CN106925280B - A kind of preparation method of support type two-component metal oxide ozone catalyst for catalytic oxidation - Google Patents
A kind of preparation method of support type two-component metal oxide ozone catalyst for catalytic oxidation Download PDFInfo
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- CN106925280B CN106925280B CN201710029846.1A CN201710029846A CN106925280B CN 106925280 B CN106925280 B CN 106925280B CN 201710029846 A CN201710029846 A CN 201710029846A CN 106925280 B CN106925280 B CN 106925280B
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
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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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
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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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/02—Non-contaminated water, e.g. for industrial water supply
- C02F2103/026—Treating water for medical or cosmetic purposes
Abstract
The present invention relates to a kind of preparation methods of support type two-component metal oxide ozone catalyst for catalytic oxidation comprising following steps: (1) by γ-Al2O3Particle is cleaned with deionized water, then impregnates 20-30h with the sulfuric acid solution that pH is 4, then with deionized water by γ-Al2O3Particle be washed till water outlet it is neutral after be placed in drying box and dry；(2): the identical Cu (NO of configuration quality concentration3)2.3H2O and Y (NO3)3·6H2O solution, the mass concentration of the solution are 0.25~0.5mol/L, configure Cu (NO3)2.3H2O and Y (NO3)3·6H2The ratio between amount of O substance is the mixed solution of 1:1~3:1；(3) by the γ-Al after step (1) drying2O3It is put into step (2) configured dipping solution, after impregnating 18-30h, filters, drying；(4) by the γ-Al after drying in step (3)2O32-5h is roasted at 450~600 DEG C；Catalyst made from the method for the present invention has the characteristics that catalytic activity is strong, stability is good, can be effectively reduced the COD and ammonia nitrogen concentration of waste water especially pharmacy waste water secondary effluent.
Description
Technical field
The invention belongs to catalyst preparation technical fields, more particularly to a kind of support type two-component metal oxide ozone
The preparation method of catalyst for catalytic oxidation.
Background technique
The object of the present invention is to provide a kind of preparations of support type two-component metal oxide ozone catalyst for catalytic oxidation
Method, catalyst obtained have the advantages that catalytic activity is strong, stability is good, can be effectively reduced waste water especially pharmacy waste water
The COD and ammonia nitrogen concentration of secondary effluent, improve the utilization efficiency of ozone.
To achieve the above object, include the following steps,
(1) it is activated catalyst carrier: by γ-Al2O3Particle is cleaned with deionized water, the sulfuric acid for being then 4 with pH
Solution impregnates 20-30h, then with deionized water by γ-Al2O3Particle be washed till water outlet it is neutral after be placed in drying box and dry；
(2) dipping solution: the identical Cu (NO of configuration quality concentration is prepared3)2.3H2O and Y (NO3)3·6H2O solution, it is described molten
The mass concentration of liquid is 0.25~0.5mol/L, configures Cu (NO3) 2.3H2O and Y (NO3) 3·6H2The ratio between amount of O substance is 1:
The mixed solution of 1~3:1；
(3) excessive dipping: by the γ-Al after step (1) drying2O3It is put into step (2) configured dipping solution, soaks
It after stain 18-30h, filters, drying；
(4) load roasting: by the γ-Al after drying in step (3)2O32-5h is roasted at 450~600 DEG C, is born
Load type two-component metal oxide ozone catalyst for catalytic oxidation.
Preferably: the γ-Al chosen in step (1)2O3The partial size of particle is 10-18 mesh, aluminum oxide mass fraction
Not less than 92%, specific surface area is not less than 380m2/ g, compression strength are not less than 100N/.
Preferably: the Cu (NO chosen in step (2)3)2·3H2O is analysis pure blue crystal, contains 3 crystallizations water, content
Not less than 99.0%, Y (NO3)3·6H2O is analysis fine white powder, contains 6 crystallizations water, and content is not less than 99.5%.
Preferably: in step (1), γ-Al2O3Carrier is first cleaned with deionized water, then by washed γ-Al2O3
It is impregnated for 24 hours with the sulfuric acid solution that pH is 4, then is placed on drying box after being washed with deionized water to water outlet neutrality and dries 2h at 90 DEG C,
To obtain the final product.
Preferably: in step (2), in step (2), the identical Cu (NO of configuration quality concentration3)2.3H2O and Y (NO3) 3·
6H2O solution, the mass concentration of the solution are 0.25mol/L, configure Cu (NO3)2.3H2O and Y (NO3)3·6H2The amount of O substance
The ratio between be 1:1 mixed solution.
