CN108097231B - A kind of ozone oxidation catalyst and its preparation method and application - Google Patents
A kind of ozone oxidation catalyst and its preparation method and application Download PDFInfo
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- CN108097231B CN108097231B CN201711447007.8A CN201711447007A CN108097231B CN 108097231 B CN108097231 B CN 108097231B CN 201711447007 A CN201711447007 A CN 201711447007A CN 108097231 B CN108097231 B CN 108097231B
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- ozone oxidation
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- 239000003054 catalyst Substances 0.000 title claims abstract description 76
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 230000003647 oxidation Effects 0.000 title claims abstract description 41
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 84
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical group [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000008188 pellet Substances 0.000 claims abstract description 23
- 230000003197 catalytic effect Effects 0.000 claims abstract description 20
- 239000011787 zinc oxide Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000005416 organic matter Substances 0.000 claims abstract description 8
- 230000003213 activating effect Effects 0.000 claims abstract description 3
- 238000001354 calcination Methods 0.000 claims abstract description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000000465 moulding Methods 0.000 claims description 9
- 238000006385 ozonation reaction Methods 0.000 claims description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 claims description 5
- 229940039790 sodium oxalate Drugs 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 3
- 239000007921 spray Substances 0.000 claims description 3
- 239000000853 adhesive Substances 0.000 claims description 2
- 230000001070 adhesive effect Effects 0.000 claims description 2
- 150000004054 benzoquinones Chemical class 0.000 claims description 2
- 238000005469 granulation Methods 0.000 claims 1
- 230000003179 granulation Effects 0.000 claims 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 15
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 7
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000002351 wastewater Substances 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 239000011324 bead Substances 0.000 description 5
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000010865 sewage Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000005751 Copper oxide Substances 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 229910000431 copper oxide Inorganic materials 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 239000002815 homogeneous catalyst Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- MXYZAIITOLWDLM-UHFFFAOYSA-N 2,3,4,5-tetranitrophenol Chemical compound OC1=CC([N+]([O-])=O)=C([N+]([O-])=O)C([N+]([O-])=O)=C1[N+]([O-])=O MXYZAIITOLWDLM-UHFFFAOYSA-N 0.000 description 1
- 238000000441 X-ray spectroscopy Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- -1 hydroxyl radical free radical Chemical class 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 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
- 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
-
- 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
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
-
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/32—Hydrocarbons, e.g. oil
- C02F2101/322—Volatile compounds, e.g. benzene
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a kind of preparation methods of ozone oxidation catalyst, comprising the following steps: mixes ρ type aluminium oxide, active component with water, prepares the spherical pellet that partial size is 1-9mm；Wherein, active component is zinc oxide；By pellet, constant temperature handles 10-24h at 60-90 DEG C, and then calcining and activating handles 2-5h at 450-550 DEG C, obtains the ozone oxidation catalyst using aluminium oxide as carrier.The present invention, which is also claimed, to be used prepared by above-mentioned preparation method using aluminium oxide as the ozone oxidation catalyst of carrier.The invention also discloses the above-mentioned applications using aluminium oxide as the ozone oxidation catalyst of carrier in ozone oxidation organic matter.Method of the invention is simple, at low cost, and catalyst has good catalytic performance in ozone oxidation catalysis reaction.
Description
Technical field
The present invention relates to catalyst preparation technical field and sewage treatment field more particularly to a kind of ozone oxidation catalysts
And its preparation method and application.
Background technique
Ozone has extremely strong oxidability, can be with direct oxidation degradation of organic substances, but its oxidation selectivity constrains
To the ability of dirty Organic substance in water depth mineralising processing.In order to improve the ability of ozone utilization rate and deeply treating wastewater, generally
Using the method that catalyst is added into ozone oxidation sewerage.Catalyst has the function of that ozone, ozone quilt is catalytically decomposed
It is converted to the stronger hydroxyl free of oxidation susceptibility, hydroxyl radical free radical can substantially aoxidize all organic matters, have depth
Manage the ability of sewage.
Currently used catalyst is divided into homogeneous and two class of out-phase.Homogeneous catalyst is not influenced by alternate diffusion, is easy to
Control, but the metal ion put into water is difficult to separate and cannot be recycled, and can make underwater gold category ion concentration is excessively high to make
The pairs of secondary pollution of environment and the increase of operating cost.The problem of different-phase catalyst can be to avoid homogeneous catalyst,
But compared with homogeneous catalyst, there are alternate diffusional resistance, active sites in heterogeneous catalysis system contacts with reaction substrate
The problems such as rate is low.Therefore different-phase catalyst performance is improved, the production cost of catalyst is reduced, simplifies scale production process, is
The essential condition of different-phase catalyst business application.
