CN108404971A - Composite photo-catalyst and the preparation method and application thereof for handling wastewater containing phenol - Google Patents
Composite photo-catalyst and the preparation method and application thereof for handling wastewater containing phenol Download PDFInfo
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- CN108404971A CN108404971A CN201810297664.7A CN201810297664A CN108404971A CN 108404971 A CN108404971 A CN 108404971A CN 201810297664 A CN201810297664 A CN 201810297664A CN 108404971 A CN108404971 A CN 108404971A
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- catalyst
- composite photo
- wastewater containing
- containing phenol
- calcium titanate
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims abstract description 169
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 109
- 239000002131 composite material Substances 0.000 title claims abstract description 107
- 239000002351 wastewater Substances 0.000 title claims abstract description 77
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 239000002808 molecular sieve Substances 0.000 claims abstract description 95
- AOWKSNWVBZGMTJ-UHFFFAOYSA-N calcium titanate Chemical compound [Ca+2].[O-][Ti]([O-])=O AOWKSNWVBZGMTJ-UHFFFAOYSA-N 0.000 claims abstract description 92
- 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 84
- 238000001035 drying Methods 0.000 claims abstract description 19
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims abstract description 17
- 230000015556 catabolic process Effects 0.000 claims abstract description 15
- 238000006731 degradation reaction Methods 0.000 claims abstract description 15
- 239000002253 acid Substances 0.000 claims abstract description 14
- 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 53
- 238000010521 absorption reaction Methods 0.000 claims description 26
- 229920006395 saturated elastomer Polymers 0.000 claims description 22
- 239000007864 aqueous solution Substances 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 18
- 239000011148 porous material Substances 0.000 claims description 13
- 239000011575 calcium Substances 0.000 claims description 11
- 229910052791 calcium Inorganic materials 0.000 claims description 11
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 8
- 238000007598 dipping method Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 230000003068 static effect Effects 0.000 claims description 6
- 238000003556 assay Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000000205 computational method Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000004364 calculation method Methods 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 14
- 150000001875 compounds Chemical class 0.000 abstract description 10
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 238000006555 catalytic reaction Methods 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 6
- 238000003837 high-temperature calcination Methods 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 17
- 238000002474 experimental method Methods 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 239000010936 titanium Substances 0.000 description 10
- 229910052719 titanium Inorganic materials 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 9
- 238000013019 agitation Methods 0.000 description 6
- 238000011161 development Methods 0.000 description 6
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- 239000003643 water by type Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 238000001027 hydrothermal synthesis Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 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
- 238000002336 sorption--desorption measurement Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007850 degeneration Effects 0.000 description 2
- 238000002242 deionisation method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 244000144992 flock Species 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 230000002045 lasting effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 229910002971 CaTiO3 Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 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
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 239000012229 microporous material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- -1 with perovskite Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- 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
- B01J29/70—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
-
- 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
-
- 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
- B01J35/60—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
-
- 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
- B01J35/60—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
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
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Abstract
It is a kind of to be used to handle composite photo-catalyst of wastewater containing phenol and the preparation method and application thereof, belong to catalysis material and field of environment protection.The composite photo-catalyst for being used to handle wastewater containing phenol is using calcium titanate as photocatalytic degradation main function substance, and molecular sieve is the photochemical catalyst of carrier.Wherein, calcium titanate is compound with molecular sieve by equi-volume impregnating, after through drying, high-temperature calcination obtain composite photo-catalyst.Using high pressure xenon lamp, illumination is used to handle the degradation rate of the composite photo-catalyst Pyrogentisinic Acid of wastewater containing phenol up to 24.6%~94.8% after one hour, be higher than the degradation rate 22.3% of the small calcium titanate Pyrogentisinic Acid pure at present of illumination one.For the more single pure calcium titanate of the composite photo-catalyst of gained, there is improvement in terms of physical characteristic, photocatalytic degradation effect.The preparation method is simple, and raw material is easy to get, and preparation process is easy to operate, and mild condition is easy to control, product high catalytic efficiency.
Description
Technical field
The present invention relates to a kind of composite photo-catalysts and the preparation method and application thereof for handling wastewater containing phenol, belong to
Catalysis material and field of environment protection.
Background technology
In recent years, along with the continuous promotion of China's industrialized level and the fast development of urbanization, the environment in China is protected
Shield problem is increasingly serious.By taking water pollution as an example, all kinds of chemical enterprises such as coal washery, coking plant, the traditional forms of enterprises's such as non-ferrous metal smelting
A large amount of organic pollution such as phenols etc. can all be contained in the sewage of generation in refinery, paper mill, textile mills etc..These pollutions
If object cannot be effectively treated and be directly discharged in environment, the presence of life will be threatened.How to realize to such dirt
Effective, the cleaning treatment for contaminating object have become the important issue for realizing sustainable development.
