CN108404971B - Composite photocatalyst for treating phenol-containing wastewater and preparation method and application thereof - Google Patents
Composite photocatalyst for treating phenol-containing wastewater and preparation method and application thereof Download PDFInfo
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- CN108404971B CN108404971B CN201810297664.7A CN201810297664A CN108404971B CN 108404971 B CN108404971 B CN 108404971B CN 201810297664 A CN201810297664 A CN 201810297664A CN 108404971 B CN108404971 B CN 108404971B
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims abstract description 188
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 128
- 239000002131 composite material Substances 0.000 title claims abstract description 121
- 239000002351 wastewater Substances 0.000 title claims abstract description 81
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000002808 molecular sieve Substances 0.000 claims abstract description 132
- 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 127
- AOWKSNWVBZGMTJ-UHFFFAOYSA-N calcium titanate Chemical compound [Ca+2].[O-][Ti]([O-])=O AOWKSNWVBZGMTJ-UHFFFAOYSA-N 0.000 claims abstract description 105
- 238000001035 drying Methods 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 23
- 230000015556 catabolic process Effects 0.000 claims abstract description 17
- 238000006731 degradation reaction Methods 0.000 claims abstract description 17
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims abstract description 17
- 238000005470 impregnation Methods 0.000 claims abstract description 11
- 229910052724 xenon Inorganic materials 0.000 claims abstract description 9
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000005286 illumination Methods 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 62
- 238000003756 stirring Methods 0.000 claims description 27
- 239000007864 aqueous solution Substances 0.000 claims description 24
- 238000010521 absorption reaction Methods 0.000 claims description 23
- 229920006395 saturated elastomer Polymers 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 238000001354 calcination Methods 0.000 claims description 15
- 239000011148 porous material Substances 0.000 claims description 15
- 238000011068 loading method Methods 0.000 claims description 13
- 238000002791 soaking Methods 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 9
- 238000004364 calculation method Methods 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 4
- 239000011575 calcium Substances 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims 2
- 230000000694 effects Effects 0.000 abstract description 9
- 239000000126 substance Substances 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 5
- 230000001699 photocatalysis Effects 0.000 abstract description 5
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- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 238000003837 high-temperature calcination Methods 0.000 abstract description 2
- 230000000704 physical effect Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000011259 mixed solution Substances 0.000 description 17
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- 238000002474 experimental method Methods 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 9
- RLFWWDJHLFCNIJ-UHFFFAOYSA-N 4-aminoantipyrine Chemical compound CN1C(C)=C(N)C(=O)N1C1=CC=CC=C1 RLFWWDJHLFCNIJ-UHFFFAOYSA-N 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 8
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 238000003760 magnetic stirring Methods 0.000 description 7
- 238000011161 development Methods 0.000 description 6
- 238000001027 hydrothermal synthesis Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- 229910052719 titanium Inorganic materials 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 5
- 230000009471 action Effects 0.000 description 5
- 238000013329 compounding Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
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- 239000003344 environmental pollutant Substances 0.000 description 4
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- 231100000719 pollutant Toxicity 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000001509 sodium citrate Substances 0.000 description 4
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-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
- 238000005516 engineering process Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
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- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
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- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
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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
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/405—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7049—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
- B01J29/7057—Zeolite Beta
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- 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
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- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
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- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
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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
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- C02F2305/10—Photocatalysts
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Abstract
A composite photocatalyst for treating phenol-containing wastewater and a preparation method and application thereof belong to the field of photocatalytic materials and environmental protection. The composite photocatalyst for treating the phenol-containing wastewater is a photocatalyst which takes calcium titanate as a main photocatalytic degradation substance and takes a molecular sieve as a carrier. Wherein, the calcium titanate is compounded with the molecular sieve by an isometric impregnation method, and then the composite photocatalyst is obtained by drying and high-temperature calcination. The degradation rate of the composite photocatalyst for treating the phenol-containing wastewater after one hour of illumination on phenol can reach 24.6-94.8% by adopting a high-pressure xenon lamp, and is 22.3% higher than that of pure calcium titanate on phenol after one hour of illumination. Compared with single pure calcium titanate, the obtained composite photocatalyst has improved physical properties and photocatalytic degradation effect. The preparation method is simple, raw materials are easy to obtain, the preparation process is easy to operate, the conditions are mild and easy to control, and the product catalysis efficiency is high.
Description
Technical Field
The invention relates to a composite photocatalyst for treating phenol-containing wastewater and a preparation method and application thereof, belonging to the fields of photocatalytic materials and environmental protection.
Background
In recent years, along with the continuous improvement of the industrialization level and the rapid development of urbanization in China, the environmental protection problem in China is increasingly severe. Taking water pollution as an example, various chemical enterprises such as coal washing plants and coking plants, and traditional enterprises such as nonferrous metal smelting plants, paper mills, textile plants, etc., generate sewage containing a large amount of organic pollutants such as phenols, etc. These pollutants, if not effectively disposed of and discharged directly into the environment, are necessarily life threatening. How to achieve effective, clean treatment of such contaminants has become an important issue for sustainable development.