Preferably: in step (3), by the γ-Al after step (1) drying2O3It is put into step (2) configured dipping solution
In, after impregnating for 24 hours, excessive maceration extract is filtered out, by γ-Al2O3It is placed on drying in drying box, adjusting temperature is dry at 90 DEG C
2h。
Preferably: in step (4), by the γ-Al after drying in step (3)2O33h is roasted at 500 DEG C, is loaded
Type two-component metal oxide ozone catalyst for catalytic oxidation.
Good effect of the present invention is as follows:
(1) preparation method production of the present invention is simple, and at low cost, Active components distribution is uniform, and catalytic activity is strong, and catalyst is steady
Qualitative good, after being used for multiple times, catalytic effect still can preferably be kept.
(2) support type two-component metal oxide produced by the present invention can effective catalysis ozone, so that it is multiple to aoxidize composition
Miscellaneous and high-concentration hardly-degradable pharmacy waste water, is effectively reduced COD (COD) and ammonia nitrogen (NH in waste water3- N) concentration,
Improve the utilization efficiency of ozone.
Detailed description of the invention
Fig. 1 is the process flow chart of half batch processing experiment in the embodiment of the present invention；
In attached drawing, 1 reactor, 1-2 sand core, 2 ozone generators, 3, oxygen cylinder, 4 pharmacy waste water casees, 5 peristaltic pumps, 6 tail gas
Absorption plant, 7 water tanks, 9 flowmeters, 10 catalyst.
Specific embodiment
It will make further narration in detail to the embodiment of the present invention below.
Embodiment 1
The present embodiment the following steps are included:
(1) it is activated catalyst carrier: by γ-Al2O3Particle is cleaned with deionized water, the sulfuric acid for being then 4 with pH
Solution impregnates 20h, then with deionized water by γ-Al2O3Particle be washed till water outlet it is neutral after be placed in drying box and dry.Step
(1) γ-Al chosen in2O3The partial size of particle is 10-18 mesh, and aluminum oxide mass fraction is not less than 92%, and specific surface area is not
Lower than 380m2/ g, compression strength are not less than 100N/.
(2) it prepares dipping solution: the Cu (NO that mass concentration is 0.25mol/L is respectively configured3)2.3H2O and Y (NO3)3·
6H2Then O solution measures the above-mentioned configured Cu (NO of 60m with graduated cylinder3)2.3H2O solution and the above-mentioned configured Y (NO of 20ml3)3·6H2O solution is placed on together in 200ml beaker, configures Cu (NO3) 2.3H2O and Y (NO3 ) 3·6H2The amount of O substance it
Than the dipping solution for 3:1.
(3) excessive dipping: by the 20g γ-Al after step (1) drying2O3It is put into step (2) configured dipping solution
In, it is excessive to impregnate, after impregnating 18h, excessive maceration extract is filtered with Buchner funnel, maceration extract is filtered out, maceration extract will be adsorbed with
γ- Al2O3The dry 1h at 100 DEG C.
(4) load roasting: by the γ-Al after drying in step (3)2O35h is roasted at 450 DEG C in Muffle furnace, is obtained
Support type two-component metal oxide ozone catalyst for catalytic oxidation, that is, embodiment 1- CuO- Y2O3 /Al2O3.Catalyst appearance
For shallow blackish green sphere, partial size 1-2mm, specific surface area is 326 m2/g。
Comparative example 1:
Prepare comparative example 1-CuO/Al2O3Catalyst: by γ-Al2O3Particle is cleaned with deionized water, is then 4 with pH
Sulfuric acid solution impregnate 20h, then with deionized water by γ-Al2O3Particle be washed till water outlet it is neutral after be placed in drying box and dry
It is dry, the γ-Al of selection2O3The partial size of particle is 10-18 mesh, and aluminum oxide mass fraction is not less than 92%, and specific surface area is not low
In 380m2/ g, compression strength are not less than 100N/.The Cu of 80ml configuration good quality concentration 0.25mol/L is measured with graduated cylinder
(NO3)2.3H2O solution takes 20g activity γ-Al in 200ml beaker2O3Carrier carries out excessive dipping, after impregnating 18h, incited somebody to action
