CN107744806B - Preparation method of catalyst for catalytically decomposing ozone by taking expanded graphite as carrier - Google Patents
Preparation method of catalyst for catalytically decomposing ozone by taking expanded graphite as carrier Download PDFInfo
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- CN107744806B CN107744806B CN201710970263.9A CN201710970263A CN107744806B CN 107744806 B CN107744806 B CN 107744806B CN 201710970263 A CN201710970263 A CN 201710970263A CN 107744806 B CN107744806 B CN 107744806B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 288
- 239000010439 graphite Substances 0.000 title claims abstract description 271
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 271
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 98
- 239000003054 catalyst Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 150
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 148
- 230000003647 oxidation Effects 0.000 claims abstract description 91
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 91
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 74
- 239000000126 substance Substances 0.000 claims abstract description 46
- 238000005470 impregnation Methods 0.000 claims abstract description 45
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000009830 intercalation Methods 0.000 claims abstract description 40
- 230000002687 intercalation Effects 0.000 claims abstract description 40
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 40
- 239000011572 manganese Substances 0.000 claims abstract description 40
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000011068 loading method Methods 0.000 claims abstract description 15
- 238000005576 amination reaction Methods 0.000 claims abstract description 14
- 238000005245 sintering Methods 0.000 claims abstract description 14
- 239000000243 solution Substances 0.000 claims description 101
- 239000008367 deionised water Substances 0.000 claims description 52
- 229910021641 deionized water Inorganic materials 0.000 claims description 52
- 238000003756 stirring Methods 0.000 claims description 46
- 239000007788 liquid Substances 0.000 claims description 45
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 42
- 238000005406 washing Methods 0.000 claims description 42
- 238000001914 filtration Methods 0.000 claims description 36
- 238000004821 distillation Methods 0.000 claims description 30
- 238000001035 drying Methods 0.000 claims description 29
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 28
- 239000011259 mixed solution Substances 0.000 claims description 28
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 230000010355 oscillation Effects 0.000 claims description 24
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 21
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 18
- 239000007789 gas Substances 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 18
- 239000002245 particle Substances 0.000 claims description 18
- 238000007789 sealing Methods 0.000 claims description 16
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 230000007935 neutral effect Effects 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 12
- 239000003755 preservative agent Substances 0.000 claims description 12
- 230000002335 preservative effect Effects 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 10
- XPULYJRIWWWQFM-UHFFFAOYSA-N CCO.NCCNCCN Chemical compound CCO.NCCNCCN XPULYJRIWWWQFM-UHFFFAOYSA-N 0.000 claims description 10
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 claims description 10
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 10
- 229960003330 pentetic acid Drugs 0.000 claims description 10
- 239000012286 potassium permanganate Substances 0.000 claims description 8
- 239000006185 dispersion Substances 0.000 claims description 7
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 7
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical group O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 6
- 238000003760 magnetic stirring Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical class [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 238000004064 recycling Methods 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 6
- 239000004480 active ingredient Substances 0.000 claims description 4
- 235000019441 ethanol Nutrition 0.000 claims description 2
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 16
- 230000001007 puffing effect Effects 0.000 abstract description 6
- 239000002351 wastewater Substances 0.000 abstract description 6
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 abstract description 2
- -1 cerium ion Chemical class 0.000 abstract description 2
- 229910001437 manganese ion Inorganic materials 0.000 abstract description 2
- 231100000331 toxic Toxicity 0.000 abstract description 2
- 230000002588 toxic effect Effects 0.000 abstract description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- 239000002131 composite material Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 239000012528 membrane Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000003463 adsorbent Substances 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 206010028400 Mutagenic effect Diseases 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 231100000243 mutagenic effect Toxicity 0.000 description 1
- 230000003505 mutagenic effect Effects 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0207—Pretreatment of the support
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0213—Preparation of the impregnating solution
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/344—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy
- B01J37/346—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy of microwave energy
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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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- 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
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Abstract
The invention provides a preparation method of a catalyst for catalytically decomposing ozone by taking expanded graphite as a carrier, which mainly comprises the steps of firstly sequentially carrying out ozone oxidation, chemical oxidation intercalation, diethylenetriamine amination, cerium ion impregnation loading treatment and subsequent microwave puffing treatment on flake graphite to prepare the expanded graphite loaded with active component cerium; then, the prepared expanded graphite is subjected to impregnation treatment, manganese ion loading treatment and high-temperature sintering treatment to prepare the catalyst which is prepared by using an expanded graphite carrier and loading active components of cerium and manganese. The catalyst prepared by the invention can efficiently catalyze ozone to generate hydroxyl radicals, so that organic pollutants which are difficult to degrade and highly toxic in water environment can be excellently removed, and the catalyst has good application prospect in the field of wastewater pollution treatment.
Description
Technical Field
The invention relates to a preparation method of a catalyst.
Background
With the rapid development of industrial and agricultural economy, the types of organic pollutants such as pesticides, herbicides, antibiotics, dyes and the like discharged into water environment are increasingly complex, the existing concentration of the organic pollutants is gradually increased, the organic matters are usually not easily biodegraded, are easy to accumulate in organisms, have carcinogenic and mutagenic effects, seriously affect the safety of aquatic organism systems, and simultaneously bring great challenges to the water supply safety of cities and towns and the health of human bodies. Therefore, the research and development of new processes and new technologies for economically and efficiently removing the pollutants of the organic matters difficult to be biodegraded in the water body are important in the current water pollution prevention and control work. The main technologies for removing the organic pollutants difficult to biodegrade in the water environment include adsorption, membrane separation, chemical coagulation, chemical oxidation and the like. Although the adsorption method can effectively remove organic pollutants which are difficult to degrade in the water body, the adsorbent is easy to saturate, and the problem that the adsorbent needs to be properly treated exists. Nanofiltration and reverse osmosis membrane technologies can effectively intercept and remove organic pollutants difficult to biodegrade, but the organic pollutants are easy to form a gel layer on the surface of the separation membrane, so that the separation membrane is seriously polluted. The chemical coagulation has limited effect on removing water-soluble organic pollutants and basically has no engineering application value. Meanwhile, the conventional chemical oxidation process hardly damages the molecular structure of the refractory organic pollutants, and then the organic pollutants cannot be mineralized effectively, so that the engineering treatment efficiency is poor. Compared with the above technology, the chemical advanced oxidation technology is the best choice for treating the difficultly biodegradable organic pollutants in the water environment at present.
Ozone oxidation and improved ozone oxidation in chemical advanced oxidation technology are of interest for the removal of refractory organics in water bodies. The quality of the comprehensive performance of the load type composite catalyst is a technical key influencing the application of the ozone wastewater advanced oxidation engineering. At present, the aspect of the supported composite catalyst also has a plurality of technical defects, such as the performance of the catalyst is greatly influenced by a carrier, the morphological structure, the components and the dispersity of the carrier are different, and the thermal stability and the catalytic performance of the catalyst are greatly different; the active components loaded on the carrier and the distribution and existing forms of the active components on the carrier also have obvious influence on the performance of the catalyst; the activity of the catalyst is unstable, and the environmental hazard in the preparation process is large; the metal oxide on the surface of the catalyst is lost in the solution due to leaching; in addition, Ag, Au and Pt noble metals are loaded on the carrier to prepare the composite catalyst, so that the catalytic activity of the catalyst can be improved, but the preparation cost of the catalyst is too high, and the catalyst basically has no engineering practical value. The comparative analysis of recent foreign research reports shows that the ozone catalytic activity of oxides such as cerium, manganese, cobalt and the like is worthy of recognition, and for the reaction process of ozone heterogeneous catalysis, the solid-gas-liquid three-phase interface reaction is involved, so that the surface of a catalyst carrier is required to be porous, the specific surface area is required to be large, the dispersion of active components is facilitated, the mechanical strength is high, and the performance of adsorbing ozone molecules and organic pollutants is excellent, so that the selection of the carrier for preparing the catalyst is worthy of attention.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a preparation method of a catalyst for catalytically decomposing ozone by taking expanded graphite as a carrier. Firstly, carrying out ozone pre-oxidation, chemical oxidation intercalation, amination and cerium ion loading impregnation treatment on flake graphite in sequence, and then carrying out microwave puffing treatment to prepare expanded graphite loaded with active component cerium; then carrying out impregnation treatment and manganese ion loading treatment on the expanded graphite loaded with the active component cerium, and finally sintering the expanded graphite to prepare the catalyst which takes the expanded graphite as a carrier and is loaded with the active components cerium and manganese and used for catalytically decomposing ozone.