Phenol, also known as carbolic acid, is an important organic chemical raw material as the simplest phenolic compound, and can be used for synthetic resins, rubbers, medicines, and the like. But the pesticide has violent toxicity and strong irritation, has great harm to human bodies and is difficult to degrade under natural conditions. The traditional methods mainly adopt physical adsorption, chemical reaction, microbial degradation and the like to treat the substances, and have the problems of secondary pollution, unsatisfactory degradation effect and the like. Since the advent of the photocatalytic technology in the 70's of the 20 th century, people have been expanding their application range, and now the photocatalytic technology has become an important research direction for treating pollutants.
The photocatalytic material is a novel catalytic material, is represented by perovskite, titanium dioxide and the like, has the advantages of high efficiency, stability, no pollution of degradation products and the like, has obvious degradation effect on common organic pollutants, heavy metal ions, mould and the like, and is widely applied to the field of environmental protection. Calcium titanate, a representative perovskite, has been widely studied because of its simple fabrication process, low cost, and good catalytic properties. However, the calcium titanate powder particles are fine and easy to agglomerate, the specific surface area is small, and suspension is easy to form in water and difficult to recover, so that the wide popularization and application of the calcium titanate powder particles in actual production are limited.
The molecular sieve is a kind of molecular sieve with skeleton structureThe microporous crystal material has two obvious characteristics of large specific surface area and high-efficiency adsorption. The molecular sieve crystal has a honeycomb structure, the volume of holes accounts for more than 50% of the volume of the molecular sieve crystal, and the high hole ratio ensures that the molecular sieve crystal has a large specific surface area which can be usually hundreds of meters2(ii) in terms of/g. The diameter of the molecular sieve cavity is generally within
Between, the aperture is about
Compared with common molecules, the large pore diameter ensures that the adsorbent has high-efficiency adsorption. In addition, the molecular sieve has the advantages of selective adsorption, high surface polarity, stable framework structure and the like, and due to the structural properties, the molecular sieve not only becomes an excellent adsorbent, but also becomes an effective catalyst and a catalyst carrier.
The molecular sieve is compounded with the calcium titanate, so that the problems of small specific surface area, easy agglomeration, difficult recycling and the like of the calcium titanate are solved, meanwhile, the adsorption effect of the molecular sieve can enrich the pollutant phenol around the photocatalyst, the catalytic degradation effect of the calcium titanate is promoted, and the catalytic degradation effect of the catalyst can be effectively improved by compounding the molecular sieve and the calcium titanate. The invention takes phenol as a catalytic degradation experimental object, and the result shows that the effect is good. Thereby providing reference for the research and development of the novel catalyst of the same type.
Disclosure of Invention
In order to solve the defects of the prior art, the invention provides a composite photocatalyst for treating phenol-containing wastewater and a preparation method thereof, and the composite photocatalyst takes calcium titanate as a main photocatalytic degradation substance and a molecular sieve as a carrier. Wherein, the calcium titanate is compounded with the molecular sieve by an isometric impregnation method, and then the composite photocatalyst is obtained by drying and high-temperature calcination. Compared with single pure calcium titanate, the obtained composite photocatalyst has improved physical properties and photocatalytic degradation effect. The preparation method is simple, raw materials are easy to obtain, the preparation process is easy to operate, the conditions are mild and easy to control, and the product catalysis efficiency is high.
In order to achieve the above object, the technical scheme adopted by the invention is as follows:
the invention relates to a composite photocatalyst for treating phenol-containing wastewater, which is a composite photocatalyst with a molecular sieve as a carrier and calcium titanate loaded by an isometric impregnation method.
In the composite photocatalyst for treating phenol-containing wastewater, the loading rate of calcium titanate is 1-15%;
the composite photocatalyst for treating phenol-containing wastewater is a white powdery solid, and the specific surface area of the composite photocatalyst is 150-470 m2A pore volume of 0.15 to 0.9 cm/g3Per g, average pore radius
The molecular sieve is a ZSM-5 molecular sieve or a beta molecular sieve.
A preparation method of a composite photocatalyst for treating phenol-containing wastewater comprises the following steps:
step 1, according to the mass M of the composite photocatalyst for treating the phenol-containing wastewater to be prepared, and according to the loading rate of calcium titanate of X%, the mass of the calcium titanate is X% multiplied by M, and the mass M of the molecular sieve isIs divided intoIs (1-X%). times.M;
adding (1.1 alpha-1.3 alpha) x m into calcium titanateIs divided intoPreparing a calcium titanate aqueous solution with the mass concentration of C by using mL of water;
step 2, adding the prepared calcium titanate aqueous solution with the concentration of C into a molecular sieve with the mass of [ (1-X%). times.M ] g, continuously stirring, stopping stirring after the system is uniformly mixed, and statically soaking for 8-12 hours at room temperature to obtain the molecular sieve soaked with the calcium titanate aqueous solution;
and 3, drying the molecular sieve impregnated with the calcium titanate aqueous solution at 110-120 ℃ for 2-4 hours, calcining at 550-850 ℃, and preserving heat for 4-6 hours to obtain the molecular sieve-loaded calcium titanate composite photocatalyst.