Amount maceration extract is filtered with Buchner funnel, is filtered out maceration extract, will be adsorbed with the γ-Al of maceration extract2O3In 100 DEG C of dry 1h, then
By the γ-Al after above-mentioned drying2O3450 DEG C of roasting 5h, obtain comparative example 1-CuO/Al in Muffle furnace2O3Finished catalyst,
The catalyst appearance is glaucous sphere, partial size 1-2mm, specific surface area about 335m2/g。
Comparative example 1- Y2O3/Al2O3: by γ-Al2O3Particle is cleaned with deionized water, and the sulfuric acid for being then 4 with pH is molten
Liquid impregnates 20h, then with deionized water by γ-Al2O3Particle be washed till water outlet it is neutral after be placed in drying box and dry, selection
γ- Al2O3The partial size of particle is 10-18 mesh, and aluminum oxide mass fraction is not less than 92%, and specific surface area is not less than 380m2/
G, compression strength are not less than 100N/.Y (the NO of 80ml configuration good quality concentration 0.25mol/L is measured with graduated cylinder3) 3·
6H2O solution takes 20g activity γ-Al in 200ml beaker2O3Carrier excessively impregnates, and uses excessive maceration extract after impregnating 18h
Buchner funnel filters, and filters out maceration extract, will be adsorbed with the γ-Al of maceration extract2O3The dry 1h at 100 DEG C, then will be above-mentioned dry
Dry object 450 DEG C of roasting 5h in Muffle furnace, obtain comparative example 1- Y2O3 /Al2O3Finished catalyst, the catalyst appearance are
The sphere of the slightly biased Huang of white, partial size 1-2mm, about 341 m of specific surface area2/g。
By above three product and individual γ-Al2O3With individual ozone, i.e. embodiment 1- CuO- Y2O3 /
Al2O3, comparative example 1-CuO/Al2O3, comparative example 1- Y2O3 /Al2O3、γ- Al2O3, ozone O3It is respectively used to catalysis ozone oxygen
Change practical pharmacy waste water, waste water COD and NH3- N initial mass concentration is respectively 431.2mg/L and 287.7mg/L.Using half batch
Processing experiment, experimental technique flow chart are shown in Fig. 1, embodiment 1- CuO- Y2O3 /Al2O3, comparative example 1-CuO/Al2O3, comparison
Example 1- Y2O3 /Al2O3、γ- Al2O3The dosage of catalyst is 10g/L, ozone dosage 23.7mg/min, through more than half
After batch processing experiment test, embodiment 1- CuO- Y2O3 /Al2O3, comparative example 1-CuO/Al2O3, comparative example 1- Y2O3 /
Al2O3、γ- Al2O3, ozone O3For COD and NH in waste water after the above-mentioned practical pharmacy processing 1h of O3 catalytic oxidation3The value of-N
Such as table 1:
1 embodiment 1- CuO- Y of table2O3 /Al2O3, comparative example 1-CuO/Al2O3, comparative example 1- Y2O3 /Al2O3、γ-
Al2O3, ozone O3For the COD and NH before and after the practical pharmacy waste water of O3 catalytic oxidation3- N value
Embodiment 2:
The present embodiment the following steps are included:
(1) it is activated catalyst carrier: by γ-Al2O3Particle is cleaned with deionized water, the sulfuric acid for being then 4 with pH
Solution impregnates 25h, then with the γ-Al after deionized water cleaning and dipping2O3Particle is placed on drying box 90 after being washed till water outlet neutrality
At DEG C dry 3h to get.γ-the Al chosen in step (1)2O3The partial size of particle is 10-18 mesh, aluminum oxide mass fraction
Not less than 92%, specific surface area is not less than 380m2/ g, compression strength are not less than 100N/.
(2) it prepares dipping solution: the Cu (NO that mass concentration is 0.35mol/L is respectively configured3) 2.3H2O solution and Y
(NO3) 3·6H2Then O solution measures the configured Cu (NO of 80ml with graduated cylinder3) 2.3H2The Y of O solution and 40ml
(NO3) 3·6H2O solution is placed into together in 250ml beaker, configures Cu (NO3) 2.3H2O and Y (NO3) 3·6H2O substance
The ratio between amount be 2:1 mixed impregnant liquor.
(3) excessive dipping: by the 30g γ-Al after step (1) drying2O3It is put into step (2) configured dipping solution
Excessive dipping is carried out to filter excessive maceration extract with Buchner funnel after impregnating for 24 hours, filter out maceration extract, maceration extract will be adsorbed with
γ- Al2O3The dry 2h at 90 DEG C.
