CN111229248A - Preparation method of supported metal oxide particle catalyst - Google Patents
Preparation method of supported metal oxide particle catalyst Download PDFInfo
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- CN111229248A CN111229248A CN202010138713.XA CN202010138713A CN111229248A CN 111229248 A CN111229248 A CN 111229248A CN 202010138713 A CN202010138713 A CN 202010138713A CN 111229248 A CN111229248 A CN 111229248A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 73
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 34
- 239000002245 particle Substances 0.000 title claims abstract description 32
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 31
- 239000002184 metal Substances 0.000 claims abstract description 31
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims abstract description 25
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 25
- 235000010413 sodium alginate Nutrition 0.000 claims abstract description 25
- 229940005550 sodium alginate Drugs 0.000 claims abstract description 25
- 239000000661 sodium alginate Substances 0.000 claims abstract description 25
- 239000000243 solution Substances 0.000 claims abstract description 25
- 239000012266 salt solution Substances 0.000 claims abstract description 21
- 239000011259 mixed solution Substances 0.000 claims abstract description 17
- 230000003197 catalytic effect Effects 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims description 15
- 239000008262 pumice Substances 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 239000000919 ceramic Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 239000005373 porous glass Substances 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 229910052723 transition metal Inorganic materials 0.000 claims description 3
- 150000003624 transition metals Chemical class 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000011435 rock Substances 0.000 abstract description 7
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 238000004134 energy conservation Methods 0.000 abstract description 3
- 238000011084 recovery Methods 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 description 11
- 238000007254 oxidation reaction Methods 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 8
- 239000002351 wastewater Substances 0.000 description 6
- 238000005273 aeration Methods 0.000 description 3
- 230000033558 biomineral tissue development Effects 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- -1 iron-manganese metal oxide Chemical class 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 3
- OSDLLIBGSJNGJE-UHFFFAOYSA-N 4-chloro-3,5-dimethylphenol Chemical compound CC1=CC(O)=CC(C)=C1Cl OSDLLIBGSJNGJE-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000002572 peristaltic effect Effects 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
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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
-
- 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
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
- C02F2101/34—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
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
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- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention discloses a preparation method of a supported metal oxide particle catalyst, which comprises the following steps: s10: preparing a sodium alginate solution; s20: preparing catalyst carrier particles; s30: preparing a mixed solution of a sodium alginate solution and a catalyst carrier; s40: preparing a metal salt solution; s50: dropwise adding the mixed solution obtained in the step S30 to the metal salt solution obtained in the step S40 to obtain a gel layer containing the catalyst carrier, and pretreating the gel layer; s60: and roasting the pretreated gel layer to obtain the supported metal oxide particle catalyst. The invention improves the catalytic efficiency of ozone by distributing the metal oxide on the surface of the catalyst carrier, and has the advantages of convenience, adjustable load metal amount proportion, energy conservation, environmental protection, easy recovery and reutilization and the like. On the other hand, the catalyst carrier in the invention can be made of natural materials such as volcanic rock, and the like, so that the catalyst carrier is convenient and easy to obtain, and the cost can be reduced.
Description
Technical Field
The invention relates to the technical field of catalytic materials, in particular to a preparation method of a catalyst loaded with metal oxide particles.
Background
With the development of industry and the improvement of the living standard of people, the water environment problem becomes one of the bottlenecks restricting the economic development. The water environment is seriously polluted, and the water treatment industry faces serious challenges for a long time in the future.
The advanced oxidation water treatment technology is a water treatment technology taking hydroxyl radicals as main oxides, and the addition of a supported metal oxide particle catalyst can promote the yield of the hydroxyl radicals. Taking the ozone oxidation technology as an example, the ozone oxidation technology is a high-efficiency advanced oxidation water treatment technology, the oxidation-reduction potential of ozone is as high as 2.07ev, most organic matters in water can be oxidized and decomposed, and the ozone oxidation technology is particularly suitable for treating organic wastewater with high chroma and difficult biodegradation.
In the prior art, ozone oxidation technology has attracted much attention due to its advantages of high treatment efficiency, strong oxidation ability, easy control, etc. However, the ozone oxidation also has the problems of low ozone utilization rate, incomplete oxidation of organic matters, mineralization and the like in the water treatment process. The introduction of the catalyst loaded with metal oxide particles not only improves the utilization efficiency of ozone, but also has remarkable promoting effect on the decomposition and mineralization of organic matters. Therefore, the development of a heterogeneous catalyst which is efficient, stable, convenient, environment-friendly and easy to separate becomes one of the key technologies of ozone oxidation.