In the step 1, the mass concentration C is the mass concentration of the prepared calcium titanate aqueous solution, and the unit is g/mL;
the calculation formula is as follows:
m is the mass of the composite photocatalyst for treating the phenol-containing wastewater, X% is the load rate of calcium titanate, and alpha is the saturated water absorption of the carrier molecular sieve;
in the step 1, the calculation method of the saturated water absorption rate alpha of the carrier molecular sieve comprises the following steps:
α＝(Vwater (W)-V)/m (2)
Alpha is the saturated water absorption of the carrier molecular sieve, and the unit is mL/g;
Vwater (W)Unit mL is the volume of water added;
m is the measured mass of the carrier molecular sieve, unit g;
v is the volume of excess water poured in mL;
the method for measuring the saturated water absorption of the carrier molecular sieve comprises the following steps:
(1) drying the carrier molecular sieve measured by m g at 100-120 deg.C for 30min, and cooling to room temperature to obtain dried molecular sieve;
(2) adding V into the dried molecular sieveWater (W)Soaking the carrier molecular sieve in mL deionized water for 8-12 h at room temperature, pouring out excessive water, measuring the volume of the poured excessive water to be VmL, and obtaining the saturated water absorption alpha of the carrier molecular sieve by a calculation method of the saturated water absorption alpha of the carrier molecular sieve.
In the method for measuring the saturated water absorption of the carrier molecular sieve, drying is carried out in an oven.
In the method for measuring the saturated water absorption of the carrier molecular sieve, furnace cooling is adopted for cooling.
In the step 2, the system is uniformly mixed, and the preferable stirring time is 5-10 min.
In the step 3, the drying equipment is an oven.
In the step 3, the equipment adopted for calcination is a muffle furnace, and the calcination temperature rise rate is 5-10 ℃/min.
The application of the composite photocatalyst for treating the phenol-containing wastewater comprises the following steps:
putting the composite photocatalyst with the molecular sieve loaded with calcium titanate into phenol-containing wastewater, and performing photocatalytic degradation by using a high-pressure xenon lamp as a reaction light source and a wavelength range of 320-780 nm;
wherein, the molecular sieve loaded calcium titanate composite photocatalyst comprises the following components in percentage by mass: phenol (0.3-0.5) g in the wastewater: 0.005 g.
In the application of the composite photocatalyst for treating the phenol-containing wastewater, the composite photocatalyst for treating the phenol-containing wastewater is matched with a magnetic stirring device for use in a reaction process, so that the composite photocatalyst for treating the phenol-containing wastewater is ensured to be fully reacted with a phenol solution.
The application of the composite photocatalyst for treating the phenol-containing wastewater adopts a high-pressure xenon lamp, and the degradation rate of the composite photocatalyst for treating the phenol-containing wastewater after one hour of illumination on phenol can reach 24.6-94.8%, which is higher than the degradation rate of pure calcium titanate on phenol 22.3% under one hour of illumination.
Compared with the prior art, the composite photocatalyst for treating the phenol-containing wastewater and the preparation method and the application thereof have the beneficial effects that:
1. the molecular sieve is compounded with the calcium titanate, and by means of the characteristics of porous structure and large specific surface area of the molecular sieve, the contact area of the calcium titanate and the reactant phenol is increased, and the catalytic effect of the catalyst is improved. Meanwhile, the problems that the calcium titanate powder is easy to agglomerate in water and is difficult to recycle are solved.
2. The molecular sieve has adsorption effect, so that the pollutant phenol can be enriched around the catalyst, and the reaction step of 'diffusion' of phenol to the composite catalyst in the reaction process is greatly reduced, thereby promoting the catalytic degradation of calcium titanate.
Drawings
FIG. 1 is a flow chart of the preparation of the composite photocatalyst for treating phenol-containing wastewater according to the present invention.
FIG. 2 is an XRD diagram of a composite photocatalyst for treating phenol-containing wastewater, which is prepared by using a ZSM-5 molecular sieve as a carrier.
FIG. 3 is an SEM image of a composite photocatalyst for treating phenol-containing wastewater, which is prepared by using a ZSM-5 molecular sieve as a carrier.
FIG. 4 is a BET plot of a composite photocatalyst prepared by using a ZSM-5 molecular sieve as a carrier and used for treating phenol-containing wastewater.
The meaning of the reference symbols in the figures: FIG. 2: a-calcium titanate, b-ZSM-5 molecular sieve and c-composite photocatalyst.
Detailed Description
The present invention will be further described and illustrated with reference to specific embodiments.
Except for special instructions, the reagents used in the examples of the present invention are all commercially available products and analytically pure.
The ZSM-5 molecular sieve and the beta molecular sieve used in the embodiment of the invention are both from Tianjin Minghanization catalyst Co.
In the following examples, a flow chart of the preparation of the composite photocatalyst for treating wastewater containing phenol is shown in FIG. 1.