As simplest phenolic compound, phenol also known as carbolic acid are a kind of important Organic Chemicals, can be used for
Synthetic resin, rubber, medicine etc..But its toxicity is violent, irritation is strong, and harm to the human body is huge, is difficult to drop under field conditions (factors)
Solution.Mainly physical absorption, chemical reaction, microbial degradation etc. is used to handle substance of this kind in conventional method, these biographies
System method there is can bring secondary pollution, degradation effect is undesirable the problems such as.And since photocatalysis technology the 1970s
Since birth, people constantly expand its application range, and even to this day, it is important that photocatalysis technology has become processing one of pollutant
Research direction.
Catalysis material is as a kind of new catalytic material, with perovskite, titanium dioxide etc. for representative, has efficiently, surely
Calmly, the advantages that catabolite is pollution-free, has apparent degradation effect to common organic pollution, heavy metal ion, mould etc.,
It is widely used in field of environment protection.One of representative as perovskite calcium titanate, it is at low cost because its manufacture craft is simple
Honest and clean, catalytic performance is good and is studied extensively by people.But reunion is also easy to produce since calcium titanate powder granule is subtle, specific surface area compared with
It is small, it easily forms suspension in water and recycles difficulty, limit its a wide range of popularization and application in actual production.
Molecular sieve is a kind of crystalline microporous material with skeleton structure, has large specific surface area and efficient absorption two bright
Aobvious feature.There is molecular sieve crystal honeycomb structure, the volume in hole to account for 50% or more of molecular sieve crystal volume, high hole
Accounting ensure that it with larger specific surface area, usually up to hundreds of m2/g.The diameter of molecular sieve cavity generally existsIt
Between, aperture about existsBetween, suitable with common molecule, larger aperture ensures it with efficient absorption.In addition, molecule
Sieve also has many advantages, such as that selective absorption, surface polarity be high, skeleton structure stabilization, these structural properties, make molecular sieve not only at
For excellent adsorbent, and become effective catalyst and catalyst carrier.
Molecular sieve is compound with calcium titanate, both solved calcium titanate specific surface area it is small, it is easy reunite, be difficult to recycle etc. ask
Topic, while the adsorption effect of molecular sieve can be such that pollutant phenol is enriched with around photochemical catalyst, and the catalysis of calcium titanate is promoted to drop
Solution acts on, the compound catalytic degradation effect that can effectively promote catalyst of the two.The present invention is using phenol as catalysis degeneration experiment
Object, the results show that it works well.To offer reference for the research and development of the new-type catalyst of same type.
Invention content
To solve the deficiencies in the prior art, the present invention provide it is a kind of for handle wastewater containing phenol composite photo-catalyst and
Preparation method is using calcium titanate as photocatalytic degradation main function substance, and molecular sieve is the photochemical catalyst of carrier.Wherein, titanium
Sour calcium is compound with molecular sieve by equi-volume impregnating, after through drying, high-temperature calcination obtain composite photo-catalyst.Gained is answered
For the more single pure calcium titanate of closing light catalyst, there is improvement in terms of physical characteristic, photocatalytic degradation effect.The present invention's
Preparation method is simple, and raw material is easy to get, and preparation process is easy to operate, and mild condition is easy to control, product high catalytic efficiency.
To realize that above-mentioned target, the used technical solution of the present invention are as follows：
A kind of composite photo-catalyst for handling wastewater containing phenol of the present invention, is passed through using molecular sieve as carrier
Volume impregnation method loads the composite photo-catalyst of calcium titanate.
In the composite photo-catalyst for handling wastewater containing phenol, the load factor of calcium titanate is 1%~15%；
The composite photo-catalyst for handling wastewater containing phenol is white powdery solids, specific surface area 150
~470m2/ g, 0.15~0.9cm of pore volume3/ g, average pore radius
The molecular sieve is ZSM-5 molecular sieve or beta-molecular sieve.
A kind of preparation method for handling the composite photo-catalyst of wastewater containing phenol includes the following steps：
Step 1, according to the mass M to be prepared for handling the composite photo-catalyst of wastewater containing phenol, according to calcium titanate
Load factor be X%, then the quality of calcium titanate be X% × M, the quality m of molecular sievePointFor (1-X%) × M；
(α of 1.1 α~1.3) × m is added into calcium titanatePointThe water of mL, it is water-soluble that preparation obtains the calcium titanate that mass concentration is C
Liquid；
Step 2, the calcium titanate aqueous solution of a concentration of C of preparation is added in the molecular sieve that quality is [(1-X%) × M] g,
Lasting stirring, when system after mixing, stop stirring, under room temperature, static dipping 8~12 hours obtains being impregnated with titanium
The molecular sieve of sour calcium aqueous solution；
Step 3, by the molecular sieve for being impregnated with calcium titanate aqueous solution be placed at 110 DEG C~120 DEG C dry 2~4 hours it is laggard
Row calcining, calcination temperature are 550~850 DEG C, keep the temperature 4~6 hours, obtain the composite photo-catalyst of molecular sieve carried calcium titanate.
