the temperature raising speed of 10-12 ℃/min, and preserving the temperature for 30-60 min; then heating to 650-700 ℃ at the heating rate of 8-10 ℃/min, and preserving the heat for 30-60min to obtain TiO2-SnO2Composite nano-microsphere active ingredient, wherein TiO2/SnO2The mass ratio of (A) to (B) is 10-15: 1;
step S2, preparing an aluminum phosphate molecular sieve;
step S3, preparing the aluminum phosphate molecular sieve and the silver phosphate composite carrier, comprising the following steps:
step S31, adding a certain amount of deionized water into the aluminum phosphate molecular sieve, uniformly stirring, gradually dropwise adding a silver nitrate solution into the aluminum phosphate molecular sieve, and then adding a certain amount of Na under the action of magnetic stirring2HPO4A solution;
step S32, drying for 2-3h in a vacuum environment after washing and filtering;
step S33, roasting for 2-3h at 650-680 ℃ to obtain an aluminum phosphate molecular sieve and a silver phosphate composite carrier, wherein the weight of the silver phosphate accounts for 30-50% of that of the aluminum phosphate molecular sieve;
step S4, preparing a composite carrier photocatalyst, comprising the steps of:
step S41, taking the composite carrier and TiO2-SnO2Mixing the composite nano microspheres, adding a certain amount of deionized water, and uniformly stirring under the action of magnetic stirring;
step S42, drying for 2-3h in vacuum environment after washing and filtering to obtain the composite carrier photocatalyst, wherein TiO2-SnO2The mixing mass ratio of the composite nano-microspheres to the composite carrier is 5-8: 100.
Furthermore, the porosity of the composite carrier is 80-86%, and the pore diameter is 6-10 nm.
Further, the aluminum phosphate molecular sieve is prepared by adopting an ionic thermal method.
Further, the preparation method of the aluminum phosphate molecular sieve comprises the following steps:
uniformly mixing the ionic liquid, phosphoric acid, pseudo-boehmite, triethylamine template agent and hydrofluoric acid;
crystallizing the mixture at the temperature of 350-400 ℃ for 30-50 min;
and centrifugally separating, washing and drying to obtain the aluminum phosphate molecular sieve.
Further, the visible light absorption wavelength of the composite carrier photocatalyst is 450-680 nm.
The invention also provides an application of the composite carrier photocatalyst in printing and dyeing wastewater treatment.
Compared with the prior art, the composite carrier photocatalyst provided by the invention has the beneficial effects that:
the composite carrier photocatalyst provided by the invention takes an aluminum phosphate molecular sieve and a silver phosphate composite as carriers and TiO2-SnO2The composite nano-microspheres are active ingredients, wherein the composite carrier is a large-aperture molecular sieve structure and has a good adsorption effect; the composite carrier has a photocatalytic effect and is combined with the active component, so that the catalytic property of the composite carrier is complementary to that of the active component, and the photocatalytic effect can be enhanced. The composite carrier photocatalyst provided by the invention has a wider visible light absorption wavelength of 450-680nm, so that the composite carrier photocatalyst can be simultaneously used for photocatalytic degradation of various printing and dyeing wastewater such as methylene blue, rhodamine B, methyl orange and the like.
II, the composite carrier photocatalyst, TiO, provided by the invention2-SnO2The active components of the composite nano microsphere simultaneously contain anatase crystal phase and rutile crystal phase, and the calcination process can control the generation of the rutile crystal phase and ensure that the catalytic performance of the formed rutile crystal phase or the formed rutile crystal phase is higher.
The composite carrier photocatalyst provided by the invention adopts an ionic thermal method to synthesize the aluminum phosphate molecular sieve, can avoid the generation of hydroxides and some amorphous substances, and can improve the catalytic efficiency of the catalyst.
