CN110449161A - A kind of ozone catalytic oxidation catalyst and its preparation method and application - Google Patents
A kind of ozone catalytic oxidation catalyst and its preparation method and application Download PDFInfo
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- CN110449161A CN110449161A CN201810429644.0A CN201810429644A CN110449161A CN 110449161 A CN110449161 A CN 110449161A CN 201810429644 A CN201810429644 A CN 201810429644A CN 110449161 A CN110449161 A CN 110449161A
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- ultraviolet radioactive
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- 239000003054 catalyst Substances 0.000 title claims abstract description 88
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 39
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 34
- 230000003647 oxidation Effects 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title abstract description 17
- 239000010881 fly ash Substances 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 29
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 20
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 10
- 239000011572 manganese Substances 0.000 claims abstract description 10
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 9
- 239000010941 cobalt Substances 0.000 claims abstract description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052742 iron Inorganic materials 0.000 claims abstract description 9
- 239000011575 calcium Substances 0.000 claims abstract description 7
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 5
- 239000010949 copper Substances 0.000 claims abstract description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052802 copper Inorganic materials 0.000 claims abstract description 3
- 230000002285 radioactive effect Effects 0.000 claims description 37
- 238000001035 drying Methods 0.000 claims description 29
- 239000000243 solution Substances 0.000 claims description 20
- 239000000843 powder Substances 0.000 claims description 16
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical group O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 15
- 229910017604 nitric acid Inorganic materials 0.000 claims description 15
- 238000005470 impregnation Methods 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 14
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 12
- 206010013786 Dry skin Diseases 0.000 claims description 11
- 230000005855 radiation Effects 0.000 claims description 11
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000001125 extrusion Methods 0.000 claims description 9
- 229910052731 fluorine Inorganic materials 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 7
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 6
- 239000011737 fluorine Substances 0.000 claims description 6
- 150000000921 Gadolinium Chemical class 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- 159000000007 calcium salts Chemical class 0.000 claims description 3
- 150000001868 cobalt Chemical class 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 238000007781 pre-processing Methods 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims 1
- 230000001681 protective effect Effects 0.000 abstract description 2
- 239000002910 solid waste Substances 0.000 abstract 2
- 239000007864 aqueous solution Substances 0.000 description 36
- 239000007789 gas Substances 0.000 description 26
- 238000002803 maceration Methods 0.000 description 18
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 18
- 230000000694 effects Effects 0.000 description 14
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 238000006555 catalytic reaction Methods 0.000 description 9
- 230000004048 modification Effects 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 229910002651 NO3 Inorganic materials 0.000 description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 238000007792 addition Methods 0.000 description 6
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 6
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 6
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 6
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 6
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 6
- 238000006385 ozonation reaction Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 238000003672 processing method Methods 0.000 description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- 239000003546 flue gas Substances 0.000 description 4
- -1 hydroxyl radical free radical Chemical class 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- MWFSXYMZCVAQCC-UHFFFAOYSA-N gadolinium(iii) nitrate Chemical compound [Gd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O MWFSXYMZCVAQCC-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 150000002696 manganese Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 235000008227 Illicium verum Nutrition 0.000 description 1
- 240000007232 Illicium verum Species 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000009303 advanced oxidation process reaction Methods 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000010883 coal ash Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 238000006213 oxygenation reaction Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/90—Injecting reactants
-
- 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
-
- B01J35/613—
-
- 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
-
- 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
- B01J37/34—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
- B01J37/345—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 ultraviolet wave energy
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/10—Oxidants
- B01D2251/104—Ozone
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Abstract
The invention discloses a kind of ozone catalytic oxidation catalysts and its preparation method and application.The carrier of the catalyst is flyash, and the active component includes with cobalt, manganese existing for oxide morphology, copper, iron and calcium.The flyash derives from the solid waste of power plant's discharge.The method that the present invention prepares catalyst is cheap, environmentally protective, and the catalyst for realizing the resource utilization of solid waste, while being prepared by means of the present invention has the characteristics that recycled for multiple times, catalytic activity height and stable in catalytic performance.
Description
Technical field
The present invention relates to industrial waste gas processing and environment protection catalytic Material Field, and in particular to be a kind of ozone catalytic
Oxidation catalyst and preparation method thereof can be used for handling the method for NOx exhaust gas.