In the following examples, the calcium titanate used was synthesized by hydrothermal method, i.e., CaTiO synthesized by hydrothermal method3The powder comprises the following steps:
taking tetrabutyl titanate as a titanium source, calcium nitrate as a calcium source, ethylene glycol monomethyl ether as a peptizing agent, deionized water as a solvent, potassium hydroxide as a mineralizer and sodium citrate as an auxiliary agent, and synthesizing CaTiO by a hydrothermal method3Powder, wherein, in terms of mole ratio, n-tetrabutyl titanate: 1:1, calcium nitrate: potassium hydroxide: 2.83g sodium citrate: 2.25 g: 0.175 g. The method specifically comprises the following steps:
(1) mixing ethylene glycol methyl ether and tetrabutyl titanate according to a ratio to obtain a mixed solution I, wherein the volume ratio of tetrabutyl titanate: ethylene glycol methyl ether 2.6-2.8 mL: 2.6-2.8 mL;
mixing deionized water and ethylene glycol monomethyl ether according to a ratio to obtain a mixed solution II, wherein the deionized water comprises the following components in percentage by volume: ethylene glycol methyl ether 25-27 mL: 2.6-2.8 mL;
(2) slowly dropping the prepared mixed solution I into the prepared mixed solution II, continuously stirring the mixed solution I simultaneously with continuous stirring, and continuously stirring the mixed solution I to obtain white flocculent titanium hydroxyl precipitation mixed solution after the mixed solution I and the mixed solution II fully react, wherein the amount of the mixed solution I is the total mixed solution I prepared in the step (1), and the amount of the mixed solution II is the total mixed solution II prepared in the step (1);
the dropping speed of the slow dropping is 4-6 mL/min.
The stirring speed of the stirring is 600-800 r/min.
The stirring mode is preferably magnetic stirring by a magnetic stirrer.
And after the mixed solution I is dropwise added, continuously stirring for 5-10 min.
(3) Centrifuging and separating the white flocculent titanium hydroxyl precipitate mixed solution by using a high-speed centrifuge, and repeatedly washing for 3-5 times by using deionized water to obtain titanium hydroxyl precipitate;
the purpose of the washing is to remove free impurities attached to the titanium hydroxyl precipitate.
The centrifugal rate is 8000-10000 r/min.
(4) Dissolving titanium hydroxyl precipitate in 70-80 mL of deionized water, uniformly stirring, adding calcium nitrate, stirring to obtain a precursor, adding potassium hydroxide after 1-3 min, adding sodium citrate after 1-3 min, continuously stirring and reacting for 10-15 min to obtain a reaction mixed solution, wherein the mass ratio of calcium nitrate: potassium hydroxide: 2.83g sodium citrate: 2.25 g: 0.175 g.
The stirring is magnetic stirring, and the stirring speed is 600-800 r/min.
(5) Adding the reaction mixed solution into a 100mL hydrothermal reaction kettle with a polytetrafluoroethylene lining for hydrothermal reaction, placing the hydrothermal reaction kettle in a muffle furnace, heating to 195-205 ℃, and preserving heat for 11-13 hours;
(6) and after the reaction is finished, naturally cooling, centrifugally washing the product, drying the product in an oven at the temperature of 70-80 ℃ for 2-4 hours, and grinding the product after drying to obtain the calcium titanate photocatalyst. Wherein, the particle size of the calcium titanate photocatalyst is below 75 μm (a sample can pass through a 200-mesh sieve).
The centrifugal washing is specifically that the washing is sequentially carried out for 3-5 times by using deionized water, absolute ethyl alcohol and 5% nitric acid solution respectively.
Example 1
A composite photocatalyst for treating phenol-containing wastewater is a composite photocatalyst which takes a molecular sieve as a carrier and is loaded with calcium titanate by an isometric impregnation method.
Wherein, calcium titanate is a main action substance for photocatalytic degradation, and the composite photocatalyst is obtained by drying and calcining the calcium titanate and a molecular sieve after the calcium titanate and the molecular sieve are compounded.
In the composite photocatalyst for treating phenol-containing wastewater, the loading rate of calcium titanate is 5%;
the composite photocatalyst for treating the phenol-containing wastewater is a white powdery solid, and the specific surface area of the composite photocatalyst is 220.259m2Per g, pore volume 0.254636cm3Per g, average pore radius
The molecular sieve is a ZSM-5 molecular sieve.
A preparation method of a composite photocatalyst for treating phenol-containing wastewater comprises the following steps:
step 1:
(1) the saturated water absorption of the carrier molecular sieve is measured by the specific measurement method:
drying 5g of ZSM-5 molecular sieve in an oven at 105 ℃ for 30min, cooling to room temperature, and placing the obtained dried molecular sieve in a 50mL beaker;
adding 20mL of deionized water into the dried molecular sieve, soaking for 12 hours at room temperature, pouring out excessive water, and measuring the volume to be 16.5mL, wherein the saturated water absorption of the carrier molecular sieve is as follows: α ═ 5(mL/g) (20-16.5), and α was calculated to be 0.70.
(2) According to the condition that the mass M of the composite photocatalyst for treating the phenol-containing wastewater is 2.5g and the loading capacity of the calcium titanate is 5%, the mass percentage of the molecular sieve occupying the composite photocatalyst for treating the phenol-containing wastewater is 95%, and the mass of the molecular sieve and the mass of the composite photocatalyst for treating the phenol-containing wastewater are 0.125g and 2.375g respectively.
(3) Adding 2.0mL of water to 1.2 × 0.70 × 2.375 to calcium titanate to prepare an aqueous calcium titanate solution;
step 2:
weighing 2.375g of ZSM-5 molecular sieve in a beaker, adding the prepared calcium titanate solution into the beaker, continuously stirring for 5min, stopping stirring after the system is uniformly mixed, and standing and soaking for 12 hours at room temperature to obtain the molecular sieve soaked with the calcium titanate aqueous solution;
and 3, placing the molecular sieve impregnated with the calcium titanate aqueous solution in an oven, drying at 120 ℃ for 3 hours, finally calcining in a muffle furnace, heating to 750 ℃ at the heating rate of 8 ℃/min, and preserving heat for 6 hours to obtain the composite photocatalyst.