In the step 1, the mass concentration C is the mass concentration for the calcium titanate aqueous solution prepared, unit g/
mL；
Its calculation formula is as follows：
M is the quality of the composite photo-catalyst for handling wastewater containing phenol, and X% is the load factor of calcium titanate, and α is carrier
The saturated water absorption of molecular sieve；
In the step 1, the computational methods of the saturated water absorption α of carrier molecule sieve are：
α=(VWater-V)/m (2)
α is the saturated water absorption of carrier molecule sieve, unit mL/g；
VWaterFor the volume of water, Unit/mL is added；
M is the quality of the carrier molecule sieve measured, unit g；
V is the volume for the excessive water toppled over, Unit/mL；
The assay method of the saturated water absorption of the described carrier molecule sieve is：
(1) carrier molecule that m g are measured is taken to sieve at 100 DEG C -120 DEG C, dry 30min is cooled to room temperature, after obtaining drying
Molecular sieve；
(2) V is added into the molecular sieve after dryingWaterThe deionized water of mL impregnates 8~12h, is poured out under room temperature
Excessive water is measured and topples over the volume of excessive water for VmL, by the computational methods of the saturated water absorption α of carrier molecule sieve, obtains
The saturated water absorption α sieved to carrier molecule.
In the assay method of the saturated water absorption of the carrier molecule sieve, drying carries out in an oven.
It is cooling to use furnace cooling in the assay method of the saturated water absorption of the carrier molecule sieve.
In the step 2, the system is uniformly mixed, and preferably mixing time is 5~10min.
In the step 3, the dry equipment used is baking oven.
In the step 3, for the equipment that the calcining uses for Muffle furnace, calcining heating rate is 5~10 DEG C/min.
A kind of application for handling the composite photo-catalyst of wastewater containing phenol includes the following steps：
The composite photo-catalyst of molecular sieve carried calcium titanate is put into wastewater containing phenol, uses high pressure xenon lamp to react light
Source, wave-length coverage are 320~780nm, carry out photocatalytic degradation；
Wherein, in mass ratio, the composite photo-catalyst of molecular sieve carried calcium titanate：Phenol=(0.3~0.5) in waste water
g：0.005g.
In the application of the composite photo-catalyst for handling wastewater containing phenol, during the reaction, coordinate magnetic force
Agitating device uses, and guarantee is fully reacted for handling the composite photo-catalyst of wastewater containing phenol with phenol solution.
The application of the composite photo-catalyst for handling wastewater containing phenol, using high pressure xenon lamp, illumination one hour
It is used to handle the degradation rate of the composite photo-catalyst Pyrogentisinic Acid of wastewater containing phenol afterwards up to 24.6%~94.8%, is higher than illumination one
The degradation rate 22.3% of small calcium titanate Pyrogentisinic Acid pure at present.
The present invention's is a kind of for handling composite photo-catalyst of wastewater containing phenol and the preparation method and application thereof, and existing
Technology is compared, and beneficial effects of the present invention are：
1, molecular sieve and calcium titanate is compound, characteristic porous by means of molecular sieve, large specific surface area increases calcium titanate
With the contact area of reactant phenol, the catalytic effect of catalyst is promoted.Simultaneously solve calcium titanate powder in water easily reunite,
The problems such as being difficult to recycle.
2, since molecular sieve has adsorption effect, pollutant phenol can be made to be enriched with around catalyst, be greatly reduced
Phenol is to composite catalyst " diffusion " this reaction step in reaction process, to promote the catalytic degradation of calcium titanate to act on.
Description of the drawings
Fig. 1 is the preparation flow figure of the composite photo-catalyst for handling wastewater containing phenol of the present invention.
Fig. 2 is the XRD diagram that the composite photo-catalyst for handling wastewater containing phenol is made using ZSM-5 molecular sieve as carrier.
Fig. 3 is the SEM figures that the composite photo-catalyst for handling wastewater containing phenol is made using ZSM-5 molecular sieve as carrier.
Fig. 4 is the BET curves that the composite photo-catalyst for handling wastewater containing phenol is made using ZSM-5 molecular sieve as carrier
Figure.
The meaning of reference numeral in figure：Fig. 2：A- calcium titanates, b-ZSM-5 molecular sieves, c- composite photo-catalysts.
Specific implementation mode
Present disclosure is described further and is supplemented with reference to specific embodiment.
Agents useful for same is commercial product in addition to specified otherwise in the embodiment of the present invention, and analysis is pure.