In addition, catalyst cost accounts for maximum a part of cost in catalytic ozonation processing sewage system, wastewater treatment
It generally requires that more fund is spent to buy catalyst in project, this handles the popularization band of waste water technology to catalytic ozonation
Very big obstruction is carried out.Therefore the cost of catalyst how is reduced under conditions of guaranteeing catalyst performance is technical staff's needs
The major issue of solution.Many researcher doors select cheap raw material such as: Fe2O3、MnO2Etc. come the spherical shape that produces 1-9mm
Catalyst, but catalyst catalytic performance is often lower, cannot meet simultaneously not only reduces cost but also guarantees catalyst performance.And
CuO、CeO2, etc. prices costly, this not only increases biggish economic pressures to production, also constrains ozone catalytic oxygen
Popularization of the change technology in sewage treatment field.
Summary of the invention
In order to solve the above technical problems, the object of the present invention is to provide a kind of ozone oxidation catalyst and preparation method thereof and
Using method of the invention is simple, and at low cost, catalyst has good catalytic performance in ozone oxidation catalysis reaction.
The present invention provides a kind of preparation methods of ozone oxidation catalyst, comprising the following steps:
(1) ρ type aluminium oxide, active component are mixed with water, prepares the spherical pellet that partial size is 1-9mm；Wherein, active group
It is divided into zinc oxide；
(2) by pellet, constant temperature handles 10-24h at 60-90 DEG C, and then calcining and activating handles 2-5h at 450-550 DEG C,
It obtains smelly using aluminium oxide as the ozone oxidation catalyst of carrier.
Further, in step (1), the partial size of ρ type aluminium oxide is 200-325 mesh.Physico-chemical property is selected to stablize, it is mechanical
Intensity is big, and easily molded ρ type alumina powder is carrier.
Further, in step (1), the mass ratio of ρ type aluminium oxide and active component is 90-96:4-10.
Further, in step (1), the mass ratio of ρ type aluminium oxide and water is 1.5-2.5:1.
Further, it in step (1), is pelletized using round as a ball moulding process.Round as a ball moulding process, have quickly,
The advantages of simple and easy amplification.
Further, it in step (1), is pelletized using spheronizator, comprising the following steps: by ρ type aluminium oxide, activity
Component is added in the disk of spheronizator, sprays into spray water and forms spherical pellet as adhesive.
Further, the revolving speed of the disk of spheronizator is 20-60rpm.
Step (2) can promote the water of ρ type alumina powder and water in more mild 60-90 DEG C of temperature range of condition
Reaction is closed, acts on obtaining the bigger sample of mechanical strength by the glue connection of ρ type aluminium oxide, and sample can be made to keep preferable spherical
Pattern does not crack.After high-temperature activation, the absorption water and the crystallization water contained in sample is removed, and forms many holes in sample, is promoted
It is spread into the mass transfer of reaction substrate ozone and organic matter in extraneous solution, to improve the catalytic performance of catalyst；ρ simultaneously
Type aluminium oxide is converted to γ type aluminium oxide.Temperature is an important factor for influencing catalyst institutional framework property, only in 450-550
The cellular structure of the catalyst sample ability specific surface area and multi-stage porous with higher that are obtained within the temperature range of DEG C.Pass through energy
The Zn-ef ficiency that dispersive x-ray spectroscopy figure (Fig. 1) can see in zinc oxide is uniformly distributed on alumina support, illustrates the work
Artistic skill accesses the uniform loaded catalyst of Active components distribution.
The present invention is also claimed using ozone oxidation catalyst prepared by above-mentioned preparation method.
The invention also discloses application of the above-mentioned ozone oxidation catalyst in catalytic ozonation organic matter.
Further, organic matter is phenol, to one in biphenol, benzoquinones, tetranitro-phenol, benzene, toluene and sodium oxalate
Kind is several.
Further, in application, the dosage of ozone is 0.2-1.2g/L, the dosage of catalyst is 5-15g/L.
According to the above aspect of the present invention, the present invention has at least the following advantages:
Use cheap and high catalytic performance zinc oxide for active component, it is round as a ball by a step using ρ type aluminium oxide as carrier
Ozone catalytic oxidation catalyst is quickly mass produced in molding technique.