The preparation method of the invention comprises the following steps:
(1) preparing an expanded graphite carrier loaded with a cerium active component:
ozone pre-oxidation treatment of flake graphite:
adding deionized water into a container according to the mass ratio of the crystalline flake graphite to the deionized water of 1:1.5, placing the container containing the deionized water on a magnetic stirrer, adding the crystalline flake graphite with the average particle size of 80 meshes into the container, and starting a stirring control switch of the magnetic stirrer; then inserting an ozone generator gas production pipe into the bottom of the beaker, starting a power switch of the ozone generator, wherein a gas source used by the ozone generator is pure oxygen, the amount of ozone introduced into the solution from the gas production pipe is 5mg/L, and carrying out ozone pre-oxidation on the crystalline flake graphite for 20-30 min at room temperature; after ozone pre-oxidation is finished, filtering the solution to collect flake graphite powder subjected to ozone pre-oxidation treatment, washing the flake graphite subjected to ozone pre-oxidation treatment for 3 times by using deionized water, and drying the flake graphite subjected to ozone pre-oxidation treatment at the temperature of 80-90 ℃ for 8 hours;
② chemical oxidation intercalation treatment of flake graphite by ozone preoxidation treatment:
according to perchloric acid: flake graphite: potassium permanganate: adding 70% of perchloric acid into a container, placing the container containing the perchloric acid on a magnetic stirrer, sequentially adding the crystalline flake graphite subjected to ozone pre-oxidation treatment and the potassium permanganate solid into the container, sealing the container with a preservative film, starting a stirring and heating switch of the magnetic stirrer, controlling the solution temperature to be 75-85 ℃, stirring for 30min, adding the saturated potassium dihydrogen phosphate aqueous solution into the container, adjusting the solution temperature in the container from 75-85 ℃ to 35-45 ℃, and stirring for 60-90 min at the temperature; filtering the mixed solution after the reaction is finished to collect the flake graphite powder after the chemical oxidation intercalation treatment, and fully washing the powder by using deionized water until the pH value of the washing water is neutral; then, drying the washed powder in a drying oven at the temperature of 60-70 ℃ for 24h to prepare the flake graphite subjected to chemical oxidation intercalation treatment;
③ amination treatment of the flake graphite treated by chemical oxidation intercalation:
firstly, according to the weight ratio of diethylenetriamine: the mass ratio of the absolute ethyl alcohol is 1: 50, adding diethylenetriamine into absolute ethyl alcohol at room temperature, and stirring to uniformly mix the diethylenetriamine in the absolute ethyl alcohol to prepare a diethylenetriamine ethyl alcohol solution; then, performing chemical oxidation intercalation treatment on the flake graphite: the mass ratio of the deionized water is 1: 30, adding the flake graphite subjected to the chemical oxidation intercalation treatment prepared in the second step and deionized water into a container, and performing ultrasonic dispersion treatment at room temperature for 10-15 min, wherein the ultrasonic power is 200W and the frequency is 40 kHz; then, dropwise adding a diethylenetriamine ethanol solution into a beaker filled with a chemical oxidation intercalation-treated crystalline flake graphite dispersion aqueous solution at room temperature, stirring for 48 hours at room temperature, filtering the mixed solution in the beaker, washing and filtering the collected amination-treated crystalline flake graphite particles for multiple times by using deionized water until the washing water is neutral, and finally placing the washed amination-treated crystalline flake graphite particles in an oven to be dried at 80 ℃ to prepare amination-treated crystalline flake graphite;
loading of cerium active component
Firstly, preparing a cerium nitrate solution with the concentration of 0.1mol/L, pH of 5.3, then adding 1g of aminated crystalline flake graphite into each 100mL of cerium nitrate solution, placing the aminated crystalline flake graphite and the cerium nitrate solution obtained in the third step into a container, sealing the opening of the container, placing the container into a constant-temperature shaking table incubator, and carrying out oscillation reaction at room temperature for 24 hours; then filtering the oscillation liquid to collect the flake graphite loaded with the active component cerium, washing the collected flake graphite loaded with the active component cerium for 3 times by using deionized water, and then placing the flake graphite in an oven to carry out drying treatment at the temperature of 80 ℃ to prepare the flake graphite loaded with the active component cerium;
preparation of expanded graphite carrier loaded with active component cerium
Placing the crystalline flake graphite loaded with the active component cerium in a crucible, then placing the crucible in a microwave oven with power of 1300W, starting a power switch, and carrying out microwave treatment on the crystalline flake graphite loaded with the active component cerium for 90s to prepare an expanded graphite carrier used for preparing the catalyst and loaded with the active component cerium on the surface;
(2) impregnation treatment of expanded graphite loaded with an active component cerium:
preparing raw materials for an expanded graphite impregnation liquid loaded with an active component cerium:
the raw materials for preparing the expanded graphite impregnation liquid loading the active component cerium comprise tetrahydrofuran, butyl titanate, 3-aminopropyl trimethoxy silane, dimethyl sulfoxide and diethylenetriamine pentaacetic acid, and the dosage of the raw materials is in the following mass proportion relation: tetrahydrofuran: butyl titanate: 3-aminopropyltrimethoxysilane: dimethyl sulfoxide: diethylenetriaminepentaacetic acid 10: 4-5: 1.0-1.2: 25-30: 0.5-0.8:
preparing the impregnation liquid:
a. firstly, pouring tetrahydrofuran into a container, then adding butyl titanate and 3-aminopropyl trimethoxy silane into tetrahydrofuran solution, sealing the container by using a preservative film, magnetically stirring for 24 hours at room temperature, and obtaining a viscous colloidal solution of butyl titanate-3-aminopropyl trimethoxy silane;
b. then placing the mixed solution of the butyl titanate-3-aminopropyl trimethoxy silane into a distillation flask for distillation treatment and recycling tetrahydrofuran, controlling the temperature to be 66 ℃ in the distillation process, stopping distillation when the volume of the mixed solution of the butyl titanate-3-aminopropyl trimethoxy silane is reduced by 85%, and cooling the temperature of the distillation flask to room temperature;
c. adding a dimethyl sulfoxide solvent into a container, carrying out ultrasonic treatment on the container for 20-30 min at room temperature, then placing the container on a multifunctional stirrer, adding diethylenetriamine pentaacetic acid into a beaker, controlling the temperature of the solution in the beaker to be 80-90 ℃, and carrying out magnetic stirring reaction for 4 h; then closing a power switch of the stirrer, and naturally cooling the solution to room temperature to prepare a solution for preparing the expanded graphite carrier loaded with the active component cerium for impregnation;
impregnation treatment of expanded graphite loaded with active component cerium:
placing the expanded graphite carrier loaded with the active component cerium prepared in the step (1) into the impregnation liquid according to the proportion that 1g of the expanded graphite carrier loaded with the active component cerium is added into every 100mL of the impregnation liquid, soaking the expanded graphite carrier at room temperature for 12 hours, taking the expanded graphite carrier out, standing and draining the residual impregnation liquid on the expanded graphite carrier loaded with the active component cerium, and then placing the expanded graphite carrier in an oven for drying treatment at 80 ℃;
(3) loading of an active ingredient manganese on the expanded graphite loaded with the active ingredient cerium:
firstly, preparing a manganese nitrate solution with the concentration of 0.1-0.3 mol/L, pH of 5.6, then adding 1g of expanded graphite loaded with active component cerium into every 150mL of the manganese nitrate solution, placing the expanded graphite loaded with active component cerium and the manganese nitrate solution which are soaked and dried in the step (2) into a container, sealing the opening of the container, placing the container into a constant-temperature shaking incubator, and carrying out oscillation reaction at room temperature for 24 hours; then filtering the oscillation liquid, collecting the solid expanded graphite loaded with active components cerium and manganese, washing the collected expanded graphite loaded with active components cerium and manganese for 3 times by using deionized water, and then placing the washed expanded graphite in an oven to be dried at the temperature of 80 ℃ to prepare an expanded graphite carrier loaded with active components cerium and manganese;
(4) sintering treatment of the expanded graphite loaded with active components of cerium and manganese:
placing the expanded graphite loaded with active components cerium and manganese in the step (3) in a high-temperature electric furnace, starting a heating switch of the electric furnace, slowly increasing the temperature from room temperature to 150 ℃ at a heating rate of 1 ℃/min, and preserving the heat for 3 hours at the temperature; then, the temperature is increased from 150 ℃ to 500 ℃ at the temperature increase rate of 5 ℃/min, and the heat preservation treatment is carried out for 5h at 500 ℃; and then, turning off the power supply of the electric furnace, and taking out the expanded graphite loaded with the active components cerium and manganese after the thermal sintering treatment after the temperature of the hearth of the electric furnace is naturally cooled to room temperature, thereby preparing the catalyst which takes the expanded graphite as a carrier and is used for catalytically decomposing ozone and loaded with the active components cerium and manganese.