ZSM-5 molecular sieve used, beta-molecular sieve are all from Tianjin Nan Hua catalyst Co., Ltd in the embodiment of the present invention.
In following embodiment, Fig. 1 is seen for handling the preparation flow figure of composite photo-catalyst of wastewater containing phenol.
In following embodiment, calcium titanate used synthesizes for hydro-thermal method, and hydro-thermal method synthesizes CaTiO3Powder, including following step
Suddenly：
Using positive four butyl ester of metatitanic acid as titanium source, calcium nitrate is calcium source, and ethylene glycol monomethyl ether is peptizing agent, and deionized water is solvent,
Potassium hydroxide is mineralizer, and sodium citrate is adjuvant, and CaTiO is synthesized using hydro-thermal method3Powder, wherein in molar ratio, metatitanic acid
Positive four butyl ester：Calcium nitrate=1:1, calcium nitrate：Potassium hydroxide：Sodium citrate=2.83g：2.25g：0.175g.Specially：
(1) according to the ratio, positive four butyl ester of ethylene glycol monomethyl ether and metatitanic acid is mixed, obtains mixed liquor I, wherein by volume, titanium
Positive four butyl ester of acid：Ethylene glycol monomethyl ether=2.6~2.8mL：2.6~2.8mL；
According to the ratio, deionized water and ethylene glycol monomethyl ether are mixed, obtains mixed liquor I I, wherein by volume, deionization
Water：Ethylene glycol monomethyl ether=25~27mL：2.6~2.8mL；
(2) mixed liquor I of preparation is slowly dropped into the mixed liquor I I of preparation, while with lasting stirring, dripped
After mixed liquor I, continue to stir, after the completion of liquid I and mixed liquor I I to be mixed fully react, obtains the titanium hydroxyl with white flock
Precipitate mixed liquor, wherein the amount of mixed liquor I is the whole mixed liquor Is prepared in step (1), and the amount of mixed liquor I I is step (1)
Whole mixed liquor I I of middle preparation；
The drop rate being slowly added dropwise is 4~6mL/min.
The stir speed (S.S.) of the stirring is 600~800r/min.
The agitating mode of the stirring preferably carries out magnetic agitation using magnetic stirrer.
It is described drip mixed liquor I after, continue to stir, be 5~10min.
(3) the titanium hydroxyl precipitation mixed liquor with white flock is centrifuged using supercentrifuge, separation, using deionization
Water carries out repeated washing 3~5 times, obtains titanium hydroxyl precipitation；
The purpose of described washing is the ionized impurity removal that will be attached in titanium hydroxyl precipitation.
The centrifugation rate is 8000~10000r/min.
(4) titanium hydroxyl precipitation is dissolved in 70~80mL deionized waters, after stirring evenly, calcium nitrate is added, while adjoint
Stirring, obtains presoma, potassium hydroxide is added after 1~3min, sodium citrate is added after 1~3min, continues for being stirred to react
10~15min obtains reaction mixture, wherein in mass ratio, calcium nitrate：Potassium hydroxide：Sodium citrate=2.83g：
2.25g：0.175g.
The stirring is magnetic agitation, and stir speed (S.S.) is 600~800r/min.
(5) it is anti-to carry out hydro-thermal in the hydrothermal reaction kettle that reaction mixture addition 100mL is had to polytetrafluoroethyllining lining
It answers, is placed in Muffle furnace and is warming up to 195~205 DEG C, keep the temperature 11~13h；
(6) after reaction, product centrifuge washing it is small to be placed in 70~80 DEG C of baking oven dry 2~4 by natural cooling
When, after dry, it is ground, obtains calcium titanate photocatalyst.Wherein, the grain size of calcium titanate photocatalyst is in 75 μm or less (samples
Product can pass through the sieve of 200 mesh).
The centrifuge washing specifically, respectively successively with deionized water, absolute ethyl alcohol, 5% salpeter solution wash 3-5
It is secondary.
Embodiment 1
A kind of composite photo-catalyst for handling wastewater containing phenol is to pass through incipient impregnation using molecular sieve as carrier
Method loads the composite photo-catalyst of calcium titanate.
Wherein, calcium titanate is photocatalytic degradation main function substance, after calcium titanate and molecular sieve are compound, through drying, high temperature
Calcining obtains composite photo-catalyst.
In the composite photo-catalyst for handling wastewater containing phenol, the load factor of calcium titanate is 5%；
The composite photo-catalyst for handling wastewater containing phenol, is white powdery solids, and specific surface area is
220.259m2/ g, pore volume 0.254636cm3/ g, average pore radius
The molecular sieve is ZSM-5 molecular sieve.