Specific surface area analysis: the specific surface area of the prepared composite photocatalyst is tested by adopting nitrogen adsorption-desorption analysis, and the result shows that the specific surface area is 220.259m2Per g, greater than 35.463m of the specific surface area of the pure calcium titanate2/g。
The application of the composite photocatalyst for treating the phenol-containing wastewater is as follows, namely, a photocatalytic degradation experiment:
mixing 50mL of phenol solution with the concentration of 100mg/L with 0.3g of the prepared composite photocatalyst, taking a high-pressure xenon lamp as a reaction light source, carrying out a photocatalytic degradation experiment under the action of ultraviolet visible light, and keeping magnetic stirring in the reaction process, wherein the wavelength range is 320-780 nm. The phenol concentration was measured by 4-aminoantipyrine color development. Experiments show that after one hour of reaction, the degradation rate of phenol reaches 74.1 percent, which is far higher than that of phenol degradation rate of pure calcium titanate by 22.3 percent under one hour of illumination.
In this example, the composite photocatalyst for treating phenol-containing wastewater was prepared by using a ZSM-5 molecular sieve as a carrier, and an XRD pattern of the composite photocatalyst for treating phenol-containing wastewater is shown in fig. 2. In the graphs in fig. 2, a is an XRD curve of calcium titanate, b is an XRD curve of ZSM-5 molecular sieve, and c is an XRD curve of the composite photocatalyst, and it can be found by comparing the peak positions and peak shapes of characteristic peaks of respective substances before and after compounding that the spectrum of the composite photocatalyst contains the characteristic peaks of calcium titanate and ZSM-5 molecular sieve, and the peak positions and peak shapes are substantially identical, indicating that the two are successfully compounded into the composite photocatalyst.
An SEM image of the composite photocatalyst for treating the phenol-containing wastewater is shown in figure 3, and the composite photocatalyst particles obtained from figure 3 are micron-sized, are relatively uniform and have no obvious agglomeration phenomenon.
The nitrogen adsorption-desorption test curve of the composite photocatalyst for treating the phenol-containing wastewater is shown in figure 4. The specific surface area of the prepared composite photocatalyst is 220.259m by calculation of the curve2Per g, pore volume 0.254636cm3Per g, average pore radius
While the specific surface area of the pure calcium titanate photocatalyst is only 35.463m2(ii) in terms of/g. The larger specific surface area ensures that it provides more attachment sites for the calcium titanate loading while providing sufficient reactant contact area for the catalytic reaction to proceed.
Example 2
A composite photocatalyst for treating phenol-containing wastewater is a photocatalyst which takes calcium titanate as a main photocatalytic degradation substance and a molecular sieve as a carrier and is loaded with the calcium titanate by an isometric impregnation method. The composite photocatalyst is obtained by compounding calcium titanate and a molecular sieve by an isometric impregnation method, drying and calcining at high temperature.
In the composite photocatalyst for treating phenol-containing wastewater, the loading rate of calcium titanate is 3%;
the composite photocatalyst for treating the phenol-containing wastewater is a white powdery solid, and the specific surface area of the composite photocatalyst is 212.924m2Per g, pore volume 0.179389cm3Per g, average pore radius
Wherein the molecular sieve is a ZSM-5 molecular sieve.
A preparation method of a composite photocatalyst for treating phenol-containing wastewater comprises the following steps:
step 1:
(1) determining the saturated water absorption of the carrier molecular sieve:
drying 5g of ZSM-5 molecular sieve in an oven at 105 ℃ for 30min, cooling to room temperature, and placing the obtained dried molecular sieve in a 50mL beaker;
adding 20mL of deionized water into the dried molecular sieve, soaking for 12 hours at room temperature, pouring out excessive water, and measuring the volume to be 16.5mL, wherein the saturated water absorption of the carrier is as follows: α ═ 5(mL/g) (20-16.5), and α was calculated to be 0.70.
(2) According to the mass M of the composite photocatalyst for treating the phenol-containing wastewater to be prepared being 2.5g and the calcium titanate load being 3%, the mass percentage of the molecular sieve occupying the composite photocatalyst for treating the phenol-containing wastewater is 97%, and the actual required mass of the molecular sieve and the composite photocatalyst for treating the phenol-containing wastewater is 0.075g and 2.425g respectively;
(3) adding 1.2 × 0.70 × 2.425 ═ 2.1mL of water to calcium titanate to prepare an aqueous calcium titanate solution;
step 2:
weighing 2.425g of ZSM-5 molecular sieve in a beaker, adding the prepared calcium titanate aqueous solution into the beaker, continuously stirring for 5min, stopping stirring after the system is uniform, and standing and soaking for 12 hours at room temperature to obtain the molecular sieve soaked with the calcium titanate aqueous solution;
and step 3: and (3) placing the molecular sieve impregnated with the calcium titanate aqueous solution in an oven, drying at 120 ℃ for 4 hours, finally calcining in a muffle furnace, heating to 650 ℃ at the heating rate of 5 ℃/min, and preserving heat for 6 hours to obtain the composite photocatalyst.