The composite carrier photocatalyst provided by the invention has high treatment efficiency on various printing and dyeing wastewater under the irradiation of visible light, the removal efficiency of COD is 97%, the removal efficiency of methylene blue is 99%, the removal efficiency of rhodamine B is 98%, the removal efficiency of methyl orange is 98%, and the removal efficiency of toluene is 99%.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 is an SEM image of an aluminum phosphate molecular sieve of example 1;
FIG. 2 is an SEM image of the aluminum phosphate molecular sieve and silver phosphate composite support of example 1;
FIG. 3 is a TEM image of a transmission electron microscope of the aluminum phosphate molecular sieve and silver phosphate composite carrier of example 1;
FIG. 4 is an SEM photograph of the composite supported photocatalyst in example 1;
FIG. 5 is a TEM image of the composite supported photocatalyst in example 1.
Detailed Description
The following 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 ranges of values, between the endpoints of each of the ranges and the individual values, and between the individual values may be combined with each other to yield one or more new ranges of values, which ranges of values should be considered as specifically disclosed herein.
A composite carrier photocatalyst is prepared from aluminium phosphate molecular sieve and silver phosphate compound as carrier and TiO2-SnO2The preparation method of the composite nano microsphere which is used as an active ingredient comprises the following steps:
step S1, preparing TiO2-SnO2The active component of the composite nano microsphere comprises the following steps:
step S11, mixing a certain amount of tetrabutyl orthotitanate and absolute ethyl alcohol to obtain a mixed solution A;
the absolute ethyl alcohol is used for dissolving the tetrabutyl orthotitanate, the dosage of the absolute ethyl alcohol is adjusted according to the amount of the tetrabutyl orthotitanate, and the amount of the absolute ethyl alcohol is 2-3 times of that of the tetrabutyl orthotitanate;
step S12, adding SnCl2Adding the solution into the mixed solution A, and obtaining a mixed solution B under the condition of ultrasonic stirring;
step S13, 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 60-70 ℃;
step S14, calcining the dried material, raising the temperature to 200 ℃ and 230 ℃ at the temperature raising speed of 10-12 ℃/min, and preserving the temperature for 30-60 min; then heating to 650-700 ℃ at the heating rate of 8-10 ℃/min, and preserving the heat for 30-60min to obtain TiO2-SnO2Composite nano-microsphere active ingredient, wherein TiO2/SnO2The mass ratio of (A) to (B) is 10-15: 1;
step S2, preparing an aluminum phosphate molecular sieve;
in the invention, the aluminum phosphate molecular sieve is prepared by adopting an ionic thermal method, which comprises the following steps:
step S21, uniformly mixing the ionic liquid, phosphoric acid, pseudo-boehmite, triethylamine template agent and hydrofluoric acid; wherein the ionic liquid is chlorinated 1-butyl-3-methylimidazole, and the mixing mass ratio is as follows: 10-12:2-3:1:5-6: 0.5-0.8;
step S22, crystallizing the mixture at the temperature of 350-400 ℃ for 30-50 min;
step S23, carrying out centrifugal separation, washing and drying to obtain an aluminum phosphate molecular sieve; wherein the drying adopts vacuum drying, and the temperature is 70-80 ℃.
Step S3, preparing the aluminum phosphate molecular sieve and the silver phosphate composite carrier, comprising the following steps:
step S31, adding a certain amount of deionized water into the aluminum phosphate molecular sieve, uniformly stirring, gradually dropwise adding a silver nitrate solution into the aluminum phosphate molecular sieve, and then adding a certain amount of Na under the action of magnetic stirring2HPO4A solution;
step S32, drying for 2-3h in a vacuum environment after washing and filtering;
step S33, roasting for 2-3h at 650-680 ℃ to obtain an aluminum phosphate molecular sieve and a silver phosphate composite carrier, wherein the weight of the silver phosphate accounts for 30-50% of that of the aluminum phosphate molecular sieve;
step S4, preparing a composite carrier photocatalyst, comprising the steps of:
step S41, taking the composite carrier and TiO2-SnO2Mixing the composite nano microspheres, adding a certain amount of deionized water, and uniformly stirring under the action of magnetic stirring;
step S42, drying for 2-3h in vacuum environment after washing and filtering to obtain the composite carrier photocatalyst, wherein TiO2-SnO2The mixing mass ratio of the composite nano-microspheres to the composite carrier is 5-8: 100.