A kind of preparation method for handling the composite photo-catalyst of wastewater containing phenol includes the following steps：
Step 1：
(1) saturated water absorption of carrier molecule sieve is measured, specific assay method is：
5g ZSM-5 molecular sieves dry 30min at 105 DEG C in baking oven is taken, is cooled to room temperature, after obtained drying
Molecular sieve is placed in the beaker of 50mL；
20mL deionized waters are added into the molecular sieve after drying, at room temperature, impregnates 12 hours, excessive water is poured out,
It is 16.5mL to measure its volume, then the saturated water absorption of carrier molecule sieve is：α=(20-16.5)/5 (mL/g), is computed α
It is 0.70.
(2) the composite photo-catalyst mass M according to be prepared for handling wastewater containing phenol is 2.5g, and calcium titanate is born
Carrying capacity is 5%, then the mass percent that molecular sieve occupies the composite photo-catalyst of processing wastewater containing phenol is 95%, and the two is real
Quality needed for border is respectively calcium titanate 0.125g, molecular sieve 2.375g.
(3) water of 1.2 × 0.70 × 2.375=2.0mL is added into calcium titanate, prepares calcium titanate aqueous solution；
Step 2：
The ZSM-5 molecular sieve of 2.375g is weighed in beaker, the metatitanic acid calcium solution of preparation is added in beaker, and is constantly stirred
5min is mixed, system after mixing, stops stirring, and at room temperature, static dipping 12 hours obtains being impregnated with calcium titanate aqueous solution
Molecular sieve；
Step 3, the molecular sieve for being impregnated with calcium titanate aqueous solution is placed in baking oven, it is 3 hours dry at 120 DEG C, finally
It is calcined in Muffle furnace, is warming up to 750 DEG C with the heating rate of 8 DEG C/min, keeps the temperature 6 hours, obtain composite photo-catalyst.
Specific surface area analysis：Composite photo-catalyst obtained above is tested it using nitrogen adsorption-desorption analysis and compares table
Area, the results showed that, specific surface area 220.259m2/ g is more than the specific surface area 35.463m of pure calcium titanate2/g。
A kind of application for handling the composite photo-catalyst of wastewater containing phenol, i.e. photocatalytic degradation experiment are：
The phenol solution of a concentration of 100mg/L of 50mL is taken to be mixed with 0.3g composite photo-catalysts obtained above, with high pressure
Xenon lamp is reaction light source, and wave-length coverage is 320~780nm, and photocatalytic degradation experiment, reaction are carried out under UV, visible light light action
Magnetic agitation is kept in the process.Phenol concentration is measured using 4-AA development process.Experiment shows reaction one hour
Afterwards, the degradation rate of phenol is far above the degradation rate 22.3% of the small calcium titanate Pyrogentisinic Acid pure at present of illumination one up to 74.1%.
To in the present embodiment, being prepared as carrier using ZSM-5 molecular sieve and being urged for handling the complex light of wastewater containing phenol
Agent is shown in Fig. 2 for handling the XRD diagram of composite photo-catalyst of wastewater containing phenol.Each curve in Fig. 2, a are calcium titanate
XRD curves, b are the XRD curves of ZSM-5 molecular sieve, and c is the XRD curves of composite photo-catalyst, by comparing compound front and back each object
The peak position and peak shape of matter characteristic peak are it can be found that the spy containing calcium titanate and ZSM-5 molecular sieve in the collection of illustrative plates of composite photo-catalyst
Peak is levied, peak position and peak shape are almost the same, show that the two is successfully complex as composite photo-catalyst.
The SEM figures of composite photo-catalyst for handling wastewater containing phenol are shown in Fig. 3, can obtain, be prepared from Fig. 3
Composite photo-catalyst particle be micron level, particle is more uniform, without apparent caking phenomenon.
The nitrogen adsorption of composite photo-catalyst for handling wastewater containing phenol-desorption test curve is shown in Fig. 4.Pass through the song
Line computation can obtain, and the specific surface area that composite photo-catalyst is made is 220.259m2/ g, pore volume 0.254636cm3/ g, average hole
RadiusAnd the specific surface area of pure calcium titanate photocatalyst is only 35.463m2/g.Larger specific surface area ensures that it is titanium
The load of sour calcium provides more attachment sites, at the same for catalysis reaction carry out enough reactant contacts area are provided.
Embodiment 2
A kind of composite photo-catalyst for handling wastewater containing phenol is using calcium titanate as photocatalytic degradation main function object
Matter, molecular sieve are carrier, and the photochemical catalyst of calcium titanate is loaded by equi-volume impregnating.By equi-volume impregnating by calcium titanate
With molecular sieve it is compound after, obtain composite photo-catalyst through drying, high-temperature calcination.
In the composite photo-catalyst for handling wastewater containing phenol, the load factor of calcium titanate is 3%；
The composite photo-catalyst for handling wastewater containing phenol, is white powdery solids, and specific surface area is
212.924m2/ g, pore volume 0.179389cm3/ g, average pore radius
Wherein, the molecular sieve is ZSM-5 molecular sieve.