Specific surface area analysis: the specific surface area of the prepared composite photocatalyst is tested by adopting nitrogen adsorption-desorption analysis, and the result shows that the specific surface area is 212.924m2Per g, greater than 35.463m of the specific surface area of the pure calcium titanate2/g。
The application of the composite photocatalyst for treating the phenol-containing wastewater is as follows, namely, a photocatalytic degradation experiment:
mixing 50mL of phenol solution with the concentration of 100mg/L with 0.3g of the prepared composite photocatalyst, taking a high-pressure xenon lamp as a reaction light source, carrying out a photocatalytic degradation experiment under the action of ultraviolet visible light, and keeping magnetic stirring in the reaction process, wherein the wavelength range is 320-780 nm. The phenol concentration was measured by 4-aminoantipyrine color development. Experiments show that after one hour of reaction, the degradation rate of phenol reaches 59.0%.
Example 3
A composite photocatalyst for treating phenol-containing wastewater is a photocatalyst which takes calcium titanate as a main photocatalytic degradation substance and a molecular sieve as a carrier and is loaded with the calcium titanate by an isometric impregnation method. The composite photocatalyst is obtained by compounding calcium titanate and a molecular sieve by an isometric impregnation method, drying and calcining at high temperature.
In the composite photocatalyst for treating phenol-containing wastewater, the loading rate of calcium titanate is 3%;
the composite photocatalyst for treating the phenol-containing wastewater is a white powdery solid, and the specific surface area of the composite photocatalyst is 340.669m2Per g, pore volume 0.664242cm3Per g, average pore radius
Wherein, the molecular sieve is beta molecular sieve.
A preparation method of a composite photocatalyst for treating phenol-containing wastewater comprises the following steps:
step 1:
(1) determining the saturated water absorption of the carrier molecular sieve:
drying 5g of beta molecular sieve in an oven at 105 ℃ for 30min, cooling to room temperature, and placing the obtained dried molecular sieve in a 50mL beaker;
adding 20mL of deionized water into the dried molecular sieve, soaking for 12 hours at room temperature, pouring out excessive water, and measuring the volume to be 4.9mL, wherein the saturated water absorption of the carrier is as follows: α ═ 5(mL/g) (20-4.9), and α was calculated to be 3.02.
(2) According to the mass M of the composite photocatalyst for treating the phenol-containing wastewater to be prepared being 2.5g and the calcium titanate load being 3%, the mass percentage of the molecular sieve occupying the composite photocatalyst for treating the phenol-containing wastewater is 97%, and the actual required mass of the molecular sieve and the composite photocatalyst for treating the phenol-containing wastewater is 0.075g and 2.425g respectively;
(3) to calcium titanate, 1.2 × 3.02 × 2.425 ═ 8.8mL of water was added to prepare a calcium titanate solution.
Step 2:
weighing 2.425g of beta molecular sieve in a beaker, adding the prepared calcium titanate aqueous solution into the beaker, continuously stirring for 8min, stopping stirring after the system is stable, and standing and soaking for 12 hours at room temperature to obtain the molecular sieve soaked with the calcium titanate aqueous solution;
and step 3: and (3) placing the molecular sieve impregnated with the calcium titanate aqueous solution in an oven, drying at 120 ℃ for 3 hours, finally calcining in a muffle furnace, heating to 850 ℃ at the heating rate of 10 ℃/min, and preserving heat for 6 hours to obtain the composite photocatalyst.
Specific surface area analysis: the specific surface area of the prepared composite photocatalyst is tested by adopting nitrogen adsorption-desorption analysis, and the result shows that the specific surface area is 340.669m2Per g, greater than 35.463m of the specific surface area of the pure calcium titanate2/g。
The application of the composite photocatalyst for treating the phenol-containing wastewater is as follows, namely, a photocatalytic degradation experiment:
mixing 50mL of phenol solution with the concentration of 100mg/L with 0.3g of the prepared composite photocatalyst, taking a high-pressure xenon lamp as a reaction light source, carrying out a photocatalytic degradation experiment under the action of ultraviolet visible light, and keeping magnetic stirring in the reaction process, wherein the wavelength range is 320-780 nm. The phenol concentration was measured by 4-aminoantipyrine color development. Experiments show that after one hour of reaction, the degradation rate of phenol reaches 94.8%.
Example 4
A composite photocatalyst for treating phenol-containing wastewater is a photocatalyst which takes calcium titanate as a main photocatalytic degradation substance and a molecular sieve as a carrier and is loaded with the calcium titanate by an isometric impregnation method. The composite photocatalyst is obtained by compounding calcium titanate and a molecular sieve by an isometric impregnation method, drying and calcining at high temperature.
In the composite photocatalyst for treating phenol-containing wastewater, the loading rate of calcium titanate is 10%;
the composite photocatalyst for treating the phenol-containing wastewater is a white powdery solid, and the specific surface area of the composite photocatalyst is 317.112m2Per g, pore volume 0.463606cm3Per g, average pore radius
Wherein, the molecular sieve is beta molecular sieve.
A preparation method of a composite photocatalyst for treating phenol-containing wastewater comprises the following steps:
step 1:
(1) determining the saturated water absorption of the carrier molecular sieve:
drying 5g of beta molecular sieve in an oven at 105 ℃ for 30min, cooling to room temperature, and placing the obtained dried molecular sieve in a 50mL beaker;
adding 20mL of deionized water into the dried molecular sieve, soaking for 12 hours at room temperature, pouring out excessive water, and measuring the volume to be 4.9mL, wherein the saturated water absorption of the carrier is as follows: α ═ 5(mL/g) (20-4.9), and α was calculated to be 3.02.