Most of the existing methods for preparing the supported metal oxide particle catalyst are impregnation method, coprecipitation method, melting method and the like, but the problems of complex flow, small load amount, difficult control and the like exist.
Disclosure of Invention
The present invention aims to provide a method for preparing a supported metal oxide particle catalyst, which is used for solving the problems.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a method for preparing a supported metal oxide particulate catalyst comprising the steps of:
s10: preparing a sodium alginate solution;
s20: preparing catalyst carrier particles;
s30: preparing a mixed solution of a sodium alginate solution and a catalyst carrier;
s40: preparing a metal salt solution;
s50: dropwise adding the mixed solution obtained in the step S30 to the metal salt solution obtained in the step S40 to obtain a gel layer containing the catalyst carrier, and pretreating the gel layer;
s60: and roasting the pretreated gel layer to obtain the supported metal oxide particle catalyst.
Further, the concentration of the sodium alginate solution in step S10 is 0.5-10 wt%.
Further, in step S20, the catalyst carrier is one or more of pumice, activated carbon, activated alumina, porous glass, and ceramics, and the particle size of the catalyst carrier particles is 1.4mm to 1.6 mm.
Further, in step S30, the mass ratio of the catalyst carrier to the sodium alginate in the sodium alginate solution is 1: (0.01-0.1).
Further, in step S40, the metal salt solution is a solution made of one or more of sulfate, nitrate and chloride of transition metal having catalytic activity for ozone, wherein the metal having catalytic activity for ozone includes, but is not limited to, Mn, Fe, Co, Ce and Ni, and the concentration of the metal salt solution is 2-30 wt%.
Further, in step S50, the mass ratio of the catalyst carrier in the mixed solution to the metal salt in the metal salt solution is 1: (0.001-0.1); the pretreatment is to stand for 12 hours, sieve and dry at the temperature of 80 ℃ for 24 hours.
Further, in step S60, the roasting temperature is 400-700 ℃, the roasting time is 2-6 h, and the heating rate is 5-10 ℃/min.
The invention has the following beneficial effects: in the preparation method of the supported metal oxide particle catalyst, the metal oxide is distributed on the surface of the catalyst carrier, so that the catalytic efficiency of ozone is improved, and the preparation method has the advantages of convenience, adjustable supported metal amount ratio, energy conservation, environmental protection, easiness in recycling and the like. On the other hand, the catalyst carrier in the invention can be made of natural materials such as volcanic rock, and the like, so that the catalyst carrier is convenient and easy to obtain, and the cost can be reduced.
Drawings
FIG. 1 is a front-back XRD spectrum of a light volcanic rock loaded with iron-manganese metal oxide.
Detailed Description
The technical solution of the present invention is further described below with reference to the following embodiments and the accompanying drawings.
Example 1
The embodiment provides a preparation method of a supported metal oxide particle catalyst which is efficient, stable, convenient, environment-friendly and easy to separate.
Specifically, the preparation method of the supported metal oxide particle catalyst comprises the following steps:
s10: preparing a sodium alginate solution;
in the embodiment of the invention, a certain mass of sodium alginate is weighed and placed in water, and the mixture is fully stirred to obtain a sodium alginate solution with the concentration of 0.5-10 wt%.
S20: preparing catalyst carrier particles;
in the embodiment of the invention, one or more of volcanic pumice, activated carbon, activated alumina, porous glass and ceramic are selected as a catalyst carrier, and the catalyst carrier is crushed and sieved to obtain catalyst carrier particles with the particle size of 1.4mm-1.6 mm.
S30: preparing a mixed solution of a sodium alginate solution and a catalyst carrier;
in the embodiment of the invention, a catalyst carrier is placed into a sodium alginate solution, and the mixture is fully stirred to obtain a mixed solution, wherein the mass ratio of the catalyst carrier to sodium alginate in the sodium alginate solution is 1: (0.01-0.1).
S40: preparing a metal salt solution;
in an embodiment of the present invention, the metal salt solution is a solution made of one or more of sulfate, nitrate and chloride of transition metal having catalytic activity of ozone, wherein the metal having catalytic activity of ozone includes, but is not limited to, Mn, Fe, Co, Ce and Ni. Specifically, the concentration of the metal salt solution is 2 to 30 wt%.
S50: dropwise adding the mixed solution obtained in the step S30 to the metal salt solution obtained in the step S40 to obtain a gel layer containing the catalyst carrier, and pretreating the gel layer;
in the embodiment of the invention, the mixed solution is slowly dripped into the metal salt solution through a peristaltic pump, and the mass ratio of the catalyst carrier in the mixed solution to the metal salt in the metal salt solution is 1: (0.001-0.1); the pretreatment is to stand for 12 hours, sieve and dry at the temperature of 80 ℃ for 24 hours.