A kind of preparation method for handling the composite photo-catalyst of wastewater containing phenol includes the following steps：
Step 1：
(1) saturated water absorption of carrier molecule sieve is measured：
5g ZSM-5 molecular sieves dry 30min at 105 DEG C in baking oven is taken, is cooled to room temperature, after obtained drying
Molecular sieve is placed in the beaker of 50mL；
Into the molecular sieve after drying, 20mL deionized waters are added, impregnates 12 hours at room temperature, excessive water is poured out,
It is 16.5mL to measure its volume, then the saturated water absorption of the carrier is：α=(20-16.5)/5 (mL/g), it is 0.70 to be computed α.
(2) the composite photo-catalyst mass M according to be prepared for handling wastewater containing phenol is 2.5g, calcium titanate load
Amount is 3%, then the mass percent that molecular sieve occupies the composite photo-catalyst of processing wastewater containing phenol is 97%, and the two is practical
Required quality is respectively calcium titanate 0.075g, molecular sieve 2.425g；
(3) water of 1.2 × 0.70 × 2.425=2.1mL is added into calcium titanate, prepares calcium titanate aqueous solution；
Step 2：
The ZSM-5 molecular sieve of 2.425g is weighed in beaker, the calcium titanate aqueous solution of preparation is added in beaker, and constantly
5min is stirred, after system is uniform, stops stirring, at room temperature, static dipping 12 hours obtains being impregnated with calcium titanate aqueous solution
Molecular sieve；
Step 3：The molecular sieve for being impregnated with calcium titanate aqueous solution is placed in baking oven, it is 4 hours dry at 120 DEG C, finally
It is calcined in Muffle furnace, is warming up to 650 DEG C with the heating rate of 5 DEG C/min, keeps the temperature 6 hours, obtain composite photo-catalyst.
Specific surface area analysis：Composite photo-catalyst obtained above is tested it using nitrogen adsorption-desorption analysis and compares table
Area, the results showed that, specific surface area 212.924m2/ g is more than the specific surface area 35.463m of pure calcium titanate2/g。
A kind of application for handling the composite photo-catalyst of wastewater containing phenol, i.e. photocatalytic degradation experiment are：
The phenol solution of a concentration of 100mg/L of 50mL is taken to be mixed with 0.3g composite photo-catalysts obtained above, with high pressure
Xenon lamp is reaction light source, and wave-length coverage is 320~780nm, and photocatalytic degradation experiment, reaction are carried out under UV, visible light light action
Magnetic agitation is kept in the process.Phenol concentration is measured using 4-AA development process.Experiment shows reaction one hour
Afterwards, the degradation rate of phenol is up to 59.0%.
Embodiment 3
A kind of composite photo-catalyst for handling wastewater containing phenol is using calcium titanate as photocatalytic degradation main function object
Matter, molecular sieve are carrier, and the photochemical catalyst of calcium titanate is loaded by equi-volume impregnating.By equi-volume impregnating by calcium titanate
With molecular sieve it is compound after, obtain composite photo-catalyst through drying, high-temperature calcination.
In the composite photo-catalyst for handling wastewater containing phenol, the load factor of calcium titanate is 3%；
The composite photo-catalyst for handling wastewater containing phenol, is white powdery solids, and specific surface area is
340.669m2/ g, pore volume 0.664242cm3/ g, average pore radius
Wherein, the molecular sieve is beta-molecular sieve.
A kind of preparation method for handling the composite photo-catalyst of wastewater containing phenol includes the following steps：
Step 1：
(1) saturated water absorption of carrier molecule sieve is measured：
5g beta-molecular sieves dry 30min at 105 DEG C in baking oven is taken, is cooled to room temperature, the molecular sieve after obtained drying
It is placed in the beaker of 50mL；
Into the molecular sieve after drying, 20mL deionized waters are added, impregnates 12 hours at room temperature, excessive water is poured out,
It is 4.9mL to measure its volume, then the saturated water absorption of the carrier is：α=(20-4.9)/5 (mL/g), it is 3.02 to be computed α.
(2) the composite photo-catalyst mass M according to be prepared for handling wastewater containing phenol is 2.5g, calcium titanate load
Amount is 3%, then the mass percent that molecular sieve occupies the composite photo-catalyst of processing wastewater containing phenol is 97%, and the two is practical
Required quality is respectively calcium titanate 0.075g, molecular sieve 2.425g；
(3) water of 1.2 × 3.02 × 2.425=8.8mL is added into calcium titanate, prepares metatitanic acid calcium solution.