(2) According to the condition that the mass M of the composite photocatalyst for treating the phenol-containing wastewater to be prepared is 2.5g, and the loading capacity of calcium titanate is 10%, the mass percentage of the molecular sieve occupying the composite photocatalyst for treating the phenol-containing wastewater is 90%, and the mass actually required by the molecular sieve and the composite photocatalyst for treating the phenol-containing wastewater is 0.25g and 2.25g respectively;
(3) to calcium titanate, 1.2 × 3.02 × 2.25 ═ 8.2mL of water was added to prepare a calcium titanate solution.
Step 2:
weighing 2.25g of beta molecular sieve in a beaker, adding the prepared calcium titanate solution in the beaker, continuously stirring for 6min, stopping stirring after the system is stable, and standing and soaking for 12 hours at room temperature to obtain the molecular sieve soaked with the calcium titanate aqueous solution;
and step 3: and (3) placing the molecular sieve impregnated with the calcium titanate aqueous solution in an oven, drying at 120 ℃ for 3 hours, finally calcining in a muffle furnace, heating to 750 ℃ at the heating rate of 5 ℃/min, and preserving heat for 6 hours to obtain the composite photocatalyst.
Specific surface area analysis: the specific surface area of the prepared composite photocatalyst is tested by adopting nitrogen adsorption-desorption analysis, and the result shows that the specific surface area is 317.112m2Per g, greater than 35.463m of the specific surface area of the pure calcium titanate2/g。
The application of the composite photocatalyst for treating the phenol-containing wastewater is as follows, namely, a photocatalytic degradation experiment:
mixing 50mL of phenol solution with the concentration of 100mg/L with 0.3g of the prepared composite photocatalyst, taking a high-pressure xenon lamp as a reaction light source, carrying out a catalytic degradation experiment under the action of ultraviolet and visible light, and keeping magnetic stirring in the reaction process, wherein the wavelength range is 320-780 nm. The phenol concentration was measured by 4-aminoantipyrine color development. Experiments show that after one hour of reaction, the degradation rate of phenol reaches 74.5%.
Claims (9)
1. The composite photocatalyst for treating the phenol-containing wastewater is characterized in that a molecular sieve is used as a carrier, and a calcium titanate composite photocatalyst is loaded by an isometric impregnation method; the method specifically comprises the following steps:
step 1, according to the quality of the composite photocatalyst to be prepared for treating the phenol-containing wastewaterMAccording to the loading ratio of calcium titanate ofX Percent, the mass of the calcium titanate isX %×MMass m of molecular sieveIs divided intoIs (1-X %)×M；
Adding to calcium titanate
Preparing a calcium titanate aqueous solution with the mass concentration of C by using mL of water; wherein,
is the saturated water absorption of the carrier molecular sieve, and the unit is mL/g;
step 2, adding the prepared calcium titanate aqueous solution with the mass concentration of C into the solution with the mass concentration of [ (1-X %)×M]Stirring continuously in the molecular sieve of g, stopping stirring after the system is uniformly mixed, and statically soaking for 8-12 hours at room temperature to obtain the molecular sieve soaked with the calcium titanate aqueous solution;
step 3, drying the molecular sieve impregnated with the calcium titanate aqueous solution at 110-120 ℃ for 2-4 hours, calcining at 550-850 ℃ for 4-6 hours to obtain the molecular sieve-loaded calcium titanate composite photocatalyst;
in the composite photocatalyst for treating phenol-containing wastewater, the loading rate of calcium titanate is 1-15%;
the composite photocatalyst for treating phenol-containing wastewater is a white powdery solid, and the specific surface area of the composite photocatalyst is 150-470 m2A pore volume of 0.15 to 0.9 cm/g3And/g, the average pore radius is 15-50 ANG.
2. The composite photocatalyst for treating phenol-containing wastewater as claimed in claim 1, wherein the molecular sieve is a ZSM-5 molecular sieve or a beta molecular sieve.
3. The preparation method of the composite photocatalyst for treating phenol-containing wastewater as claimed in any one of claims 1 to 2, characterized by comprising the following steps:
step 1, according to the quality of the composite photocatalyst to be prepared for treating the phenol-containing wastewaterMAccording to the loading ratio of calcium titanate ofX Percent, the mass of the calcium titanate isX %×MMass m of molecular sieveIs divided intoIs (1-X %)×M；
Adding to calcium titanate
Preparing a calcium titanate aqueous solution with the mass concentration of C by using mL of water;
step 2, the prepared mass concentration isC calcium titanate aqueous solution with the mass of [ (1-X %)×M]Stirring continuously in the molecular sieve of g, stopping stirring after the system is uniformly mixed, and statically soaking for 8-12 hours at room temperature to obtain the molecular sieve soaked with the calcium titanate aqueous solution;
and 3, drying the molecular sieve impregnated with the calcium titanate aqueous solution at 110-120 ℃ for 2-4 hours, calcining at 550-850 ℃ for 4-6 hours, and thus obtaining the composite photocatalyst of the molecular sieve loaded with calcium titanate.