(4) load roasting: by the γ-Al after drying in step (3)2O34h is roasted at 500 DEG C in Muffle furnace, is obtained
Support type two-component metal oxide ozone catalyst for catalytic oxidation.Catalyst appearance is shallow blackish green sphere, partial size 1-
2mm, specific surface area are 327 m2/g。
Comparative example 2:
Prepare comparative example 2-CuO/Al2O3Catalyst: by γ-Al2O3Particle is cleaned with deionized water, is then with pH
4 sulfuric acid solution impregnates 25h, then with deionized water by γ-Al2O3Particle is placed in drying box after being washed till water outlet neutrality
3h, the γ-Al of selection are dried at 90 DEG C2O3The partial size of particle is 10-18 mesh, and aluminum oxide mass fraction is not less than 92%, than
Surface area is not less than 380m2/ g, compression strength are not less than 100N/.Measuring 120ml configuration good quality score with graduated cylinder is
Cu (the NO of 0.35mol/L3 ) 2.3H2O solution takes 30g activity γ-Al in 250ml beaker2O3Carrier carries out excessive leaching
Excessive maceration extract is filtered with Buchner funnel after impregnating for 24 hours, filters out maceration extract, will be adsorbed with the γ-Al of maceration extract by stain2O3?
Dry 2h at 90 DEG C, then by the γ-Al after above-mentioned drying2O34h is roasted at 500 DEG C in Muffle furnace, obtains comparative example 2-
CuO /Al2O3Finished catalyst, the catalyst appearance are glaucous sphere, partial size 1-2mm, specific surface area about 331m2/g。
Prepare comparative example 2- Y2O3 /Al2O3: by γ-Al2O3Particle is cleaned with deionized water, the sulphur for being then 4 with pH
Acid solution impregnates 25h, then with deionized water by γ-Al2O3Particle is placed in drying box at 90 DEG C after being washed till water outlet neutrality
Dry 3h, the γ-Al of selection2O3The partial size of particle is 10-18 mesh, and aluminum oxide mass fraction is not less than 92%, specific surface area
Not less than 380m2/ g, compression strength are not less than 100N/.80ml, which is measured, with graduated cylinder configures good quality score 0.35mol/L
Y (NO3) 3·6H2O solution takes 30g activity γ-Al in 250ml beaker2O3Carrier excessively impregnates, and dipping afterwards will for 24 hours
Excessive maceration extract is filtered with Buchner funnel, filters out maceration extract, will be adsorbed with the γ-Al of maceration extract2O3The dry 2h at 90 DEG C, so
Above-mentioned dried object is roasted into 4h at 500 DEG C in Muffle furnace afterwards, obtains comparative example 2- Y2O3 /Al2O3Finished catalyst, this is urged
Agent appearance is the sphere of the slightly biased Huang of white, partial size 1-2mm, specific surface area about 336m2/g。
By above three product and individual γ-Al2O3With individual ozone, i.e. embodiment 2- CuO- Y2O3 /
Al2O3, comparative example 2-CuO/Al2O3, comparative example 2- Y2O3 /Al2O3、γ- Al2O3, ozone O3It is respectively used to catalysis ozone oxygen
Change practical pharmacy waste water, waste water COD and NH3- N initial mass concentration is respectively 516.9mg/L and 293.6mg/L.Experiment uses
Half batch processing experiment, experimental technique flow chart are shown in Fig. 1, embodiment 2- CuO- Y2O3 /Al2O3, comparative example 2-CuO/Al2O3、
Comparative example 2- Y2O3 /Al2O3、γ- Al2O3The dosage of catalyst is 10g/L, ozone dosage 23.7mg/min, warp
It crosses after being tested with identical half batch experimental method of embodiment 1, embodiment 2- CuO- Y2O3 /Al2O3, comparative example 2-CuO
/Al2O3, comparative example 2- Y2O3 /Al2O3、γ- Al2O3, ozone O31h is handled for the above-mentioned practical pharmacy of O3 catalytic oxidation
COD and NH in waste water afterwards3The value of-N such as table 2:
2 embodiment 2- CuO- Y of table2O3 /Al2O3, comparative example 2-CuO/Al2O3, comparative example 2- Y2O3 /Al2O3、γ-
Al2O3, ozone O3For the COD and NH before and after the practical pharmacy waste water of O3 catalytic oxidation3- N value
Embodiment 3:
The present embodiment the following steps are included:
(1) it is activated catalyst carrier: by γ-Al2O3Particle is cleaned with deionized water, the sulfuric acid for being then 4 with pH
Solution impregnates 30h, then with deionized water by γ-Al2O3Particle be washed till water outlet it is neutral after be placed in drying box and dry.Step
(1) γ-Al chosen in2O3The partial size of particle is 10-18 mesh, and aluminum oxide mass fraction is not less than 92%, and specific surface area is not
Lower than 380m2/ g, compression strength are not less than 100N/.
(2) it prepares dipping solution: the Cu (NO that mass concentration is 0.5mol/L is respectively configured3)2.3H2O solution and Y (NO3)3·6H2Then O solution measures the configured Cu (NO of 40ml with graduated cylinder3)2.3H2Y (the NO of O solution and 40ml3) 3·6H2
Solution configures Cu (NO in 200ml beaker3)2.3H2O and Y (NO3)3·6H2The ratio between amount of O substance is the hybrid infusion of 1:1
Liquid.