The present invention solves the problems, such as that ozone oxidation catalyst cost input and catalytic performance are low in sewage treatment.Chemical industry is former
ZnO powder price is 20000 yuan/ton to material in the market, hence it is evident that lower than common production ozone catalytic oxidation catalyst active component CuO
(40000 yuan/ton), CeO2Etc. prices (40000 yuan/ton).The interaction of ZnO and ozone are better than CuO and CeO2, in aluminium oxide
Loading zinc oxide is in catalyst catalytic ozonation degrading waste water in the system of organic matter, and solubility of the ozone in waste water is big
In the system in other two kinds of catalyst；To reduce the concentration of ozone in exhaust gas, the utilization efficiency of ozone is improved and to waste water
The removal rate of middle organic matter.
The above description is only an overview of the technical scheme of the present invention, in order to better understand the technical means of the present invention,
And can be implemented in accordance with the contents of the specification, the following is a detailed description of the preferred embodiments of the present invention and the accompanying drawings.
Detailed description of the invention
Fig. 1 is the energy dispersion X-ray spectrogram of ozone oxidation catalyst prepared by example 1；
Fig. 2 is the X-ray diffraction spectrogram of ozone oxidation catalyst prepared by embodiment 1；
Fig. 3 is the X-ray diffraction spectrogram of ozone oxidation catalyst prepared by embodiment 4；
Fig. 4 is the X-ray diffraction spectrogram of ozone oxidation catalyst prepared by embodiment 5；
Fig. 5 is the nitrogen adsorption curve of ozone oxidation catalyst prepared by embodiment 1；
Fig. 6 is the pore size distribution curve of ozone oxidation catalyst prepared by embodiment 1；
Fig. 7 is different catalysts phenol concentration versus time curve in the experiment of catalytic ozonation phenol.
Specific embodiment
With reference to the accompanying drawings and examples, specific embodiments of the present invention will be described in further detail.Implement below
Example is not intended to limit the scope of the invention for illustrating the present invention.
Embodiment 1
(1) the ρ type aluminium oxide of 325 mesh and zinc oxide are mixed, obtains mixture, wherein contain 4-10% in mixture
The zinc oxide of mass percent.Round as a ball molding is carried out using spheronizator.The round as a ball disk of 1-3m is chosen, is fed with 100kg/h fast
It spends into the rounding disk opened and is continuously added to mixture, while spraying into water into rounding disk according to 50kg/L rate, it is to be obtained straight
When diameter is the bead of 1-9mm or so, taking-up is spare, obtains required pellet.
(2) pellet gathered is placed in closed system, and constant temperature is handled for 24 hours at 90 DEG C.
(3) by step (2), treated that pellet is added continuously in vertical kiln, passes through control furnace bottom discharging speed, adjusts
Material-saving ball stops 3h in 450 DEG C of regions of kiln constant temperature, obtains ozone oxidation catalyst.
Fig. 1,2,5,6 are the energy dispersion X-ray spectrogram of ozone oxidation catalyst prepared by embodiment 1, X-ray respectively
Diffraction spectrogram, nitrogen adsorption curve, pore size distribution curve, the results showed that, ozone oxidation catalyst prepared by embodiment 1 contains
ZnO and gamma-alumina crystal form, sample have biggish specific surface area (251m2/ g), wider pore-size distribution.Table 1 is 1 sample of example
Product mechanical strength data form, 1 sample mechanical strength of example is all larger than 80N as can be seen from the table, illustrates using the technique
The sample of preparation has preferable mechanical strength.
Table 1 is 1 sample of test case five times mechanical strength tables of data
Embodiment 2
(1) the ρ type aluminium oxide of 200 mesh and zinc oxide are mixed, obtains mixture, wherein contain 4-10% in mixture
The zinc oxide of mass percent.Round as a ball molding is carried out using spheronizator.The round as a ball disk of 1-3m is chosen, is fed with 100kg/h fast
Spend and be continuously added to mixture into the rounding disk opened, at the same sprayed into rounding disk according to 50kg/L rate water be then sprayed into it is suitable
The water of amount, when diameter to be obtained is the bead of 6-9mm or so, taking-up is spare, obtains required pellet.
(2) pellet gathered is placed in closed system, and constant temperature is handled for 24 hours at 60 DEG C.
(3) by step (2), treated that pellet is added continuously in vertical kiln, passes through control furnace bottom discharging speed, adjusts
Material-saving ball stops 3h in 500 DEG C of regions of kiln constant temperature, obtains ozone oxidation catalyst.