4. The method for preparing the composite photocatalyst for treating phenol-containing wastewater as claimed in claim 3, wherein in the step 1, the mass concentration isCThe unit of the mass concentration of the prepared calcium titanate aqueous solution is g/mL;
the calculation formula is as follows:
Min order to treat the quality of the composite photocatalyst of the phenol-containing wastewater,X % is the loading rate of the calcium titanate,
is the saturated water absorption of the carrier molecular sieve.
5. The method for preparing the composite photocatalyst for treating phenol-containing wastewater as claimed in claim 3, wherein in the step 1, the method for calculating the saturated water absorption rate α of the carrier molecular sieve comprises the following steps:
Vwater (W)Unit mL is the volume of water added;
m is the measured mass of the carrier molecular sieve, unit g;
v is the volume of excess water poured in mL.
6. The method for preparing the composite photocatalyst for treating phenol-containing wastewater according to claim 5, wherein the method for measuring the saturated water absorption of the carrier molecular sieve comprises the following steps:
(1) drying the carrier molecular sieve measured by m g at 100-120 deg.C for 30min, and cooling to room temperature to obtain dried molecular sieve;
(2) adding V into the dried molecular sieveWater (W)Soaking the substrate in mL deionized water for 8-12 h at room temperature, pouring out excessive water, measuring that the volume of the poured excessive water is VmL, and the saturated water absorption of the substrate through a carrier molecular sieve
The saturated water absorption of the carrier molecular sieve is obtained by the calculation method of (1)
。
7. The preparation method of the composite photocatalyst for treating phenol-containing wastewater as claimed in claim 3, wherein in the step 3, the equipment adopted for calcination is a muffle furnace, and the temperature rise rate of calcination is 5-10 ℃/min.
8. The use of a composite photocatalyst for the treatment of phenol-containing wastewater as claimed in claim 1, comprising the steps of:
putting the composite photocatalyst with the molecular sieve loaded with calcium titanate into phenol-containing wastewater, and performing photocatalytic degradation by using a high-pressure xenon lamp as a reaction light source and a wavelength range of 320-780 nm;
wherein, the molecular sieve loaded calcium titanate composite photocatalyst comprises the following components in percentage by mass: phenol = (0.3 to 0.5) g in wastewater: 0.005 g.
9. The application of the composite photocatalyst for treating phenol-containing wastewater as claimed in claim 1, wherein the composite photocatalyst for treating phenol-containing wastewater is applied by using a high-pressure xenon lamp, and the degradation rate of the composite photocatalyst for treating phenol-containing wastewater after one hour of illumination is 24.6% -94.8%.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010069997A1 (en) * | 2008-12-16 | 2010-06-24 | Dyrup A/S | Self-cleaning coating composition |
| CN102019184A (en) * | 2010-12-27 | 2011-04-20 | 内蒙古大学 | Preparation method and application of novel perovskite photocatalyst containing bismuth |
| CN102847529A (en) * | 2012-02-09 | 2013-01-02 | 江苏大学 | Graphene/titanate nanometer composite visible-light activated photocatalyst and preparation method thereof |
| CN103736476A (en) * | 2014-01-23 | 2014-04-23 | 云南大学 | Calcium titanate/calcium oxide composite photocatalyst as well as preparation method and application thereof |
| CN104307563A (en) * | 2014-10-14 | 2015-01-28 | 沈阳理工大学 | Molecular sieve material loaded with bismuth titanate photocatalyst and preparation method of molecular sieve material |
| CN105879871A (en) * | 2016-05-03 | 2016-08-24 | 上海交通大学 | Method for preparing plasma gold nanorod composite photocatalytic material with butterfly wing structure |
-
2018
- 2018-03-30 CN CN201810297664.7A patent/CN108404971B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010069997A1 (en) * | 2008-12-16 | 2010-06-24 | Dyrup A/S | Self-cleaning coating composition |
| CN102019184A (en) * | 2010-12-27 | 2011-04-20 | 内蒙古大学 | Preparation method and application of novel perovskite photocatalyst containing bismuth |
| CN102847529A (en) * | 2012-02-09 | 2013-01-02 | 江苏大学 | Graphene/titanate nanometer composite visible-light activated photocatalyst and preparation method thereof |
| CN103736476A (en) * | 2014-01-23 | 2014-04-23 | 云南大学 | Calcium titanate/calcium oxide composite photocatalyst as well as preparation method and application thereof |
| CN104307563A (en) * | 2014-10-14 | 2015-01-28 | 沈阳理工大学 | Molecular sieve material loaded with bismuth titanate photocatalyst and preparation method of molecular sieve material |
| CN105879871A (en) * | 2016-05-03 | 2016-08-24 | 上海交通大学 | Method for preparing plasma gold nanorod composite photocatalytic material with butterfly wing structure |
Non-Patent Citations (2)
| Title |
|---|
| "Photocatalytic degradation of phenol on strontium titanate supported on HZSM-5";Sun Yufeng;《JOURNAL OF ADVANCED OXIDATION TECHNOLOGIES》;20170101;第20卷(第1期);第2页第2.1节，第4页表1，第2页2.3节 * |
| "ZSM-5分子筛催化剂的制备及协同硫酸盐降解含酚废水的研究";沙俊鹏;《中国优秀硕士学位论文全文数据库工程科技I辑》;20170215(第02期);第22页3.2.3节 * |
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