Step 2：
The beta-molecular sieve of 2.425g is weighed in beaker, the calcium titanate aqueous solution of preparation is added in beaker, and is stirred continuously
8min stops stirring after stable system, and at room temperature, static dipping 12 hours obtains the molecule for being impregnated with calcium titanate aqueous solution
Sieve；
Step 3：The molecular sieve for being impregnated with calcium titanate aqueous solution is placed in baking oven, it is 3 hours dry at 120 DEG C, finally
It is calcined in Muffle furnace, is warming up to 850 DEG C with the heating rate of 10 DEG C/min, keeps the temperature 6 hours, obtain composite photo-catalyst.
Specific surface area analysis：Composite photo-catalyst obtained above is tested it using nitrogen adsorption-desorption analysis and compares table
Area, the results showed that, specific surface area 340.669m2/ g is more than the specific surface area 35.463m of pure calcium titanate2/g。
A kind of application for handling the composite photo-catalyst of wastewater containing phenol, i.e. photocatalytic degradation experiment are：
The phenol solution of a concentration of 100mg/L of 50mL is taken to be mixed with 0.3g composite photo-catalysts obtained above, with high pressure
Xenon lamp is reaction light source, and wave-length coverage is 320~780nm, and photocatalytic degradation experiment, reaction are carried out under UV, visible light light action
Magnetic agitation is kept in the process.Phenol concentration is measured using 4-AA development process.Experiment shows reaction one hour
Afterwards, the degradation rate of phenol is up to 94.8%.
Embodiment 4
A kind of composite photo-catalyst for handling wastewater containing phenol is using calcium titanate as photocatalytic degradation main function object
Matter, molecular sieve are carrier, and the photochemical catalyst of calcium titanate is loaded by equi-volume impregnating.By equi-volume impregnating by calcium titanate
With molecular sieve it is compound after, obtain composite photo-catalyst through drying, high-temperature calcination.
In the composite photo-catalyst for handling wastewater containing phenol, the load factor of calcium titanate is 10%；
The composite photo-catalyst for handling wastewater containing phenol, is white powdery solids, and specific surface area is
317.112m2/ g, pore volume 0.463606cm3/ g, average pore radius
Wherein, the molecular sieve is beta-molecular sieve.
A kind of preparation method for handling the composite photo-catalyst of wastewater containing phenol includes the following steps：
Step 1：
(1) saturated water absorption of carrier molecule sieve is measured：
5g beta-molecular sieves dry 30min at 105 DEG C in baking oven is taken, is cooled to room temperature, the molecular sieve after obtained drying
It is placed in the beaker of 50mL；
Into the molecular sieve after drying, 20mL deionized waters are added, impregnates 12 hours at room temperature, excessive water is poured out,
It is 4.9mL to measure its volume, then the saturated water absorption of the carrier is：α=(20-4.9)/5 (mL/g), it is 3.02 to be computed α.
(2) the composite photo-catalyst mass M according to be prepared for handling wastewater containing phenol is 2.5g, calcium titanate load
Amount is 10%, then the mass percent that molecular sieve occupies the composite photo-catalyst of processing wastewater containing phenol is 90%, and the two is real
Quality needed for border is respectively calcium titanate 0.25g, molecular sieve 2.25g；
(3) water of 1.2 × 3.02 × 2.25=8.2mL is added into calcium titanate, prepares metatitanic acid calcium solution.
Step 2：
The beta-molecular sieve of 2.25g is weighed in beaker, the metatitanic acid calcium solution of preparation is added in beaker, and is stirred continuously
6min stops stirring after stable system, and at room temperature, static dipping 12 hours obtains the molecule for being impregnated with calcium titanate aqueous solution
Sieve；
Step 3：The molecular sieve for being impregnated with calcium titanate aqueous solution is placed in baking oven, it is 3 hours dry at 120 DEG C, finally
It is calcined in Muffle furnace, is warming up to 750 DEG C with the heating rate of 5 DEG C/min, keeps the temperature 6 hours, obtain composite photo-catalyst.
Specific surface area analysis：Composite photo-catalyst obtained above is tested it using nitrogen adsorption-desorption analysis and compares table
Area, the results showed that, specific surface area 317.112m2/ g is more than the specific surface area 35.463m of pure calcium titanate2/g。
A kind of application for handling the composite photo-catalyst of wastewater containing phenol, i.e. photocatalytic degradation experiment are：
The phenol solution of a concentration of 100mg/L of 50mL is taken to be mixed with 0.3g composite photo-catalysts obtained above, with high pressure
Xenon lamp is reaction light source, and wave-length coverage is 320~780nm, and catalysis degeneration experiment is carried out under UV, visible light light action, was reacted
Magnetic agitation is kept in journey.Phenol concentration is measured using 4-AA development process.After experiment shows reaction one hour,
The degradation rate of phenol is up to 74.5%.