Background technique
With the development of power industry, the flyash discharge capacity of coal-burning power plant increases year by year.Place is not added in a large amount of flyash
Reason will generate fugitive dust, pollute atmosphere, and accumulate by prolonged, the heavy metal element in flyash can be diffused into soil
In earth and water body, the serious existence and health that can jeopardize the mankind is caused to the development of the national economy and ecological environment in China
Huge negative effect.The specific surface area of flyash is larger, and how adsorption activity with higher realizes the resource of flyash
Change, higher value application, is the previous big problem in the urgent need to address of mesh.
NOx is one of major pollutants of atmosphere, it easily forms acid rain and photochemical fog in air, destroys ozone
Layer seriously affects ecological environment and the mankind that are detrimental to health.Traditional denitration technology using selective catalytic reduction (SCR) and
Selective non-catalytic reduction (SNCR) technology, but for the relatively low industrial furnace of some exhaust gas temperatures, sintering machine, catalytic cracking dress
It sets, SCR and SNCR are without suitable temperature window.In recent years, the high-level oxidation technologies such as ozone (AOPs) processing NOx at
For the technology of most prospects for commercial application.
Chinese publication CN 104128079A discloses a kind of ozone oxidization combination lye and absorbs processing NOx exhaust gas
Method, but individually ozone oxidation efficiency is not high, and ozone escape causes secondary pollution, and the alkali-wash waste water that lye absorption tower generates
It is handled.Compare independent ozone oxidation, under the action of catalyst, ozone can be rapidly decomposed into hydroxyl radical free radical (
OH), OH is very active, can be quickly by NO and NO2It is oxidized to the nitrogen oxides of high-valence state.Patent is rarely reported for taking off at present
The ozone catalytic oxidation catalyst of nitre needs to develop a kind of high catalytic efficiency, catalysis for the deficiency of existing ozonation technology
Performance is stable and does not generate the denitrating catalyst of secondary pollution.
Summary of the invention
The purpose of the present invention is to provide a kind of ozone catalytic oxidation catalysts.The catalyst catalysis with higher is lived
Property and stability, it is environmentally protective, it can recycled for multiple times.
It is another object of the present invention to provide the preparation methods of the catalyst.
It is another object of the present invention to provide the catalyst in the method for handling NOx exhaust gas, the processing
Method is simple and easy, and treatment effeciency is high, can be effectively treated to NOx exhaust gas, not generate secondary pollution.
To achieve the goals above, The technical solution adopted by the invention is as follows:
A kind of ozone catalytic oxidation catalyst, including carrier and active component, affiliated carrier are flyash；The active group
Dividing includes with cobalt, manganese existing for oxide form, copper, iron and calcium；It is counted on the basis of the weight of the carrier, the catalyst packet
It includes:
1.0~5.5wt% of Co, preferably 2.0~4.0wt%；
Mn0.5~4.5wt%, preferably 2.5~4.0wt%；
1.5~6.5wt% of Cu, preferably 3.0~5.0wt%；
2.5~9.5wt% of Fe, preferably 3.0~6.5wt%；
10~50wt% of Ca, preferably 20~30wt%.
Flyash is the fine ash that catching is got off from the flue gas after coal combustion.Flyash is mainly from power plant, flyash tool
There is very big specific surface area, loose porous structure has the Al of very high-content2O3And SiO2, there is good absorption property,
Therefore the carrier that can be used as catalyst uses.
In the present invention, flyash is used by pretreatment as carrier, and specific preprocess method is the following steps are included: by powder
Coal ash is ground into fine powder, and after crossing 60-200 mesh, after 600 DEG C of -800 DEG C of roasting temperature 4h-6h, washing and drying is added viscous
Agent, the preferred nitric acid solution of binder are tied, the preferred 5%-10% of concentration of nitric acid is counted, nitric acid solution dosage on the basis of carrier quality
It is preferred that 3wt%-5wt%, extrusion forming obtains pretreated carrier then in 500 DEG C of -600 DEG C of roasting temperature 3h-5h.
Preferably, it carries out ultraviolet radioactive to pretreated carrier to be modified, comprising the following steps: using at ultraviolet modified lamp radiation
Manage the pretreated carrier, ultraviolet modified lamp uses high-pressure sodium lamp, power 200-1000W, preferably 1000W, dominant wavelength 365nm,
Irradiation time is 6-12h, obtains the modified carrier of ultraviolet radioactive.