(3) excessive dipping: by the γ-Al after 20g step (1) drying2O3It is put into step (2) configured dipping solution
Excessive dipping is carried out to filter excessive maceration extract with Buchner funnel after impregnating 30h, filter out maceration extract, maceration extract will be adsorbed with
γ- Al2O3The dry 3h at 80 DEG C.
(4) load roasting: by the γ-Al after drying in step (3)2O32h is roasted at 600 DEG C in Muffle furnace, is obtained
Support type two-component metal oxide ozone catalyst for catalytic oxidation.Catalyst appearance is shallow blackish green sphere, partial size 1-
2mm, specific surface area 357m2/g。
Comparative example 3:
Prepare comparative example 3-CuO/Al2O3Catalyst: by γ-Al2O3Particle is cleaned with deionized water, is then with pH
4 sulfuric acid solution impregnates 30h, then with deionized water by γ-Al2O3Particle be washed till water outlet it is neutral after be placed in drying box and dry
It is dry, the γ-Al of selection2O3The partial size of particle is 10-18 mesh, and aluminum oxide mass fraction is not less than 92%, and specific surface area is not low
In 380m2/ g, compression strength are not less than 100N/.The Cu of 80ml configuration good quality concentration 0.5mol/L is measured with graduated cylinder
(NO3) 2.3H2O solution takes 20g activity γ-Al in 200ml beaker2O3Carrier carries out excessive dipping, will after impregnating 30h
Excessive maceration extract is filtered with Buchner funnel, filters out maceration extract, will be adsorbed with the γ-Al of maceration extract2O3The dry 3h at 80 DEG C, so
Afterwards by the γ-Al after above-mentioned drying2O3600 DEG C of roasting 2h, obtain comparative example 3-CuO/Al in Muffle furnace2O3Catalyst at
Product, the catalyst appearance are glaucous sphere, partial size 1-2mm, about 345 m of specific surface area2/g。
Prepare comparative example 3- Y2O3 /Al2O3: by γ-Al2O3Particle is cleaned with deionized water, the sulphur for being then 4 with pH
Acid solution impregnates 30h, then with deionized water by γ-Al2O3Particle be washed till water outlet it is neutral after be placed in drying box and dry, select
γ-the Al taken2O3The partial size of particle is 10-18 mesh, and aluminum oxide mass fraction is not less than 92%, and specific surface area is not less than
380m2/ g, compression strength are not less than 100N/.Y (the NO that 80ml has configured 0.5mol/L is measured with graduated cylinder3) 3·6H2O
Solution takes 20g activity γ-Al in 200ml beaker2O3Carrier excessively impregnates, and leaks excessive maceration extract with Bu Shi after impregnating 30h
Bucket filters, and filters out maceration extract, will be adsorbed with the γ-Al of maceration extract2O3The dry 3h at 80 DEG C, then by above-mentioned dried object in horse
Not 600 DEG C of roasting 2h in furnace, obtain comparative example 3- Y2O3 /Al2O3Finished catalyst, the catalyst appearance are the slightly biased Huang of white
Sphere, partial size 1-2mm, about 351 m of specific surface area2/g。
By above three product and individual γ-Al2O3With individual ozone, i.e. 3 CuO- Y of embodiment2O3 /
Al2O3, comparative example 3-CuO/Al2O3, comparative example 3- Y2O3 /Al2O3、γ- Al2O3, ozone O3It is respectively used to catalysis ozone oxygen
Change practical pharmacy waste water, waste water COD and NH3- N initial mass concentration is respectively 569.7mg/L and 332.5g/L.Experiment is using half
Batch processing experiment, experimental technique flow chart are shown in Fig. 1, embodiment 3- CuO- Y2O3 /Al2O3, comparative example 3-CuO/Al2O3, it is right
Ratio 3- Y2O3 /Al2O3、γ- Al2O3The dosage of catalyst is 10g/L, ozone dosage 23.7mg/min, is passed through
After the test of identical half batch experimental method of embodiment 1, embodiment 1- CuO- Y2O3 /Al2O3, comparative example 1-CuO/
Al2O3, comparative example 1- Y2O3 /Al2O3、γ- Al2O3, ozone O3After the above-mentioned practical pharmacy processing 1h of O3 catalytic oxidation
COD and NH in waste water3The value of-N such as table 1:
3 embodiment 3- CuO- Y of table2O3 /Al2O3, comparative example 3-CuO/Al2O3, comparative example 3- Y2O3 /Al2O3、γ-
Al2O3, ozone O3For the COD and NH before and after the practical pharmacy waste water of O3 catalytic oxidation3- N value
Embodiment 4:
The present embodiment the following steps are included:
(1) it is activated catalyst carrier: by γ-Al2O3Particle is cleaned with deionized water, the sulfuric acid for being then 4 with pH
Solution impregnates 28h, then with deionized water by γ-Al2O3Particle be washed till water outlet it is neutral after be placed in drying box and dry.Step
(1) γ-Al chosen in2O3The partial size of particle is 10-18 mesh, and aluminum oxide mass fraction is not less than 92%, and specific surface area is not
Lower than 380m2/ g, compression strength are not less than 100N/.