Embodiment 3
(1) the ρ type aluminium oxide of 325 mesh and zinc oxide are mixed, obtains mixture, wherein contain 4-10% in mixture
The zinc oxide of mass percent.Round as a ball molding is carried out using spheronizator.The round as a ball disk of 1-3m is chosen, is fed with 100kg/h fast
Spend and be continuously added to mixture into the rounding disk opened, at the same sprayed into rounding disk according to 50kg/L rate water be then sprayed into it is suitable
The water of amount, when diameter to be obtained is the bead of 1-3mm or so, taking-up is spare, obtains required pellet.
(2) pellet gathered is placed in closed system, and constant temperature is handled for 24 hours at 90 DEG C.
(3) by step (2), treated that pellet is added continuously in vertical kiln, passes through control furnace bottom discharging speed, adjusts
Material-saving ball stops 3h in 550 DEG C of regions of kiln constant temperature, obtains ozone oxidation catalyst.
Embodiment 4
In order to prepare catalyst using copper oxide as active component as control, the specific steps are as follows:
(1) the ρ type aluminium oxide of 325 mesh and copper oxide are mixed, obtains mixture, wherein contain 4-10% in mixture
The copper oxide of mass percent.Round as a ball molding is carried out using spheronizator.The round as a ball disk of 1-3m is chosen, is fed with 100kg/h fast
Spend and be continuously added to mixture into the rounding disk opened, at the same sprayed into rounding disk according to 50kg/L rate water be then sprayed into it is suitable
The water of amount, when diameter to be obtained is the bead of 3-5mm or so, taking-up is spare, obtains required pellet.
(2) pellet gathered is placed in closed system, and constant temperature is handled for 24 hours at 90 DEG C.
(3) by step (2), treated that pellet is added continuously in vertical kiln, passes through control furnace bottom discharging speed, adjusts
Material-saving ball stops 3h in 450 DEG C of regions of kiln constant temperature, obtains ozone oxidation catalyst.
Fig. 2 is the X-ray diffraction spectrogram of ozone oxidation catalyst prepared by embodiment 4, the results showed that, 4 sample of embodiment
For CuO and gamma-alumina crystal form.
Embodiment 5
In order to prepare catalyst using ceria as active component as control, the specific steps are as follows:
(1) the ρ type aluminium oxide of 325 mesh and ceria are mixed, obtains mixture, wherein contain 4- in mixture
The ceria of 10% mass percent.Round as a ball molding is carried out using spheronizator.The round as a ball disk of 1-3m is chosen, with 100kg/h
Charging rate is continuously added to mixture into the rounding disk opened, while spraying into water then into rounding disk according to 50kg/L rate
Suitable water is sprayed into, when diameter to be obtained is the bead of 3-5mm or so, taking-up is spare, obtains required pellet.
(2) pellet gathered is placed in closed system, and constant temperature is handled for 24 hours at 90 DEG C.
(3) by step (2), treated that pellet is added continuously in vertical kiln, passes through control furnace bottom discharging speed, adjusts
Material-saving ball stops 3h in 450 DEG C of regions of kiln constant temperature, obtains ozone oxidation catalyst.
Fig. 3 is the X-ray diffraction spectrogram of ozone oxidation catalyst prepared by embodiment 5, the results showed that, 5 sample of embodiment
For CeO2With gamma-alumina crystal form.
Embodiment 6
It is the useless of simulating pollution object that catalyst prepared in embodiment 1,4,5, which is used for catalytic ozonation degradation of phenol,
In water, specific implementation step is as follows:
Select phenol as simulating pollution object, phenol concentration 100ppm.Respectively into configured phenol solution
Above-mentioned catalyst is added, wherein the mass volume ratio of catalyst and aqueous solution is 10g:1L.Open magnetic agitation or mechanical stirring
Guarantee that the reaction of reaction vessel interior uniformly occurs, is passed through ozone, the dosage of ozone and the ratio of waste water are 0.5g:1L.
Reaction time is 1h.The phenol concentration under different time in solution is measured, as a result as shown in figure 4, it is seen that embodiment
The removal rate and removal speed of 1 catalyst Pyrogentisinic Acid is substantially better than control experiment (embodiment 4 and 5), in embodiment 1,4,5
The removal rate of catalyst Pyrogentisinic Acid is respectively 99.3%, 88.8%, 82.5%, illustrates to provide using method preparation of the invention
There is the catalyst of good catalytic, and reduces production cost.And aluminium oxide is carrier loaded zinc oxide materialization
Matter is stablized, and is insoluble in water, greatly reduces the loss of catalyst, extends the service life of catalyst.