In the invention, the aluminum phosphate molecular sieve is prepared 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. In addition, the aluminum phosphate molecular sieve can also be prepared by a precipitation method, a hydrothermal fermentation method and the like.
The visible light absorption wavelength of the composite carrier photocatalyst prepared by the invention is 450-680nm, so that the composite photocatalyst can be used for carrying out photocatalytic degradation on printing and dyeing wastewater under the irradiation of sunlight.
The composite carrier photocatalyst of the present invention will be described in detail below with reference to specific examples.
Example 1
A composite carrier photocatalyst and a preparation method thereof comprise the following steps:
step S1, preparing TiO2-SnO2The active component of the composite nano microsphere comprises the following steps:
step S11, mixing a certain amount of tetrabutyl orthotitanate and absolute ethyl alcohol to obtain a mixed solution A;
step S12, adding SnCl2Adding the solution into the mixed solution A, and obtaining a mixed solution B under the condition of ultrasonic stirring;
step S13, 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 S14, calcining the dried material, heating to 200 ℃ at a heating rate of 10-12 ℃/min, and keeping the temperature for 30-60 min; heating to 650 ℃ at a heating rate of 8-10 ℃/min, and keeping the temperature for 30-60min to obtain TiO2-SnO2Composite nano-microsphere active ingredient, wherein TiO2/SnO2The mass ratio of (A) to (B) is 10: 1;
step S2, preparing an aluminum phosphate molecular sieve;
in the invention, the aluminum phosphate molecular sieve is prepared by adopting an ionic thermal method, which comprises the following steps:
step S21, uniformly mixing the ionic liquid, phosphoric acid, pseudo-boehmite, triethylamine template agent and hydrofluoric acid; wherein the ionic liquid is chlorinated 1-butyl-3-methylimidazole, and the mixing mass ratio of the ionic liquid to the methylimidazole is 10:2:1:5: 0.6;
step S22, crystallizing the mixture at 350 ℃ for 30-50 min;
step S23, carrying out centrifugal separation, washing and drying to obtain an aluminum phosphate molecular sieve; wherein the drying adopts vacuum drying, and the temperature is 70-80 ℃.
Step S3, preparing the aluminum phosphate molecular sieve and the silver phosphate composite carrier, comprising the following steps:
step S31, adding a certain amount of deionized water into the aluminum phosphate molecular sieve, uniformly stirring, gradually dropwise adding a silver nitrate solution into the aluminum phosphate molecular sieve, and then adding a certain amount of Na under the action of magnetic stirring2HPO4A solution;
step S32, drying for 2-3h in a vacuum environment after washing and filtering;
step S33, roasting for 2-3h at 650 ℃ to obtain an aluminum phosphate molecular sieve and a silver phosphate composite carrier, wherein the weight of the silver phosphate accounts for 30% of that of the aluminum phosphate molecular sieve; the porosity of the composite carrier is 86%, and the pore diameter is 6-10 nm;
step S4, preparing a composite carrier photocatalyst, comprising the steps of:
step S41, taking the composite carrier and TiO2-SnO2Mixing the composite nano microspheres, adding a certain amount of deionized water, and uniformly stirring under the action of magnetic stirring;
step S42, drying for 2-3h in vacuum environment after washing and filtering to obtain the composite carrier photocatalyst, wherein TiO2-SnO2The mixing mass ratio of the composite nano microspheres to the composite carrier is 5: 100.