(2) it prepares dipping solution: the Cu (NO that mass concentration is 0.25mol/L is respectively configured3) 2.3H2O solution and Y
(NO3) 3·6H2Then O solution measures the configured Cu (NO of 40ml with graduated cylinder3)2.3H2Y (the NO of O solution and 40ml3)3·6H2Solution configures Cu (NO in 200ml beaker3) 2.3H2O and Y (NO3) 3·6H2The ratio between amount of O substance is 1:1's
Mixed impregnant liquor.Cu (the NO of selection3) 2·3H2O is analysis pure blue crystal, contains 3 crystallizations water, and content is not less than 99.0%
(mass fraction), Y (NO3) 3·6H2O is analysis fine white powder, contains 6 crystallizations water, content is not less than 99.5%(mass point
Number).
(3) excessive dipping: by the γ-Al after 20g step (1) drying2O3It is put into step (2) configured dipping solution
Excessive dipping is carried out to filter excessive maceration extract with Buchner funnel after impregnating for 24 hours, filter out maceration extract, maceration extract will be adsorbed with
γ- Al2O3The dry 2h at 90 DEG C.
(4) load roasting: by the γ-Al after drying in step (3)2O33h is roasted at 500 DEG C in Muffle furnace, is obtained
Support type two-component metal oxide ozone catalyst for catalytic oxidation.Catalyst appearance is shallow blackish green sphere, partial size 1-
2mm, specific surface area 321m2/g。
Comparative example 4:
Prepare comparative example 4-CuO/Al2O3Catalyst: by γ-Al2O3Particle is cleaned with deionized water, is then with pH
4 sulfuric acid solution impregnates 28h, then with deionized water by γ-Al2O3Particle be washed till water outlet it is neutral after be placed in drying box and dry
It is dry, the γ-Al of selection2O3The partial size of particle is 10-18 mesh, and aluminum oxide mass fraction is not less than 92%, and specific surface area is not low
In 380m2/ g, compression strength are not less than 100N/.The Cu of 80ml configuration good quality concentration 0.25mol/L is measured with graduated cylinder
(NO3) 2.3H2O solution is placed in 200ml beaker, takes 20g activity γ-Al2O3Carrier carries out excessive dipping, and dipping is for 24 hours
Afterwards, excessive maceration extract is filtered with Buchner funnel, filters out maceration extract, the γ-Al of maceration extract will be adsorbed with2O3It is dry at 90 DEG C
2h, then by the γ-Al after above-mentioned drying2O3500 DEG C of roasting 3h, obtain comparative example 4-CuO/Al in Muffle furnace2O3Catalysis
Agent finished product, the catalyst appearance are glaucous sphere, partial size 1-2mm, about 339 m of specific surface area2/g.The Cu wherein chosen
(NO3) 2·3H2O is analysis pure blue crystal, contains 3 crystallizations water, and content is not less than 99.0%(mass fraction), Y (NO3) 3·
6H2O is analysis fine white powder, contains 6 crystallizations water, and content is not less than 99.5%(mass fraction).