S60: and roasting the pretreated gel layer to obtain the supported metal oxide particle catalyst.
In the embodiment of the invention, the roasting temperature is 400-700 ℃, the roasting time is 2-6 h, and the heating rate is 5-10 ℃/min.
The catalyst prepared by the preparation method of the supported metal oxide particle catalyst is mainly used for the water treatment process of ozone catalytic oxidation. Specifically, after being catalyzed by the catalyst, the ozone can generate more hydroxyl radicals, so that the catalytic efficiency of the ozone is improved, organic pollutants in the wastewater can be effectively degraded, and the degradation efficiency and the mineralization degree of organic matters in the wastewater are improved. On the other hand, the metal oxide is loaded on the surface of the carrier, so that the catalytic efficiency is promoted, the loss of the catalytic active component can be reduced, and the metal oxide and the carrier are easy to separate, so that the cost loss is reduced, and the catalyst has multiple environmental protection values.
In the preparation method of the catalyst loaded with the metal oxide particles, the catalyst carrier and a sodium alginate solution are mixed to obtain a mixed solution, the mixed solution is slowly dripped into a metal salt solution to form a sodium alginate gel layer wrapping the catalyst carrier, and after the sodium alginate gel layer is screened, dried, roasted at high temperature, decomposed and oxidized by metal salt to obtain the metal oxide with fine particles, and the metal oxide is distributed on the surface of the catalyst carrier, so that the catalytic efficiency of ozone is improved. Compared with the prior art, the preparation method of the supported metal oxide particle catalyst has the advantages of convenience, adjustable supported metal amount proportion, energy conservation, environmental protection, easy recycling, and the like, and has certain industrial popularization value. On the other hand, the catalyst carrier in the invention can be made of natural materials such as volcanic rock, and the like, so that the catalyst carrier is convenient and easy to obtain, and the cost can be reduced.
Example 2
A method for preparing a supported metal oxide particulate catalyst comprising the steps of:
s10: preparing a sodium alginate solution with the concentration of 2 wt%;
s20: selecting volcanic pumice as a catalyst carrier, crushing and sieving to obtain volcanic pumice particles with the particle size of 1.5;
s30: preparing a mixed solution of a sodium alginate solution and a catalyst carrier, wherein the mass ratio of the volcanic pumice to the sodium alginate is 50: 1;
s40: respectively preparing metal salt solutions of Fe and Mn with the concentration of 2 wt%;
s50: slowly dripping the mixed solution obtained in the step S30 into the two metal salt solutions prepared in the step S40 through a peristaltic pump to obtain a gel layer containing the catalyst carrier, standing the gel layer for 12 hours, sieving, and drying at the temperature of 80 ℃ for 24 hours;
s60: and (4) roasting the gel layer treated in the step (S50) in a muffle furnace at the temperature of 600 ℃ for 4 hours in the air atmosphere, wherein the heating rate is 8 ℃/min, and naturally cooling to obtain the volcanic pumice catalyst loaded with the iron-manganese metal oxide.
Phase analysis is carried out on the light volcanic rock loaded with the iron-manganese metal oxide by an X-ray diffractometer (XRD), the result is shown in figure 1, and Fe appears in the XRD spectrum2O3With Mn3O4Characteristic diffraction peaks, indicating that the two metal oxides have been loaded on volcanic rock.
Example 3
Takes parachlorometaxylenol simulated wastewater as a main research object, and uses an ozone aeration device to treat the simulated wastewater. Preparing simulated wastewater with the initial concentration of 100mg/L, wherein the adding amount of ozone is 50mg/L, the treatment time is 30min, the catalyst is a light volcanic rock catalyst loaded with cerium oxide and manganese oxide, the adding amount of the catalyst is 5g/L, and the removal rate of parachlorometaxylenol in the ozone aeration device added with the catalyst is improved to 89% from 68% compared with the ozone aeration treatment device without the catalyst.
The sequence of the above embodiments is only for convenience of description and does not represent the advantages and disadvantages of the embodiments.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (7)
1. A method for preparing a supported metal oxide particulate catalyst, comprising the steps of:
s10: preparing a sodium alginate solution;
s20: preparing catalyst carrier particles;
s30: preparing a mixed solution of a sodium alginate solution and a catalyst carrier;
s40: preparing a metal salt solution;
s50: dropwise adding the mixed solution obtained in the step S30 to the metal salt solution obtained in the step S40 to obtain a gel layer containing the catalyst carrier, and pretreating the gel layer;
s60: and roasting the pretreated gel layer to obtain the supported metal oxide particle catalyst.