Example 2
A composite carrier photocatalyst and a preparation method thereof comprise the following steps:
step S1, preparing TiO2-SnO2The active component of the composite nano microsphere comprises the following steps:
step S11, mixing a certain amount of tetrabutyl orthotitanate and absolute ethyl alcohol to obtain a mixed solution A;
step S12, adding SnCl2Adding the solution into the mixed solution A, and obtaining a mixed solution B under the condition of ultrasonic stirring;
step S13, 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 70 ℃;
step S14, calcining the dried material, heating to 230 ℃ at a heating rate of 10-12 ℃/min, and keeping the temperature for 30-60 min; heating to 700 deg.C at a heating rate of 8-10 deg.C/min, and maintaining for 30-60min to obtain TiO2-SnO2Composite nano-microsphere active ingredient, wherein TiO2/SnO2The mass ratio of (A) to (B) is 15: 1;
step S2, preparing an aluminum phosphate molecular sieve;
in the invention, the aluminum phosphate molecular sieve is prepared by adopting an ionic thermal method, which comprises the following steps:
step S21, uniformly mixing the ionic liquid, phosphoric acid, pseudo-boehmite, triethylamine template agent and hydrofluoric acid; wherein the ionic liquid is chlorinated 1-butyl-3-methylimidazole, and the mixing mass ratio of the ionic liquid to the methylimidazole is 12:4:1:6: 0.5;
step S22, crystallizing the mixture at 400 ℃ for 30-50 min;
step S23, carrying out centrifugal separation, washing and drying to obtain an aluminum phosphate molecular sieve; wherein the drying adopts vacuum drying, and the temperature is 80 ℃.
Step S3, preparing the aluminum phosphate molecular sieve and the silver phosphate composite carrier, comprising the following steps:
step S31, adding a certain amount of deionized water into the aluminum phosphate molecular sieve, uniformly stirring, gradually dropwise adding a silver nitrate solution into the aluminum phosphate molecular sieve, and then adding a certain amount of Na under the action of magnetic stirring2HPO4A solution;
step S32, drying for 2-3h in a vacuum environment after washing and filtering;
step S33, roasting for 2-3h at 680 ℃ to obtain an aluminum phosphate molecular sieve and a silver phosphate composite carrier, wherein the weight of the silver phosphate accounts for 40% of that of the aluminum phosphate molecular sieve; the porosity of the composite carrier is 80%, and the pore diameter is 6-10 nm;
step S4, preparing a composite carrier photocatalyst, comprising the steps of:
step S41, taking the composite carrier and TiO2-SnO2Mixing the composite nano microspheres, adding a certain amount of deionized water, and uniformly stirring under the action of magnetic stirring;
step S42, drying for 2-3h in vacuum environment after washing and filtering to obtain the composite carrier photocatalyst, wherein TiO2-SnO2The mixing mass ratio of the composite nano-microspheres to the composite carrier is 8: 100.
Example 3
A composite carrier photocatalyst and a preparation method thereof comprise the following steps:
step S1, preparing TiO2-SnO2The active component of the composite nano microsphere comprises the following steps:
step S11, mixing a certain amount of tetrabutyl orthotitanate and absolute ethyl alcohol to obtain a mixed solution A;
step S12, adding SnCl2Adding the solution into the mixed solution A, and obtaining a mixed solution B under the condition of ultrasonic stirring;
step S13, 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 65 ℃;
step S14, calcining the dried material, heating to 220 ℃ at a heating rate of 10-12 ℃/min, and keeping the temperature for 30-60 min; heating to 680 deg.C at a heating rate of 8-10 deg.C/min, and maintaining for 30-60min to obtain TiO2-SnO2Composite nano-microsphere active ingredient, wherein TiO2/SnO2The mass ratio of (A) to (B) is 12: 1;
step S2, preparing an aluminum phosphate molecular sieve;
in the invention, the aluminum phosphate molecular sieve is prepared by adopting an ionic thermal method, which comprises the following steps:
step S21, uniformly mixing the ionic liquid, phosphoric acid, pseudo-boehmite, triethylamine template agent and hydrofluoric acid; wherein the ionic liquid is chlorinated 1-butyl-3-methylimidazole, and the mixing mass ratio of the ionic liquid to the methylimidazole is 11:2:1:6: 0.8;
step S22, crystallizing the mixture at 375 ℃ for 30-50 min;
step S23, carrying out centrifugal separation, washing and drying to obtain an aluminum phosphate molecular sieve; wherein the drying adopts vacuum drying, and the temperature is 75 ℃.