Comparative example 4- Y2O3 /Al2O3: by γ-Al2O3Particle is cleaned with deionized water, and the sulfuric acid for being then 4 with pH is molten
Liquid impregnates 28h, then with deionized water by γ-Al2O3Particle be washed till water outlet it is neutral after be placed in drying box and dry, selection
γ- Al2O3The partial size of particle is 10-18 mesh, and aluminum oxide mass fraction is not less than 92%, and specific surface area is not less than 380m2/
G, compression strength are not less than 100N/.Y (the NO of 80ml configuration good quality concentration 0.25mol/L is measured with graduated cylinder3) 3·
6H2O solution takes 20g activity γ-Al in 200ml beaker2O3Carrier excessively impregnates, and dipping for 24 hours afterwards uses excessive maceration extract
Buchner funnel filters, and filters out maceration extract, will be adsorbed with the γ-Al of maceration extract2O3The dry 2h at 90 DEG C, then by above-mentioned drying
Object roasts 3h at 500 DEG C in Muffle furnace, obtains comparative example 4- Y2O3 /Al2O3Finished catalyst, the catalyst appearance are white
The sphere of the slightly biased Huang of color, partial size 1-2mm, about 343 m of specific surface area2/g。
By above three product and individual γ-Al2O3With individual ozone, i.e. embodiment 4- CuO- Y2O3 /
Al2O3, comparative example 4-CuO/Al2O3, comparative example 4- Y2O3 /Al2O3、γ- Al2O3, ozone O3It is respectively used to catalysis ozone oxygen
Change practical pharmacy waste water, waste water COD and NH3- N initial mass concentration is respectively 541.8mg/L and 429.1mg/L.Experiment uses
Half batch processing experiment, experimental technique flow chart are shown in Fig. 1, embodiment 4- CuO- Y2O3 /Al2O3, comparative example 4-CuO/Al2O3、
Comparative example 4- Y2O3 /Al2O3、γ- Al2O3The dosage of catalyst is 10g/L, ozone dosage 23.7mg/min, warp
It crosses after being tested with identical half batch experimental method of embodiment 1, embodiment 4- CuO- Y2O3 /Al2O3, comparative example 4-CuO
/Al2O3, comparative example 4- Y2O3 /Al2O3、γ- Al2O3, ozone O31h is handled for the above-mentioned practical pharmacy of O3 catalytic oxidation
COD and NH in waste water afterwards3The value of-N such as table 4:
4 embodiment 4- CuO- Y of table2O3 /Al2O3, comparative example 4-CuO/Al2O3, comparative example 4- Y2O3 /Al2O3、γ-
Al2O3, ozone O3For the COD and NH before and after the practical pharmacy waste water of O3 catalytic oxidation3- N value
Half batch processing experiment is all made of in 1-4 of the embodiment of the present invention and comparative example 1-4 to test each embodiment and right
CuO- Y made from ratio2O3 /Al2O3、CuO /Al2O3、Y2O3 /Al2O3、γ- Al2O3With ozone O3For catalysis ozone oxygen
Change the effect of practical pharmacy waste water, and records the COD and NH of pharmacy waste water before and after the processing3- N value, experimentation flow chart such as Fig. 1
Shown, the process flow of half batch processing experiment includes following equipment: ozone generator 2, flowmeter 9, pharmacy waste water case 4,
Reactor 1, oxygen cylinder 3, peristaltic pump 5, water tank 7 and device for absorbing tail gas 6.The reactor 1 is closed cylindrical glass
Container, internal diameter 60mm, high 400mm, dischargeable capacity about 1000mL are about 20 μm micro- away from aperture is arranged at the 40mm of reactor bottom end
Hole sand core aerator, the micropore sand core aerator include sand core 1-2.Distilled water flushing reactor 1 is first used before experiment, then
Reactor 1 is pre-processed with the ozone generated in ozone generator 2 to remove the interference that may consume ozone in reactor 1
Composition.The ozone generator 2 is cooled down using high pure oxygen as gas source, with tap water, is prepared in situ, and oxygen cylinder 3 is ozone generator 2
High pure oxygen is provided, flowmeter 9, adjustable air inlet size are provided between oxygen cylinder 3 and ozone generator 2.Ozone passes through blueness
The CF-G-3-10G type ozone generator 2 of woods Co., Ltd, island country production provides, in use, pharmacy waste water to be processed is stored in
In pharmacy waste water case 4, pharmacy waste water BT300-1F type peristaltic pump 5 in the form of continuous flow with ozone gas simultaneously from reaction
1 bottom end of device enters inside reactor 1, meanwhile, the ozone of the generation in ozone generator 2 is with the pharmacy waste water together from reaction
1 bottom end of device enters inside reactor 1, and ozone forms tiny bubble and tested catalysis by the sand core 1-1 of 1 bottom of reactor
Agent 10 and pharmacy waste water contact, so that gas, liquid, solid phase reaction occur.By the revolving speed and the reaction column water inlet that adjust peristaltic pump 5
Tongs on pipe control hydraulic detention time.Away from overflow outlet sampling at 1 bottom end 30mm of reactor, with excessive thiosulfuric acid
Sodium solution measures after terminating reaction.(" hydrochemistry is aerobic by GB/T11914-1989 using potassium dichromate method by COD in pharmacy waste water
The measurement potassium dichromate method of amount ") measurement.NH3(HJ 535-2009 be " Water quality ammonia nitrogen using nessler reagent optical analysis by-N
Measure Berthelot spectrophotometry ") measurement.It is 2% that the ozone of reaction is not participated in by the mass concentration in device for absorbing tail gas 6
KI solution absorb heel row amplify gas, do not generate pollution to environment.