Example 7
It is the useless of simulating pollution object that catalyst prepared in embodiment 1,4,5, which is used for catalytic ozonation degradation of phenol,
In water, specific implementation step is as follows:
Select sodium oxalate as simulating pollution object, oxalic acid na concn is 1.2kg/L.Toward configured sodium oxalate water solution
In be separately added into above-mentioned catalyst, wherein the mass volume ratio of catalyst and aqueous solution be 10g:1L.Open magnetic agitation or machine
Tool stirs to guarantee that the reaction of reaction vessel interior uniformly occurs, and is passed through ozone, the dosage of ozone and the ratio of waste water are
0.65kg:1L.Reaction time is 120min.The COD concentration under different time in solution is measured, the results are shown in Table 1, from table
It can be seen that, the catalyst of embodiment 1 is better than check experiment (embodiment 4 and 5) to the removal rate of COD in solution, embodiment 1,4,5
In catalyst be respectively 41.8%, 36.3%, 30.9% to the removal rate of COD, illustrate to prepare using method of the invention
Catalyst with good catalytic.
2 catalyst of table COD concentration in the experiment of catalytic ozonation sodium oxalate changes with time data
The above is only a preferred embodiment of the present invention, it is not intended to restrict the invention, it is noted that for this skill
For the those of ordinary skill in art field, without departing from the technical principles of the invention, can also make it is several improvement and
Modification, these improvements and modifications also should be regarded as protection scope of the present invention.
Claims (7)
1. a kind of preparation method of ozone oxidation catalyst, which comprises the following steps:
(1) ρ type aluminium oxide, active component are mixed with water, prepares the spherical pellet that partial size is 1-9mm；Wherein, the active group
It is divided into zinc oxide；The partial size of the ρ type aluminium oxide is 200-325 mesh；The mass ratio of the ρ type aluminium oxide and zinc oxide is 90-
96:4-10；The mass ratio of the ρ type aluminium oxide and water is 1.5-2.5:1；
(2) by the pellet, constant temperature handles 10-24h at 60-90 DEG C, and then calcining and activating handles 2-5h at 450-550 DEG C,
Obtain the ozone oxidation catalyst.
2. preparation method according to claim 1, it is characterised in that: in step (1), carried out using round as a ball moulding process
Granulation.
3. preparation method according to claim 2, it is characterised in that: in step (1), pelletized using spheronizator,
The following steps are included: the ρ type aluminium oxide, active component are added in the disk of spheronizator, spray water is sprayed into as adhesive
To form spherical pellet.
4. preparation method according to claim 3, it is characterised in that: the revolving speed of the disk of the spheronizator is 20-
60rpm。
5. ozone oxidation catalyst prepared by a kind of preparation method described in any one of -4 according to claim 1.
6. application of the ozone oxidation catalyst according to claim 5 in catalytic ozonation organic matter.
7. application according to claim 6, it is characterised in that: the organic matter is phenol, to biphenol, benzoquinones, four nitre
One or more of base phenol, benzene, toluene and sodium oxalate.
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| CN109718803A (en) * | 2018-06-29 | 2019-05-07 | 光大水务（深圳）有限公司 | A kind of catalyst and its preparation, application method for handling waste water nbsCOD |
| CN109731574A (en) * | 2018-06-29 | 2019-05-10 | 光大水务（深圳）有限公司 | A kind of preparation method of catalyst complex carrier, the catalyst based on the carrier and catalyst |
| CN109772358A (en) * | 2018-06-29 | 2019-05-21 | 光大水务（深圳）有限公司 | A kind of preparation method of catalyst pore creating material and the high porosity catalyst based on pore creating material |
| CN109718749B (en) * | 2019-01-11 | 2019-12-13 | 南京大学盐城环保技术与工程研究院 | method for preparing ozone catalyst by stepped gradient temperature rise calcining method and application |
| CN110026180A (en) * | 2019-05-10 | 2019-07-19 | 上海纳米技术及应用国家工程研究中心有限公司 | A kind of preparation method of catalytic ozonation catalyst and products thereof and application |
| CN114950338B (en) * | 2022-05-16 | 2023-11-24 | 苏州大学 | Preparation method and application of alumina permanganate composite adsorbent |
| CN115025768B (en) * | 2022-05-23 | 2024-02-09 | 苏州大学 | Spherical alumina-based hydrophobic ozone catalytic oxidation catalyst and preparation method and application thereof |
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