Compared with the prior art, the invention has the following advantages:
1. the process is simple and the cost is low;
2. the prepared catalyst taking the expanded graphite as the carrier has no potential harm to a water environment, the surface and the inside of the catalyst have developed network-shaped pore system structures, the catalyst has large specific surface area, rich active point positions for adsorption and excellent adsorption performance on organic pollutants;
3. cerium and manganese active components are uniformly loaded on the surface and inside of the prepared catalyst, so that ozone in a liquid phase can be effectively catalyzed to generate hydroxyl radicals, the treatment efficiency of ozone-degraded organic pollutants is greatly improved, the organic pollutants which are difficult to degrade and highly toxic in a water environment are well removed, and the application prospect of the catalyst in the field of wastewater pollution treatment is good.
Drawings
Fig. 1 is a graph comparing the removal rates of phenol and total organic carbon using the catalyst for catalytically decomposing ozone using expanded graphite as a carrier, which was prepared in example 1 of the present invention, with that without using the present catalyst.
Detailed Description
Example 1
(1) Preparing an expanded graphite carrier loaded with a cerium active component:
firstly, carrying out ozone pre-oxidation treatment on flake graphite: adding 150g of deionized water into a beaker with the volume of 500mL, placing the beaker filled with the deionized water on a multifunctional stirrer, then adding 100g of crystalline flake graphite with the particle size of 80 meshes into the beaker, and starting a stirring control switch of the stirrer; then inserting an ozone generator gas production pipe into the bottom of the beaker, starting a power switch of the ozone generator, wherein a gas source used by the ozone generator is pure oxygen, the amount of ozone introduced into the solution from the gas production pipe is 5mg/L, and carrying out ozone pre-oxidation on the crystalline flake graphite for 20min at room temperature; after ozone pre-oxidation is finished, filtering the solution to collect flake graphite powder subjected to ozone pre-oxidation treatment, washing the flake graphite subjected to ozone pre-oxidation treatment for 3 times by using deionized water, and drying the flake graphite subjected to ozone pre-oxidation treatment at the temperature of 80 ℃ for 8 hours;
secondly, carrying out chemical oxidation intercalation treatment on the flake graphite subjected to ozone pre-oxidation treatment: firstly, adding 25g of perchloric acid with the mass concentration of 70% into a beaker with the volume of 200mL, placing the beaker filled with the perchloric acid on a multifunctional stirrer, then sequentially adding 3g of flake graphite subjected to ozone preoxidation and drying treatment and 1.5g of potassium permanganate solid into the beaker, sealing the opening of the beaker by using a preservative film, starting a stirring and heating switch of the stirrer, controlling the temperature of the solution to be 75 ℃, adding 50g of saturated potassium dihydrogen phosphate aqueous solution into the beaker after stirring and reacting for 30min, adjusting the temperature of the solution in the beaker from 75 ℃ to 35 ℃, and stirring and reacting for 60min at the temperature; filtering the mixed solution after the reaction is finished to collect the flake graphite powder after the chemical oxidation intercalation treatment, and fully washing the powder by using deionized water until the pH value of the washing water is neutral; then, putting the washed powder into a drying oven to be dried for 24 hours at the temperature of 60 ℃ to prepare the flake graphite after the chemical oxidation intercalation treatment;
then, carrying out amination treatment on the flake graphite subjected to chemical oxidation intercalation treatment: firstly, preparing a diethylenetriamine ethanol solution, adding 1g of diethylenetriamine into 50g of absolute ethanol at room temperature, and stirring to uniformly mix the diethylenetriamine in the absolute ethanol; then adding 150g of deionized water into a beaker, adding 5g of flake graphite subjected to chemical oxidation intercalation treatment into the beaker, and carrying out ultrasonic dispersion treatment at room temperature for 10min, wherein the ultrasonic power is 200W and the frequency is 40 kHz; then dropwise adding the diethylenetriamine ethanol solution into a beaker filled with the scale graphite dispersion aqueous solution subjected to the chemical oxidation intercalation treatment at room temperature, and stirring for 48 hours at room temperature; stirring for 48h, filtering the mixed solution in the beaker, washing the aminated crystalline flake graphite particles collected by filtering with deionized water for multiple times until the washing water is neutral, and finally placing the washed aminated crystalline flake graphite particles in a drying oven to be dried at 80 ℃ to prepare aminated crystalline flake graphite;
then carrying out loading of a cerium active component: firstly, preparing a cerium nitrate solution with the concentration of 0.1mol/L, pH of 5.3, then placing 1g of aminated flake graphite into a flask containing 100mL of the cerium nitrate solution, placing the flask into a constant-temperature shaking table incubator after the flask mouth is sealed, and carrying out oscillation reaction for 24 hours at room temperature; then filtering the oscillation liquid to collect the crystalline flake graphite loaded with the active component cerium, washing the collected crystalline flake graphite loaded with the active component cerium for 3 times by using deionized water, and then placing the crystalline flake graphite in an oven to be dried at the temperature of 80 ℃ to prepare the crystalline flake graphite loaded with the active component cerium;
and finally, performing microwave puffing treatment on the treated flake graphite: placing 0.3g of the crystalline flake graphite loaded with the active component cerium into a crucible with the volume of 200mL, then placing the crucible into a household microwave oven with the power of 1300W, starting a power switch, and carrying out microwave treatment on the crystalline flake graphite loaded with the active component cerium for 90s to prepare an expanded graphite carrier used for preparing the catalyst and loaded with the active component cerium on the surface;
(2) impregnation treatment of expanded graphite loaded with an active component cerium:
firstly, preparing an expanded graphite impregnation liquid loaded with an active component cerium: pouring 10g of tetrahydrofuran into a container, then adding 4g of butyl titanate and 1.0g of 3-aminopropyltrimethoxysilane into the solution, sealing the container by using a preservative film, and magnetically stirring for 24 hours at room temperature, wherein the solution is viscous and colloidal, and thus the mixed solution of butyl titanate-3-aminopropyltrimethoxysilane is prepared; then placing the mixed solution of the butyl titanate-3-aminopropyl trimethoxy silane into a distillation flask for distillation treatment and recycling tetrahydrofuran, controlling the temperature to be 66 ℃ in the distillation process, stopping distillation when the volume of the mixed solution of the butyl titanate-3-aminopropyl trimethoxy silane is reduced by 85%, and cooling the temperature of the distillation flask to room temperature; then adding 25g of dimethyl sulfoxide solvent into the flask, carrying out ultrasonic treatment on the flask for 20min at room temperature, transferring and pouring the solution in the flask into a beaker, then placing the beaker on a multifunctional stirrer, adding 0.5g of diethylenetriamine pentaacetic acid into the beaker, controlling the temperature of the solution in the beaker to be 80 ℃, and carrying out magnetic stirring reaction for 4 h; then closing a power switch of the stirrer, and naturally cooling the solution to room temperature to prepare a solution for impregnating the expanded graphite carrier loaded with the active component cerium;
then carrying out impregnation treatment on the expanded graphite loaded with the active component cerium, firstly putting 1g of the expanded graphite carrier loaded with the active component cerium into 100mL of impregnation liquid, soaking at room temperature for 12h, then taking out the impregnated liquid, standing to drain the residual impregnation liquid on the expanded graphite carrier loaded with the active component cerium, and then putting the impregnated liquid in an oven to carry out drying treatment at 80 ℃;
(3) impregnating expanded graphite loaded with an active component cerium with active component manganese:
firstly, manganese nitrate solution with the concentration of 0.1mol/L, pH being 5.6 is prepared, then 1g of dipped and dried expanded graphite loaded with active component cerium is placed in a 150mL manganese nitrate solution flask, the flask mouth is sealed and placed in a constant temperature shaking table incubator, and oscillation reaction is carried out for 24 hours at room temperature; then filtering the oscillation liquid, collecting the solid expanded graphite loaded with active components cerium and manganese, washing the collected expanded graphite loaded with active components cerium and manganese for 3 times by using deionized water, and then placing the washed expanded graphite in an oven to be dried at the temperature of 80 ℃ to prepare an expanded graphite carrier loaded with active components cerium and manganese;
(4) sintering treatment of the expanded graphite loaded with active components of cerium and manganese:
placing the expanded graphite loaded with active components of cerium and manganese in a high-temperature electric furnace, starting a heating switch of the electric furnace, slowly raising the temperature from room temperature to 150 ℃ at a heating rate of 1 ℃/min, and preserving the heat for 3 hours at the temperature; then, the temperature is increased from 150 ℃ to 500 ℃ at the temperature increase rate of 5 ℃/min, and the heat preservation treatment is carried out for 5h at 500 ℃; and then, turning off the power supply of the electric furnace, and taking out the expanded graphite subjected to thermal sintering treatment after the temperature of the hearth of the electric furnace is naturally cooled to room temperature to prepare the catalyst which takes the expanded graphite as a carrier and loads active components of cerium and manganese for catalytically decomposing ozone.
Preparing phenol wastewater with pH value of 5 and concentration of 80mg/L, introducing ozone into the phenol wastewater at room temperature to make the concentration of the ozone in the solution be 5mg/L, adding 0.2g of the prepared composite catalyst into the phenol wastewater, and reacting for 1h to obtain the removal effect shown in figure 1, wherein the removal rate of phenol is 94% and the removal rate of total organic carbon is 83%. Compared with the method without adding the catalyst, the removal rate of phenol and the removal rate of total organic carbon are respectively improved by 46 percent and 34 percent after adding the composite catalyst prepared in the embodiment. Therefore, the composite catalyst prepared in the embodiment has excellent performance of catalyzing the ozone to degrade organic pollutants.
Example 2
(1) Preparing an expanded graphite carrier loaded with a cerium active component:
firstly, carrying out ozone pre-oxidation treatment on flake graphite: firstly, 150g of deionized water is added into a beaker with the volume of 500mL, the beaker filled with the deionized water is placed on a multifunctional stirrer, then 100g of crystalline flake graphite with the particle size of 80 meshes is added into the beaker, and a stirring control switch of the stirrer is turned on; then inserting an ozone generator gas production pipe into the bottom of the beaker, starting a power switch of the ozone generator, wherein a gas source used by the ozone generator is pure oxygen, the amount of ozone introduced into the solution from the gas production pipe is 5mg/L, and carrying out ozone pre-oxidation on the crystalline flake graphite for 24min at room temperature; after ozone pre-oxidation is finished, filtering the solution to collect flake graphite powder subjected to ozone pre-oxidation treatment, washing the flake graphite subjected to ozone pre-oxidation treatment for 3 times by using deionized water, and drying the flake graphite subjected to ozone pre-oxidation treatment at the temperature of 84 ℃ for 8 hours;
secondly, carrying out chemical oxidation intercalation treatment on the flake graphite subjected to ozone pre-oxidation treatment: adding 28g of perchloric acid with the mass concentration of 70% into a beaker with the volume of 200mL, placing the beaker filled with the perchloric acid on a multifunctional stirrer, sequentially adding 3g of flake graphite subjected to ozone preoxidation and drying treatment and 1.7g of potassium permanganate solid into the beaker, sealing the opening of the beaker by using a preservative film, starting a stirring and heating switch of the stirrer, controlling the temperature of the solution to be 81 ℃, adding 53g of saturated potassium dihydrogen phosphate aqueous solution into the beaker after stirring and reacting for 30min, adjusting the temperature of the solution in the beaker from 81 ℃ to 37 ℃, and stirring and reacting for 70min at the temperature; filtering the mixed solution after the reaction is finished to collect the flake graphite powder after the chemical oxidation intercalation treatment, and fully washing the powder by using deionized water until the pH value of the washing water is neutral; then, putting the washed powder into a drying oven to be dried for 24 hours at the temperature of 63 ℃ to prepare the chemical oxidation intercalation-treated crystalline flake graphite;
then, carrying out amination treatment on the flake graphite subjected to chemical oxidation intercalation treatment: firstly, preparing a diethylenetriamine ethanol solution, namely adding 1g of diethylenetriamine into 50g of absolute ethanol at room temperature, and stirring to uniformly mix the diethylenetriamine in the absolute ethanol; then 150g of deionized water is added into a beaker, 5g of flake graphite after chemical oxidation intercalation treatment is added into the beaker, and ultrasonic dispersion treatment is carried out for 12min at room temperature, wherein the ultrasonic power is 200W, and the frequency is 40 kHz; then dropwise adding the diethylenetriamine ethanol solution into a beaker filled with the scale graphite dispersion aqueous solution subjected to the chemical oxidation intercalation treatment at room temperature, and stirring for 48 hours at room temperature; stirring for 48h, filtering the mixed solution in the beaker, washing the aminated crystalline flake graphite particles collected by filtering with deionized water for multiple times until the washing water is neutral, and finally placing the washed aminated crystalline flake graphite particles in a drying oven to be dried at 80 ℃ to prepare aminated crystalline flake graphite;
then carrying out loading of a cerium active component: firstly, preparing a cerium nitrate solution with the concentration of 0.1mol/L, pH of 5.3, then placing 1g of aminated flake graphite into a flask containing 100mL of the cerium nitrate solution, placing the flask into a constant-temperature shaking table incubator after the flask mouth is sealed, and carrying out oscillation reaction for 24 hours at room temperature; then filtering the oscillation liquid to collect the crystalline flake graphite loaded with the active component cerium, washing the collected crystalline flake graphite loaded with the active component cerium for 3 times by using deionized water, and then placing the crystalline flake graphite in an oven to be dried at the temperature of 80 ℃ to prepare the crystalline flake graphite loaded with the active component cerium;
and finally, performing microwave puffing treatment on the treated flake graphite: placing 0.3g of the crystalline flake graphite loaded with the active component cerium into a crucible with the volume of 200mL, then placing the crucible into a household microwave oven with the power of 1300W, starting a power switch, and carrying out microwave treatment on the crystalline flake graphite loaded with the active component cerium for 90s to prepare an expanded graphite carrier used for preparing the catalyst and loaded with the active component cerium on the surface;
(2) impregnation treatment of expanded graphite loaded with an active component cerium:
firstly, preparing an expanded graphite impregnation liquid loaded with an active component cerium, firstly pouring 10g of tetrahydrofuran into a container, then adding 4.4g of butyl titanate and 1.0g of 3-aminopropyltrimethoxysilane into the tetrahydrofuran solution, sealing the container by using a preservative film, and magnetically stirring for 24 hours at room temperature, wherein the solution is viscous and colloidal, thus obtaining a butyl titanate-3-aminopropyltrimethoxysilane mixed solution; then placing the mixed solution of the butyl titanate-3-aminopropyl trimethoxy silane into a distillation flask for distillation treatment and recycling tetrahydrofuran, controlling the temperature to be 66 ℃ in the distillation process, stopping distillation when the volume of the mixed solution of the butyl titanate-3-aminopropyl trimethoxy silane is reduced by 85%, and cooling the temperature of the distillation flask to room temperature; adding 27g of dimethyl sulfoxide solvent into the flask, carrying out ultrasonic treatment on the flask for 24min at room temperature, transferring and pouring the solution in the flask into a beaker, then placing the beaker on a multifunctional stirrer, adding 0.6g of diethylenetriamine pentaacetic acid into the beaker, controlling the temperature of the solution in the beaker to be 84 ℃, and carrying out magnetic stirring reaction for 4 h; then closing a power switch of the stirrer, and naturally cooling the solution to room temperature to prepare a solution for preparing the expanded graphite carrier loaded with the active component cerium for impregnation;