Step S3, preparing the aluminum phosphate molecular sieve and the silver phosphate composite carrier, comprising the following steps:
step S31, adding a certain amount of deionized water into the aluminum phosphate molecular sieve, uniformly stirring, gradually dropwise adding a silver nitrate solution into the aluminum phosphate molecular sieve, and then adding a certain amount of Na under the action of magnetic stirring2HPO4A solution;
step S32, drying for 2-3h in a vacuum environment after washing and filtering;
step S33, roasting for 2-3h at 670 ℃ to obtain an aluminum phosphate molecular sieve and a silver phosphate composite carrier, wherein the weight of the silver phosphate accounts for 50% of that of the aluminum phosphate molecular sieve; the porosity of the composite carrier is 84%, and the pore diameter is 6-10 nm;
step S4, preparing a composite carrier photocatalyst, comprising the steps of:
step S41, taking the composite carrier and TiO2-SnO2Mixing the composite nano microspheres, adding a certain amount of deionized water, and uniformly stirring under the action of magnetic stirring;
step S42, drying for 2-3h in vacuum environment after washing and filtering to obtain the composite carrier photocatalyst, wherein TiO2-SnO2The mixing mass ratio of the composite nano microspheres to the composite carrier is 6: 100.
Referring to fig. 1 to 5, fig. 1 is a SEM image of the aluminum phosphate molecular sieve of example 1; FIG. 2 is an SEM image of the aluminum phosphate molecular sieve and silver phosphate composite support of example 1; FIG. 3 is a TEM image of a transmission electron microscope of the aluminum phosphate molecular sieve and silver phosphate composite carrier of example 1; FIG. 4 is an SEM photograph of the composite supported photocatalyst in example 1; FIG. 5 is a TEM image of the composite supported photocatalyst in example 1.
The composite supported catalysts of examples 1 to 3 were used for printing and dyeing wastewater treatment and tested for performance. The test method is as follows:
the composite supported catalysts of examples 1-3 were respectively added to different types of printing and dyeing wastewater (containing methylene blue, rhodamine B and methyl orange printing and dyeing wastewater), stirred for 90-120min under the irradiation of visible light, and then the purified water quality index was detected, wherein the amount of the catalyst was 3% of the wastewater amount. The water quality indexes before and after purification are shown in tables 1-3:
table 1: methyl blue printing wastewater purification effect data
Table 2: rhodamine B printing and dyeing wastewater purification effect data
Table 3: methyl orange printing and dyeing wastewater purification effect data
The composite carrier photocatalyst provided by the invention can be used for carrying out photocatalytic degradation treatment on various printing and dyeing wastewater under the irradiation of visible light, and has a good purification effect.
Compared with the prior art, the composite carrier photocatalyst provided by the invention has the beneficial effects that:
the composite carrier photocatalyst provided by the invention takes an aluminum phosphate molecular sieve and a silver phosphate composite as carriers and TiO2-SnO2The composite nano-microspheres are active ingredients, wherein the composite carrier is a large-aperture molecular sieve structure and has a good adsorption effect; the composite carrier has photocatalysis at the same timeThe effect, in combination with the active ingredient, makes the catalytic properties of the composite carrier complementary to those of the active ingredient, and thus enhances the photocatalytic effect. The composite carrier photocatalyst provided by the invention has a wider visible light absorption wavelength of 450-680nm, so that the composite carrier photocatalyst can be simultaneously used for photocatalytic degradation of various printing and dyeing wastewater such as methylene blue, rhodamine B, methyl orange and the like.
II, the composite carrier photocatalyst, TiO, provided by the invention2-SnO2The active components of the composite nano microsphere simultaneously contain anatase crystal phase and rutile crystal phase, and the calcination process can control the generation of the rutile crystal phase and ensure that the catalytic performance of the formed rutile crystal phase or the formed rutile crystal phase is higher.