By embodiment 4- CuO- Y2O3 /Al2O3, comparative example 4-CuO/Al2O3, comparative example 4- Y2O3 /Al2O3Respectively
After reusing 80 times, catalytic activity reduces 7.3%, 8.6,9.2% respectively, it can be seen that support type bi-component of the present invention
Metal oxide catalyst stability is good, and after being used for multiple times, catalytic effect still can preferably be kept.
The foregoing description of the disclosed embodiments enables those skilled in the art to implement or use the present invention.
Various modifications to these embodiments will be readily apparent to those skilled in the art, as defined herein
General Principle can be realized in other embodiments in the case where not departing from the spirit or scope of the invention patent.Therefore, originally
Invention is not intended to be limited to the embodiments shown herein, and is to fit to and the principles and novel features disclosed herein
Consistent widest scope.
Claims (7)
1. a kind of preparation method of support type two-component metal oxide ozone catalyst for catalytic oxidation, it is characterised in that: including
Following steps,
(1) it is activated catalyst carrier: by γ-Al2O3Particle is cleaned with deionized water, the sulfuric acid solution for being then 4 with pH
20-30h is impregnated, then with deionized water by γ-Al2O3Particle be washed till water outlet it is neutral after be placed in drying box and dry；
(2) dipping solution: the identical Cu (NO of configuration concentration is prepared3)2.3H2O and Y (NO3)3·6H2O solution, the concentration of the solution
For 0.25~0.5mol/L, Cu (NO is configured3) 2.3H2O and Y (NO3) 3·6H2The ratio between amount of O substance is the mixing of 1:1~3:1
Solution；
(3) excessive dipping: by the γ-Al after step (1) drying2O3It is put into step (2) configured dipping solution, impregnates
It after 18-30h, filters, drying；
(4) load roasting: by the γ-Al after drying in step (3)2O32-5h is roasted at 450~600 DEG C, obtains support type
Two-component metal oxide ozone catalyst for catalytic oxidation.
2. a kind of preparation side of support type two-component metal oxide ozone catalyst for catalytic oxidation according to claim 1
Method, it is characterised in that: the γ-Al chosen in step (1)2O3The partial size of particle is 10-18 mesh, and aluminum oxide mass fraction is not
Lower than 92%, specific surface area is not less than 380m2/ g, compression strength are not less than 100N/.
3. a kind of preparation side of support type two-component metal oxide ozone catalyst for catalytic oxidation according to claim 1
Method, it is characterised in that: the Cu (NO chosen in step (2)3)2·3H2O is analysis pure blue crystal, contains 3 crystallizations water, content is not
Lower than 99.0%, Y (NO3)3·6H2O is analysis fine white powder, contains 6 crystallizations water, and content is not less than 99.5%.
4. a kind of preparation side of support type two-component metal oxide ozone catalyst for catalytic oxidation according to claim 1
Method, it is characterised in that: in step (1), γ-Al2O3Carrier is first cleaned with deionized water, then by washed γ-Al2O3
It is impregnated for 24 hours with the sulfuric acid solution that pH is 4, then is placed on drying box after being washed with deionized water to water outlet neutrality and dries 2h at 90 DEG C,
To obtain the final product.
5. a kind of preparation side of support type two-component metal oxide ozone catalyst for catalytic oxidation according to claim 1
Method, it is characterised in that: in step (2), the identical Cu (NO of configuration concentration3) 2.3H2O and Y (NO3) 3·6H2O solution, the solution
Concentration be 0.25mol/L, configure Cu (NO3) 2.3H2O and Y (NO3) 3·6H2The ratio between amount of O substance is that the mixing of 1:1 is molten
Liquid.
6. a kind of preparation side of support type two-component metal oxide ozone catalyst for catalytic oxidation according to claim 1
Method, it is characterised in that: in step (3), by the γ-Al after step (1) drying2O3It is put into step (2) configured dipping solution
In, after impregnating for 24 hours, excessive maceration extract is filtered out, by γ-Al2O3It is placed on drying in drying box, adjusting temperature is dry at 90 DEG C
2h。
7. a kind of preparation side of support type two-component metal oxide ozone catalyst for catalytic oxidation according to claim 1
Method, it is characterised in that: in step (4), by the γ-Al after drying in step (3)2O33h is roasted at 500 DEG C, obtains support type
Two-component metal oxide ozone catalyst for catalytic oxidation.
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