then carrying out impregnation treatment on the expanded graphite loaded with the active component cerium, firstly putting 1g of the expanded graphite carrier loaded with the active component cerium into 100mL of impregnation liquid, soaking at room temperature for 12h, then taking out the impregnated liquid, standing to drain the residual impregnation liquid on the expanded graphite carrier loaded with the active component cerium, and then putting the impregnated liquid in an oven to carry out drying treatment at 80 ℃;
(3) impregnating expanded graphite loaded with an active component cerium with active component manganese:
firstly, manganese nitrate solution with the concentration of 0.15mol/L, pH being 5.6 is prepared, then 1g of dipped and dried expanded graphite loaded with active component cerium is placed in a 150mL manganese nitrate solution flask, the flask mouth is sealed and placed in a constant temperature shaking table incubator, and oscillation reaction is carried out for 24 hours at room temperature; then filtering the oscillation liquid, collecting the solid expanded graphite loaded with active components cerium and manganese, washing the collected expanded graphite loaded with active components cerium and manganese for 3 times by using deionized water, and then placing the washed expanded graphite in an oven to be dried at the temperature of 80 ℃ to prepare an expanded graphite carrier loaded with active components cerium and manganese;
(4) sintering treatment of the expanded graphite loaded with active components of cerium and manganese:
placing the expanded graphite loaded with active components of cerium and manganese in a high-temperature electric furnace, starting a heating switch of the electric furnace, slowly raising the temperature from room temperature to 150 ℃ at a heating rate of 1 ℃/min, and preserving the heat for 3 hours at the temperature; then, the temperature is increased from 150 ℃ to 500 ℃ at the temperature increase rate of 5 ℃/min, and the heat preservation treatment is carried out for 5h at 500 ℃; and then, turning off the power supply of the electric furnace, and taking out the expanded graphite subjected to thermal sintering treatment after the temperature of the hearth of the electric furnace is naturally cooled to room temperature to prepare the catalyst which takes the expanded graphite as a carrier and loads active components of cerium and manganese for catalytically decomposing ozone.
Example 3
(1) Preparing an expanded graphite carrier loaded with a cerium active component:
firstly, carrying out ozone pre-oxidation treatment on flake graphite: firstly, 150g of deionized water is added into a beaker with the volume of 500mL, the beaker filled with the deionized water is placed on a multifunctional stirrer, then 100g of crystalline flake graphite with the particle size of 80 meshes is added into the beaker, and a stirring control switch of the stirrer is turned on; then inserting an ozone generator gas production pipe into the bottom of the beaker, starting a power switch of the ozone generator, wherein a gas source used by the ozone generator is pure oxygen, the amount of ozone introduced into the solution from the gas production pipe is 5mg/L, and carrying out ozone pre-oxidation on the crystalline flake graphite for 27min at room temperature; after ozone pre-oxidation is finished, filtering the solution to collect flake graphite powder subjected to ozone pre-oxidation treatment, washing the flake graphite subjected to ozone pre-oxidation treatment for 3 times by using deionized water, and drying the flake graphite subjected to ozone pre-oxidation treatment at the temperature of 87 ℃ for 8 hours;
secondly, carrying out chemical oxidation intercalation treatment on the flake graphite subjected to ozone pre-oxidation treatment: adding 32g of perchloric acid with the mass concentration of 70% into a beaker with the volume of 200mL, placing the beaker filled with the perchloric acid on a multifunctional stirrer, sequentially adding 3g of flake graphite subjected to ozone preoxidation and drying treatment and 1.8g of potassium permanganate solid into the beaker, sealing the opening of the beaker by using a preservative film, starting a stirring and heating switch of the stirrer, controlling the temperature of the solution to be 83 ℃, adding 57g of saturated potassium dihydrogen phosphate aqueous solution into the beaker after stirring and reacting for 30min, adjusting the temperature of the solution in the beaker from 83 ℃ to 42 ℃, and stirring and reacting for 80min at the temperature; filtering the mixed solution after the reaction is finished to collect the flake graphite powder after the chemical oxidation intercalation treatment, and fully washing the powder by using deionized water until the pH value of the washing water is neutral; then, putting the washed powder into a drying oven to be dried for 24 hours at the temperature of 67 ℃ to prepare the flake graphite after the chemical oxidation intercalation treatment;
then carrying out amination treatment on the flake graphite by chemical oxidation intercalation treatment: firstly, preparing a diethylenetriamine ethanol solution, namely adding 1g of diethylenetriamine into 50g of absolute ethanol at room temperature, and stirring to uniformly mix the diethylenetriamine in the absolute ethanol; then adding 150g of deionized water into a beaker, adding 5g of flake graphite subjected to chemical oxidation intercalation treatment into the beaker, and carrying out ultrasonic dispersion treatment at room temperature for 13min, wherein the ultrasonic power is 200W and the frequency is 40 kHz; then dropwise adding the diethylenetriamine ethanol solution into a beaker filled with the scale graphite dispersion aqueous solution subjected to the chemical oxidation intercalation treatment at room temperature, and stirring for 48 hours at room temperature; stirring for 48h, filtering the mixed solution in the beaker, washing the aminated crystalline flake graphite particles collected by filtering with deionized water for multiple times until the washing water is neutral, and finally placing the washed aminated crystalline flake graphite particles in a drying oven to be dried at 80 ℃ to prepare aminated crystalline flake graphite;
then loading cerium active components, firstly preparing a cerium nitrate solution with the concentration of 0.1mol/L, pH of 5.3, then placing 1g of aminated flake graphite into a flask containing 100mL of the cerium nitrate solution, placing the flask into a constant-temperature shaking table incubator after the flask mouth is sealed, and carrying out oscillation reaction for 24 hours at room temperature; then filtering the oscillation liquid to collect the crystalline flake graphite powder loaded with the active component cerium, firstly washing the collected crystalline flake graphite loaded with the active component cerium for 3 times by using deionized water, and then placing the crystalline flake graphite into an oven to be dried at the temperature of 80 ℃ to prepare the crystalline flake graphite loaded with the active component cerium;
and finally, performing microwave puffing treatment on the treated flake graphite: placing 0.3g of the crystalline flake graphite loaded with the active component cerium into a crucible with the volume of 200mL, then placing the crucible into a household microwave oven with the power of 1300W, starting a power switch, and carrying out microwave treatment on the crystalline flake graphite loaded with the active component cerium for 90s to prepare an expanded graphite carrier used for preparing the catalyst and loaded with the active component cerium on the surface;
(2) impregnation treatment of expanded graphite loaded with an active component cerium:
firstly, preparing an expanded graphite impregnation liquid loaded with an active component cerium, firstly pouring 10g of tetrahydrofuran into a container, then adding 4.7g of butyl titanate and 1.2g of 3-aminopropyltrimethoxysilane into the tetrahydrofuran solution, sealing the container by using a preservative film, and magnetically stirring for 24 hours at room temperature, wherein the solution is viscous and colloidal, thus obtaining a butyl titanate-3-aminopropyltrimethoxysilane mixed solution; then placing the mixed solution of the butyl titanate-3-aminopropyl trimethoxy silane into a distillation flask for distillation treatment and recycling tetrahydrofuran, controlling the temperature to be 66 ℃ in the distillation process, stopping distillation when the volume of the mixed solution of the butyl titanate-3-aminopropyl trimethoxy silane is reduced by 85%, and cooling the temperature of the distillation flask to room temperature; then adding 28g of dimethyl sulfoxide solvent into the flask, carrying out ultrasonic treatment on the flask for 27min at room temperature, transferring and pouring the solution in the flask into a beaker, then placing the beaker on a multifunctional stirrer, adding 0.7g of diethylenetriamine pentaacetic acid into the beaker, controlling the temperature of the solution in the beaker to be 87 ℃, and carrying out magnetic stirring reaction for 4 h; then closing a power switch of the stirrer, and naturally cooling the solution to room temperature to prepare a solution for preparing the expanded graphite carrier loaded with the active component cerium for impregnation;
then carrying out impregnation treatment on the expanded graphite loaded with the active component cerium, firstly putting 1g of the expanded graphite carrier loaded with the active component cerium into 100mL of impregnation liquid, soaking at room temperature for 12h, then taking out the impregnated liquid, standing to drain the residual impregnation liquid on the expanded graphite carrier loaded with the active component cerium, and then putting the impregnated liquid in an oven to carry out drying treatment at 80 ℃;
(3) impregnating expanded graphite loaded with an active component cerium with active component manganese:
firstly, manganese nitrate solution with the concentration of 0.2mol/L, pH being 5.6 is prepared, then 1g of dipped and dried expanded graphite loaded with active component cerium is placed in a 150mL manganese nitrate solution flask, the flask mouth is sealed and placed in a constant temperature shaking table incubator, and oscillation reaction is carried out for 24 hours at room temperature; then filtering the oscillation liquid, collecting the solid expanded graphite loaded with active components cerium and manganese, washing the collected expanded graphite loaded with active components cerium and manganese for 3 times by using deionized water, and then placing the washed expanded graphite in an oven to be dried at the temperature of 80 ℃, thus preparing the expanded graphite carrier loaded with active components cerium and manganese;
(4) sintering treatment of the expanded graphite loaded with active components of cerium and manganese:
placing the expanded graphite loaded with active components of cerium and manganese in a high-temperature electric furnace, starting a heating switch of the electric furnace, slowly raising the temperature from room temperature to 150 ℃ at a heating rate of 1 ℃/min, and preserving the heat for 3 hours at the temperature; then, the temperature is increased from 150 ℃ to 500 ℃ at the temperature increase rate of 5 ℃/min, and the heat preservation treatment is carried out for 5h at 500 ℃; and then, turning off the power supply of the electric furnace, and taking out the expanded graphite subjected to thermal sintering treatment after the temperature of the hearth of the electric furnace is naturally cooled to room temperature to prepare the catalyst which takes the expanded graphite as a carrier and loads active components of cerium and manganese for catalytically decomposing ozone.
Example 4
(1) Preparing an expanded graphite carrier loaded with a cerium active component:
firstly, carrying out ozone pre-oxidation treatment on flake graphite: firstly, 150g of deionized water is added into a beaker with the volume of 500mL, the beaker filled with the deionized water is placed on a multifunctional stirrer, then 100g of crystalline flake graphite with the particle size of 80 meshes is added into the beaker, and a stirring control switch of the stirrer is turned on; then inserting an ozone generator gas production pipe into the bottom of the beaker, starting a power switch of the ozone generator, wherein a gas source used by the ozone generator is pure oxygen, the amount of ozone introduced into the solution from the gas production pipe is 5mg/L, and carrying out ozone pre-oxidation on the crystalline flake graphite for 30min at room temperature; after ozone pre-oxidation is finished, filtering the solution to collect flake graphite powder subjected to ozone pre-oxidation treatment, washing the flake graphite subjected to ozone pre-oxidation treatment for 3 times by using deionized water, and drying the flake graphite subjected to ozone pre-oxidation treatment at the temperature of 90 ℃ for 8 hours;
secondly, carrying out chemical oxidation intercalation treatment on the flake graphite subjected to ozone pre-oxidation treatment: adding 35g of perchloric acid with the mass concentration of 70% into a beaker with the volume of 200mL, placing the beaker filled with the perchloric acid on a multifunctional stirrer, sequentially adding 3g of flake graphite subjected to ozone preoxidation and drying treatment and 2.0g of potassium permanganate solid into the beaker, sealing the opening of the beaker by using a preservative film, starting a stirring and heating switch of the stirrer, controlling the temperature of the solution to be 85 ℃, adding 60g of saturated potassium dihydrogen phosphate aqueous solution into the beaker after stirring and reacting for 30min, adjusting the temperature of the solution in the beaker from 85 ℃ to 45 ℃, and stirring and reacting for 90min at the temperature; filtering the mixed solution after the reaction is finished to collect the flake graphite powder after the chemical oxidation intercalation treatment, and fully washing the powder by using deionized water until the pH value of the washing water is neutral; then, putting the washed powder into a drying oven to dry for 24 hours at the temperature of 70 ℃ to prepare the flake graphite after the chemical oxidation intercalation treatment;
then, carrying out amination treatment on the flake graphite subjected to chemical oxidation intercalation treatment: firstly, preparing a diethylenetriamine ethanol solution, adding 1g of diethylenetriamine into 50g of absolute ethanol at room temperature, and stirring to uniformly mix the diethylenetriamine in the absolute ethanol; then adding 150g of deionized water into a beaker, adding 5g of flake graphite subjected to chemical oxidation intercalation treatment into the beaker, and carrying out ultrasonic dispersion treatment for 15min at room temperature, wherein the ultrasonic power is 200W and the frequency is 40 kHz; then dropwise adding the diethylenetriamine ethanol solution into a beaker filled with the scale graphite dispersion aqueous solution subjected to the chemical oxidation intercalation treatment at room temperature, and stirring for 48 hours at room temperature; stirring for 48h, filtering the mixed solution in the beaker, washing the aminated crystalline flake graphite particles collected by filtering with deionized water for multiple times until the washing water is neutral, and finally placing the washed aminated crystalline flake graphite particles in a drying oven to be dried at 80 ℃ to prepare aminated crystalline flake graphite;
then carrying out loading of a cerium active component: firstly, preparing a cerium nitrate solution with the concentration of 0.1mol/L, pH of 5.3, then placing 1g of aminated flake graphite into a flask containing 100mL of the cerium nitrate solution, placing the flask into a constant-temperature shaking table incubator after the flask mouth is sealed, and carrying out oscillation reaction for 24 hours at room temperature; then filtering the oscillation liquid to collect the crystalline flake graphite loaded with the active component cerium, washing the collected crystalline flake graphite loaded with the active component cerium for 3 times by using deionized water, and then placing the crystalline flake graphite in an oven to be dried at the temperature of 80 ℃ to prepare the crystalline flake graphite loaded with the active component cerium;
and finally, performing microwave puffing treatment on the treated flake graphite: placing 0.3g of the crystalline flake graphite loaded with the active component cerium into a crucible with the volume of 200mL, then placing the crucible into a household microwave oven with the power of 1300W, starting a power switch, and carrying out microwave treatment on the crystalline flake graphite loaded with the active component cerium for 90s to prepare an expanded graphite carrier used for preparing the catalyst and loaded with the active component cerium on the surface;