The composite carrier photocatalyst provided by the invention adopts an ionic thermal method to synthesize the aluminum phosphate molecular sieve, can avoid the generation of hydroxides and some amorphous substances, and can improve the catalytic efficiency of the catalyst.
The composite carrier photocatalyst provided by the invention has high treatment efficiency on various printing and dyeing wastewater under the irradiation of visible light, the removal efficiency of COD is 97%, the removal efficiency of methylene blue is 99%, the removal efficiency of rhodamine B is 98%, the removal efficiency of methyl orange is 98%, and the removal efficiency of toluene is 99%.
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 (6)
1. The composite carrier photocatalyst is characterized in that an aluminum phosphate molecular sieve and a silver phosphate composite are used as carriers, and TiO is used as a carrier2-SnO2The preparation method of the composite nano microsphere which is used as an active ingredient comprises the following steps:
step S1, preparing TiO2-SnO2The active component of the composite nano microsphere comprises the following steps:
step S11, mixing a certain amount of tetrabutyl orthotitanate and absolute ethyl alcohol to obtain a mixed solution A;
step S12, adding SnCl2Adding the solution into the mixed solution A, and obtaining a mixed solution B under the condition of ultrasonic stirring;
step S13, 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 60-70 ℃;
step S14, calcining the dried material, raising the temperature to 200 ℃ and 230 ℃ at the temperature raising speed of 10-12 ℃/min, and preserving the temperature for 30-60 min; then heating to 650-700 ℃ at the heating rate of 8-10 ℃/min, and preserving the heat for 30-60min to obtain TiO2-SnO2Composite nano-microsphere active ingredient, wherein TiO2/SnO2The mass ratio of (A) to (B) is 10-15: 1;
step S2, preparing an aluminum phosphate molecular sieve;
step S3, preparing the aluminum phosphate molecular sieve and the silver phosphate composite carrier, comprising the following steps:
step S31, adding a certain amount of deionized water into the aluminum phosphate molecular sieve, uniformly stirring, gradually dropwise adding a silver nitrate solution into the aluminum phosphate molecular sieve, and then adding a certain amount of Na under the action of magnetic stirring2HPO4A solution;
step S32, drying for 2-3h in a vacuum environment after washing and filtering;
step S33, roasting for 2-3h at 650-680 ℃ to obtain an aluminum phosphate molecular sieve and a silver phosphate composite carrier, wherein the weight of the silver phosphate accounts for 30-50% of that of the aluminum phosphate molecular sieve;
step S4, preparing a composite carrier photocatalyst, comprising the steps of:
step S41, taking the composite carrier and TiO2-SnO2Mixing the composite nano microspheres, adding a certain amount of deionized water, and uniformly stirring under the action of magnetic stirring;
step S42, drying for 2-3h in vacuum environment after washing and filtering to obtain the composite carrier photocatalyst, wherein TiO2-SnO2The mixing mass ratio of the composite nano-microspheres to the composite carrier is 5-8: 100.
2. The composite supported photocatalyst according to claim 1, wherein the porosity of the composite support is 80 to 86% and the pore diameter is 6 to 10 nm.
3. The composite carrier photocatalyst as claimed in claim 1, wherein the aluminum phosphate molecular sieve is prepared by ionothermal method.
4. The composite supported photocatalyst of claim 3, wherein the preparation method of the aluminum phosphate molecular sieve comprises the following steps:
uniformly mixing the ionic liquid, phosphoric acid, pseudo-boehmite, triethylamine template agent and hydrofluoric acid;
crystallizing the mixture at the temperature of 350-400 ℃ for 30-50 min;
and centrifugally separating, washing and drying to obtain the aluminum phosphate molecular sieve.
5. The composite supported photocatalyst as claimed in any one of claims 1 to 4, wherein the composite supported photocatalyst has a visible light absorption wavelength of 450-680 nm.
6. Use of a composite carrier photocatalyst as claimed in any one of claims 1 to 5 in the treatment of printing and dyeing wastewater.
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