2. The process for producing a supported metal oxide particle catalyst as claimed in claim 1, wherein the concentration of the sodium alginate solution in the step S10 is 0.5 to 10% by weight.
3. The method of claim 1, wherein in step S20, the catalyst support is one or more selected from the group consisting of pumice, activated carbon, activated alumina, porous glass, and ceramics, and the particle size of the catalyst support particles is 1.4mm to 1.6 mm.
4. The method of producing a supported metal oxide particle catalyst as claimed in claim 1, wherein in step S30, the mass ratio of the catalyst carrier to sodium alginate in the sodium alginate solution is 1: (0.01-0.1).
5. The method of claim 1, wherein in step S40, the metal salt solution is a solution of one or more of sulfate, nitrate and chloride of a transition metal having catalytic activity for ozone, wherein the metal having catalytic activity for ozone includes but is not limited to Mn, Fe, Co, Ce and Ni, and the concentration of the metal salt solution is 2-30 wt%.
6. The method of claim 1, wherein in step S50, the mass ratio of the catalyst carrier in the mixed solution to the metal salt in the metal salt solution is 1: (0.001-0.1); the pretreatment is to stand for 12 hours, sieve and dry at the temperature of 80 ℃ for 24 hours.
7. The method for producing a supported metal oxide particulate catalyst according to claim 1, wherein in step S60, the calcination temperature is 400 to 700 ℃, the calcination time is 2 to 6 hours, and the temperature increase rate is 5 to 10 ℃/min.
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| CN111841659A (en) * | 2020-07-28 | 2020-10-30 | 福建省农业科学院农业工程技术研究所 | Preparation of magnetic suspended 3D microspheres and application thereof in catalyzing ozone to mineralize refractory organic matters |
| CN111939924A (en) * | 2020-08-21 | 2020-11-17 | 赣州有色冶金研究所 | Composite catalyst for ozone oxidation and preparation method thereof |
| CN112704959A (en) * | 2020-11-23 | 2021-04-27 | 安徽元琛环保科技股份有限公司 | Preparation method of denitration and dedusting integrated filter material and prepared filter material |
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| CN114797887A (en) * | 2021-01-21 | 2022-07-29 | 广东卓信环境科技股份有限公司 | Ozone catalyst and preparation method and application thereof |
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| CN111841659A (en) * | 2020-07-28 | 2020-10-30 | 福建省农业科学院农业工程技术研究所 | Preparation of magnetic suspended 3D microspheres and application thereof in catalyzing ozone to mineralize refractory organic matters |
| CN111939924A (en) * | 2020-08-21 | 2020-11-17 | 赣州有色冶金研究所 | Composite catalyst for ozone oxidation and preparation method thereof |
| CN112704959A (en) * | 2020-11-23 | 2021-04-27 | 安徽元琛环保科技股份有限公司 | Preparation method of denitration and dedusting integrated filter material and prepared filter material |
| CN114797887A (en) * | 2021-01-21 | 2022-07-29 | 广东卓信环境科技股份有限公司 | Ozone catalyst and preparation method and application thereof |
| CN114471708A (en) * | 2021-12-30 | 2022-05-13 | 北京核力同创科技有限公司 | Composite catalyst for ionizing radiation sewage treatment and preparation method and treatment process thereof |
| CN115055174A (en) * | 2022-06-29 | 2022-09-16 | 北京化工大学 | Ca-based ozone catalytic oxidation catalyst for advanced treatment of salt-containing organic wastewater and preparation method thereof |
| CN115055174B (en) * | 2022-06-29 | 2023-12-15 | 北京化工大学 | Ca-based ozone catalytic oxidation catalyst for advanced treatment of salt-containing organic wastewater and preparation method thereof |
| CN115025767A (en) * | 2022-07-08 | 2022-09-09 | 北京化工大学 | Calcium-based porous carbon sphere catalyst for ozone catalytic oxidation advanced treatment of salt-containing organic wastewater |
| CN115025767B (en) * | 2022-07-08 | 2023-12-15 | 北京化工大学 | Calcium-based porous carbon sphere catalyst for advanced treatment of ozone catalytic oxidation of salt-containing organic wastewater |
| CN117960251A (en) * | 2024-04-01 | 2024-05-03 | 陕西科技大学 | Catalytic filter element, preparation method and application thereof |
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