(2) impregnation treatment of expanded graphite loaded with an active component cerium:
firstly, preparing an expanded graphite impregnation liquid loaded with an active component cerium, firstly pouring 10g of tetrahydrofuran into a container, then adding 5g of butyl titanate and 1.2g of 3-aminopropyltrimethoxysilane into the tetrahydrofuran solution, sealing the container by using a preservative film, magnetically stirring for 24 hours at room temperature, and obtaining a butyl titanate-3-aminopropyltrimethoxysilane mixed solution, wherein the solution is sticky and colloidal; then placing the mixed solution of the butyl titanate-3-aminopropyl trimethoxy silane into a distillation flask for distillation treatment and recycling tetrahydrofuran, controlling the temperature to be 66 ℃ in the distillation process, stopping distillation when the volume of the mixed solution of the butyl titanate-3-aminopropyl trimethoxy silane is reduced by 85%, and cooling the temperature of the distillation flask to room temperature; then adding 30g of dimethyl sulfoxide solvent into the flask, carrying out ultrasonic treatment on the flask for 30min at room temperature, transferring and pouring the solution in the flask into a beaker, then placing the beaker on a multifunctional stirrer, adding 0.8g of diethylenetriamine pentaacetic acid into the beaker, controlling the temperature of the solution in the beaker to be 90 ℃, and carrying out magnetic stirring reaction for 4 h; then closing a power switch of the stirrer, and naturally cooling the solution to room temperature to prepare a solution for preparing the expanded graphite carrier loaded with the active component cerium for impregnation;
then carrying out impregnation treatment on the expanded graphite loaded with the active component cerium, firstly putting 1g of the expanded graphite carrier loaded with the active component cerium into 100mL of impregnation liquid, soaking at room temperature for 12h, then taking out the impregnated liquid, standing to drain the residual impregnation liquid on the expanded graphite carrier loaded with the active component cerium, and then putting the impregnated liquid in an oven to carry out drying treatment at 80 ℃;
(3) impregnating expanded graphite loaded with an active component cerium with active component manganese:
firstly, manganese nitrate solution with the concentration of 0.3mol/L, pH being 5.6 is prepared, then 1g of dipped and dried expanded graphite loaded with active component cerium is placed in a 150mL manganese nitrate solution flask, the flask mouth is sealed and placed in a constant temperature shaking table incubator, and oscillation reaction is carried out for 24 hours at room temperature; then filtering the oscillation liquid, collecting the solid expanded graphite loaded with active components cerium and manganese, washing the collected expanded graphite loaded with active components cerium and manganese for 3 times by using deionized water, and then placing the washed expanded graphite in an oven to be dried at the temperature of 80 ℃ to prepare an expanded graphite carrier loaded with active components cerium and manganese;
(4) sintering treatment of the expanded graphite loaded with active components of cerium and manganese:
placing the expanded graphite loaded with active components of cerium and manganese in a high-temperature electric furnace, starting a heating switch of the electric furnace, slowly raising the temperature from room temperature to 150 ℃ at a heating rate of 1 ℃/min, and preserving the heat for 3 hours at the temperature; then, the temperature is increased from 150 ℃ to 500 ℃ at the temperature increase rate of 5 ℃/min, and the heat preservation treatment is carried out for 5h at 500 ℃; and then, turning off the power supply of the electric furnace, and taking out the expanded graphite subjected to thermal sintering treatment after the temperature of the hearth of the electric furnace is naturally cooled to room temperature, thus preparing the catalyst which takes the expanded graphite as a carrier and loads active components of cerium and manganese for catalytically decomposing ozone.
Claims (1)
1. A preparation method of a catalyst for catalytically decomposing ozone by taking expanded graphite as a carrier is characterized by comprising the following steps of: the preparation method comprises the following steps:
(1) preparing an expanded graphite carrier loaded with a cerium active component:
ozone pre-oxidation treatment of flake graphite:
adding deionized water into a container according to the mass ratio of the crystalline flake graphite to the deionized water of 1:1.5, placing the container containing the deionized water on a magnetic stirrer, adding the crystalline flake graphite with the average particle size of 80 meshes into the container, and starting a stirring control switch of the magnetic stirrer; then inserting an ozone generator gas production pipe into the bottom of the beaker, starting a power switch of the ozone generator, wherein a gas source used by the ozone generator is pure oxygen, the amount of ozone introduced into the solution from the gas production pipe is 5mg/L, and carrying out ozone pre-oxidation on the crystalline flake graphite for 20-30 min at room temperature; after ozone pre-oxidation is finished, filtering the solution to collect flake graphite powder subjected to ozone pre-oxidation treatment, washing the flake graphite subjected to ozone pre-oxidation treatment for 3 times by using deionized water, and drying the flake graphite subjected to ozone pre-oxidation treatment at the temperature of 80-90 ℃ for 8 hours;
② chemical oxidation intercalation treatment of flake graphite by ozone preoxidation treatment:
according to perchloric acid: flake graphite: potassium permanganate: adding 70% of perchloric acid into a container, placing the container containing the perchloric acid on a magnetic stirrer, sequentially adding the crystalline flake graphite subjected to ozone pre-oxidation treatment and the potassium permanganate solid into the container, sealing the container with a preservative film, starting a stirring and heating switch of the magnetic stirrer, controlling the solution temperature to be 75-85 ℃, stirring for 30min, adding the saturated potassium dihydrogen phosphate aqueous solution into the container, adjusting the solution temperature in the container from 75-85 ℃ to 35-45 ℃, and stirring for 60-90 min at the temperature; filtering the mixed solution after the reaction is finished to collect the flake graphite powder after the chemical oxidation intercalation treatment, and fully washing the powder by using deionized water until the pH value of the washing water is neutral; then, drying the washed powder in a drying oven at the temperature of 60-70 ℃ for 24h to prepare the flake graphite subjected to chemical oxidation intercalation treatment;
③ amination treatment of the flake graphite treated by chemical oxidation intercalation:
firstly, according to the weight ratio of diethylenetriamine: the mass ratio of the absolute ethyl alcohol is 1: 50, adding diethylenetriamine into absolute ethyl alcohol at room temperature, and stirring to uniformly mix the diethylenetriamine and the absolute ethyl alcohol to prepare a diethylenetriamine ethyl alcohol solution; then, performing chemical oxidation intercalation treatment on the flake graphite: the mass ratio of the deionized water is 1: 30, adding the flake graphite subjected to the chemical oxidation intercalation treatment prepared in the second step and deionized water into a container, and performing ultrasonic dispersion treatment at room temperature for 10-15 min, wherein the ultrasonic power is 200W and the frequency is 40 kHz; then, dropwise adding a diethylenetriamine ethanol solution into a beaker filled with a chemical oxidation intercalation-treated crystalline flake graphite dispersion aqueous solution at room temperature, stirring for 48 hours at room temperature, filtering the mixed solution in the beaker, washing and filtering the collected amination-treated crystalline flake graphite particles for multiple times by using deionized water until the washing water is neutral, and finally placing the washed amination-treated crystalline flake graphite particles in an oven to be dried at 80 ℃ to prepare amination-treated crystalline flake graphite;
loading of cerium active component