Claims (10)
1. a kind of composite photo-catalyst for handling wastewater containing phenol, which is characterized in that this is used to handle wastewater containing phenol
Composite photo-catalyst is that the composite photo-catalyst of calcium titanate is loaded by equi-volume impregnating using molecular sieve as carrier；
In the composite photo-catalyst for handling wastewater containing phenol, the load factor of calcium titanate is 1%~15%.
2. the composite photo-catalyst as described in claim 1 for handling wastewater containing phenol, which is characterized in that described is used for
The composite photo-catalyst of wastewater containing phenol is handled, is white powdery solids, specific surface area is 150~470m2/ g, pore volume
0.15~0.9cm3/ g, average pore radius
3. the composite photo-catalyst as described in claim 1 for handling wastewater containing phenol, which is characterized in that the molecule
Sieve is ZSM-5 molecular sieve or beta-molecular sieve.
4. the preparation method of the composite photo-catalyst for handling wastewater containing phenol described in any one of claims 1 to 3,
It is characterized by comprising the following steps：
Step 1, according to the mass M to be prepared for handling the composite photo-catalyst of wastewater containing phenol, according to the negative of calcium titanate
Load rate is X%, then the quality of calcium titanate is X% × M, the quality m of molecular sievePointFor (1-X%) × M；
(α of 1.1 α~1.3) × m is added into calcium titanatePointThe water of mL is prepared and obtains the calcium titanate aqueous solution that mass concentration is C；
Step 2, the calcium titanate aqueous solution of a concentration of C of preparation is added in the molecular sieve that quality is [(1-X%) × M] g, is continued
Stirring, when system after mixing, stop stirring, under room temperature, it is static dipping 8~12 hours, obtain being impregnated with calcium titanate
The molecular sieve of aqueous solution；
Step 3, the molecular sieve for being impregnated with calcium titanate aqueous solution drying at 110 DEG C~120 DEG C is placed in forge after 2~4 hours
It burns, calcination temperature is 550~850 DEG C, keeps the temperature 4~6 hours, obtains the composite photo-catalyst of molecular sieve carried calcium titanate.
5. the preparation method as claimed in claim 4 for handling the composite photo-catalyst of wastewater containing phenol, which is characterized in that
In the step 1, the mass concentration C is the mass concentration for the calcium titanate aqueous solution prepared, unit g/mL；
Its calculation formula is as follows：
M is the quality of the composite photo-catalyst for handling wastewater containing phenol, and X% is the load factor of calcium titanate, and α is carrier molecule
The saturated water absorption of sieve.
6. the preparation method as claimed in claim 4 for handling the composite photo-catalyst of wastewater containing phenol, which is characterized in that
In the step 1, the computational methods of the saturated water absorption α of carrier molecule sieve are：
α=(VWater-V)/m (2)
α is the saturated water absorption of carrier molecule sieve, unit mL/g；
VWaterFor the volume of water, Unit/mL is added；
M is the quality of the carrier molecule sieve measured, unit g；
V is the volume for the excessive water toppled over, Unit/mL.
7. the preparation method as claimed in claim 6 for handling the composite photo-catalyst of wastewater containing phenol, which is characterized in that
The assay method of the saturated water absorption of the described carrier molecule sieve is：
(1) carrier molecule that m g are measured is taken to sieve at 100 DEG C -120 DEG C, dry 30min is cooled to room temperature, point after being dried
Son sieve；
(2) V is added into the molecular sieve after dryingWaterThe deionized water of mL impregnates 8~12h, excess is poured out under room temperature
Water, measure topple over excessive water volume be VmL, by carrier molecule sieve saturated water absorption α computational methods, carried
The saturated water absorption α of body molecular sieve.
8. the preparation method as claimed in claim 4 for handling the composite photo-catalyst of wastewater containing phenol, which is characterized in that
In the step 3, for the equipment that the calcining uses for Muffle furnace, calcining heating rate is 5~10 DEG C/min.
9. the application as described in claim 1 for handling the composite photo-catalyst of wastewater containing phenol, which is characterized in that including
Following steps：
The composite photo-catalyst of molecular sieve carried calcium titanate is put into wastewater containing phenol, uses high pressure xenon lamp to react light source,
Wave-length coverage is 320~780nm, carries out photocatalytic degradation；
Wherein, in mass ratio, the composite photo-catalyst of molecular sieve carried calcium titanate：Phenol=(0.3~0.5) g in waste water：
0.005g。
10. the application as described in claim 1 for handling the composite photo-catalyst of wastewater containing phenol, which is characterized in that institute
The application for the composite photo-catalyst for handling wastewater containing phenol stated, using high pressure xenon lamp, illumination is used to handle after one hour
The degradation rate of the composite photo-catalyst Pyrogentisinic Acid of wastewater containing phenol is 24.6%~94.8%.
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