Firstly, preparing a cerium nitrate solution with the concentration of 0.1mol/L, pH of 5.3, then adding 1g of aminated crystalline flake graphite into each 100mL of cerium nitrate solution, placing the aminated crystalline flake graphite and the cerium nitrate solution obtained in the third step into a container, sealing the opening of the container, placing the container into a constant-temperature shaking table incubator, and carrying out oscillation reaction at room temperature for 24 hours; then filtering the oscillation liquid to collect the crystalline flake graphite powder loaded with the active component cerium, washing the collected crystalline flake graphite loaded with the active component cerium for 3 times by using deionized water, and then placing the crystalline flake graphite into an oven to be dried at the temperature of 80 ℃ to prepare crystalline flake graphite loaded with the active component cerium;
preparation of expanded graphite carrier loaded with active component cerium
Placing the crystalline flake graphite loaded with the active component cerium in a crucible, then placing the crucible in a microwave oven with power of 1300W, starting a power switch, and carrying out microwave treatment on the crystalline flake graphite loaded with the active component cerium for 90s to prepare an expanded graphite carrier used for preparing the catalyst and loaded with the active component cerium on the surface;
(2) impregnation treatment of expanded graphite loaded with an active component cerium:
preparing raw materials for an expanded graphite impregnation liquid loaded with an active component cerium:
the raw materials for preparing the expanded graphite impregnation liquid loading the active component cerium comprise tetrahydrofuran, butyl titanate, 3-aminopropyl trimethoxy silane, dimethyl sulfoxide and diethylenetriamine pentaacetic acid, and the dosage of the raw materials is in the following mass proportion relation: tetrahydrofuran: butyl titanate: 3-aminopropyltrimethoxysilane: dimethyl sulfoxide: diethylenetriaminepentaacetic acid 10: 4-5: 1.0-1.2: 25-30: 0.5-0.8:
preparing the impregnation liquid:
a. firstly, pouring tetrahydrofuran into a container, then adding butyl titanate and 3-aminopropyl trimethoxy silane into tetrahydrofuran solution, sealing the container by using a preservative film, magnetically stirring for 24 hours at room temperature, and obtaining a viscous colloidal solution of butyl titanate-3-aminopropyl trimethoxy silane;
b. then placing the mixed solution of the butyl titanate-3-aminopropyl trimethoxy silane into a distillation flask for distillation treatment and recycling tetrahydrofuran, controlling the temperature to be 66 ℃ in the distillation process, stopping distillation when the volume of the mixed solution of the butyl titanate-3-aminopropyl trimethoxy silane is reduced by 85%, and cooling the temperature of the distillation flask to room temperature;
c. adding a dimethyl sulfoxide solvent into a flask, carrying out ultrasonic treatment on the flask for 20-30 min at room temperature, transferring and pouring the solution in the flask into a beaker, then placing the beaker on a multifunctional stirrer, adding diethylenetriamine pentaacetic acid into the beaker, controlling the temperature of the solution in the beaker to be 80-90 ℃, and carrying out magnetic stirring reaction for 4 h; then closing a power switch of the stirrer, and naturally cooling the solution to room temperature to prepare a solution for preparing the expanded graphite carrier loaded with the active component cerium for impregnation;
impregnation treatment of expanded graphite loaded with active component cerium:
adding 1g of expanded graphite carrier loaded with active component cerium into every 100mL of impregnation liquid, placing the expanded graphite carrier loaded with active component cerium prepared in the step (1) into the impregnation liquid, soaking at room temperature for 12h, taking out, standing, draining residual impregnation liquid on the expanded graphite carrier loaded with active component cerium, and then placing in an oven for drying treatment at 80 ℃;
(3) loading of an active ingredient manganese on the expanded graphite loaded with the active ingredient cerium:
firstly, preparing a manganese nitrate solution with the concentration of 0.1-0.3 mol/L, pH of 5.6, then adding 1g of expanded graphite loaded with active component cerium into every 150mL of the manganese nitrate solution, placing the expanded graphite loaded with active component cerium and the manganese nitrate solution which are soaked and dried in the step (2) into a container, sealing the opening of the container, placing the container into a constant-temperature shaking incubator, and carrying out oscillation reaction at room temperature for 24 hours; then filtering the oscillation liquid, collecting the solid expanded graphite loaded with active components cerium and manganese, washing the collected expanded graphite loaded with active components cerium and manganese for 3 times by using deionized water, and then placing the washed expanded graphite in an oven to be dried at the temperature of 80 ℃ to prepare an expanded graphite carrier loaded with active components cerium and manganese;
(4) sintering treatment of the expanded graphite loaded with active components of cerium and manganese:
placing the expanded graphite loaded with the active components cerium and manganese in the step (3) in a high-temperature electric furnace, starting a heating switch of the electric furnace, slowly increasing the temperature from room temperature to 150 ℃ at a heating rate of 1 ℃/min, and preserving the heat for 3 hours at the temperature; then, the temperature is increased from 150 ℃ to 500 ℃ at the temperature increase rate of 5 ℃/min, and the heat preservation treatment is carried out for 5h at 500 ℃; and then, turning off the power supply of the electric furnace, and taking out the expanded graphite subjected to thermal sintering treatment after the temperature of the hearth of the electric furnace is naturally cooled to room temperature, thus preparing the catalyst which takes the expanded graphite as a carrier and loads active components of cerium and manganese for catalytically decomposing ozone.
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| CN110575848B (en) * | 2019-09-19 | 2020-11-27 | 燕山大学 | Preparation method of catalyst for catalyzing ozone to oxidize volatile organic compounds |
| CN111068513A (en) * | 2019-12-27 | 2020-04-28 | 东华大学 | Method for treating coating waste gas by manganese-loaded expanded graphite adsorption coupling catalysis ozone oxidation |
| CN111217442B (en) * | 2020-03-19 | 2022-06-03 | 辽宁中舟得水环保科技有限公司 | Multistage ozone reaction tower |
| CN111871368A (en) * | 2020-07-06 | 2020-11-03 | 武汉科技大学 | Adsorbing material for removing rare metal ions in wastewater and preparation method thereof |
| CN114367281A (en) * | 2021-12-31 | 2022-04-19 | 江苏省环境工程技术有限公司 | Metal supported catalyst and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102335600A (en) * | 2011-07-12 | 2012-02-01 | 哈尔滨工业大学 | Preparation method of expandable graphite catalyst and method for treating ozonized water of catalysis |
| CN102701195A (en) * | 2012-06-27 | 2012-10-03 | 华南理工大学 | Method for preparing expandable graphite by using ozone |
| RU2498945C1 (en) * | 2012-06-08 | 2013-11-20 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Саратовский государственный аграрный университет имени Н.И. Вавилова" | Water treatment apparatus |
| CN105502360A (en) * | 2015-12-25 | 2016-04-20 | 燕山大学 | Preparation method of sulfur-free expansible graphite |
| KR101644565B1 (en) * | 2015-04-03 | 2016-08-02 | 한국건설기술연구원 | PVC Pipe Having High Incombustibility and Heat Extensibility and Pipe Structure Using the Same |
| CN107226520A (en) * | 2017-07-14 | 2017-10-03 | 哈尔滨工业大学 | A kind of method that catalytic ozonation removes Organic substance in water |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6503652B2 (en) * | 2000-06-29 | 2003-01-07 | Graftech Inc. | Fuel cell assembly method with selective catalyst loading |
-
2017
- 2017-10-16 CN CN201710970263.9A patent/CN107744806B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102335600A (en) * | 2011-07-12 | 2012-02-01 | 哈尔滨工业大学 | Preparation method of expandable graphite catalyst and method for treating ozonized water of catalysis |
| RU2498945C1 (en) * | 2012-06-08 | 2013-11-20 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Саратовский государственный аграрный университет имени Н.И. Вавилова" | Water treatment apparatus |
| CN102701195A (en) * | 2012-06-27 | 2012-10-03 | 华南理工大学 | Method for preparing expandable graphite by using ozone |
| KR101644565B1 (en) * | 2015-04-03 | 2016-08-02 | 한국건설기술연구원 | PVC Pipe Having High Incombustibility and Heat Extensibility and Pipe Structure Using the Same |
| CN105502360A (en) * | 2015-12-25 | 2016-04-20 | 燕山大学 | Preparation method of sulfur-free expansible graphite |
| CN107226520A (en) * | 2017-07-14 | 2017-10-03 | 哈尔滨工业大学 | A kind of method that catalytic ozonation removes Organic substance in water |
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