After being modified processing to flyash using ultraviolet radioactive, the pore structure of flyash can be effectively expanded, increases and carries
The functional group quantity and concentration in body surface face improve specific surface area, Kong Rong, aperture and the surface functional group property of flyash, by force
Change suction-operated, deactivation time can be extended, improves catalytic ozonation removal effect.
It is further preferred that be modified using Gd and F to through the modified carrier of ultraviolet radioactive, modified with ultraviolet radioactive
It is counted on the basis of vehicle weight, the content of gadolinium is 0.1%-0.5%, the content of preferably 0.15%-0.25%, F is 0.5~
3.0wt%, preferably 0.7~1.0wt%.
In the present invention, the method that the carrier being modified through ultraviolet radioactive is modified using Gd and F, including it is following
Step: gadolinium salt and ammonium fluoride are mixed to form solution and carry out incipient impregnation through the modified carrier of ultraviolet radioactive, and dip time is
10-12h then by obtained solid in 80~120 DEG C of dry 4-6h, then in 500~600 DEG C of 3~5h of roasting, obtains ultraviolet radioactive
The modified carrier with Gd-F.Gadolinium salt is selected from one of nitrate, acetate and carbonate of gadolinium or a variety of, preferably nitrate.
Ammonium fluoride is modified flyash and both keeps the integrality of carrier original structure and property and draw as modifying agent
- F base is entered, load factor and Load Balanced of the active metal on flyash carrier can be significantly improved.
Gadolinium is introduced to can be improved in flyash carrier after the dispersion degree of active metal that introduces, play synergistic effect with-F base and change
The catalytic activity at kind active metal particles interface, while gadolinium is a kind of storage oxygen element well, will can diffuse to flyash in time
The ozone of carrier surface carries out capture storage, is catalytically decomposed and uses for active component, promotes the removal efficiency of NOx exhaust gas.
A kind of preparation method of ozone catalytic oxidation catalyst, includes the following steps:
(1) flyash is pre-processed to obtain pretreated carrier；
(2) ultraviolet radioactive and Gd-F modification are carried out to pretreated carrier, obtains the carrier of ultraviolet radioactive and Gd-F modification；
(3) incipient impregnation is carried out with through the modified carrier of ultraviolet radioactive and Gd-F containing active component salt solution, obtained smelly
Oxygen catalyst for catalytic oxidation；
In preparation method of the invention, step (1) is specifically: collected flyash being ground into fine powder, crosses 60-
After 200 meshes, after 600 DEG C of -800 DEG C of roasting temperature 4h-6h, binder nitric acid solution, nitric acid solution is added in washing and drying
The preferred 5%-10% of concentration, is counted on the basis of carrier quality, the preferred 3wt%-5wt% of nitric acid solution dosage, extrusion forming, then
In 500 DEG C of -600 DEG C of roasting temperature 3h-5h, pretreated carrier is obtained.
In preparation method of the invention, step (2) is specifically: being carried using pre-processing described in ultraviolet modified lamp radiation treatment
Body, ultraviolet modified lamp use high-pressure sodium lamp, power 200-1000W, preferably 1000W, dominant wavelength 365nm, irradiation time 6-
12h obtains the modified carrier of ultraviolet radioactive.Gadolinium salt and ammonium fluoride mixed solution and the carrier being modified through ultraviolet radioactive carry out waiting bodies
Product dipping, dip time 10-12h, then by obtained solid in 80~120 DEG C of dry 4-6h, then in 500~600 DEG C of roastings 3
~5h obtains the carrier of ultraviolet radioactive and Gd-F modification.
In preparation method of the invention, step (3) is specifically: will contain cobalt salt, manganese salt, mantoquita, molysite and calcium salt
In the carrier that solution is added to the ultraviolet radioactive and Gd-F is modified, progress incipient impregnation, dip time 10-12h, then
By obtained solid in 80~120 DEG C of dryings, drying time 4-6h, then in 500~600 DEG C of 3~5h of roasting, preferably calcination atmosphere is
CO or H2, obtain ozone catalytic oxidation catalyst.Wherein the cobalt salt, manganese salt, mantoquita, molysite and calcium salt be respectively derived from containing
One of nitrate, acetate and carbonate of respective metal element are a variety of, preferably nitrate.
Most of catalytic ozonation process follows free radical mechanism, and ozone acts on a catalyst is degraded to hydroxyl certainly
By base (OH), industry is generally acknowledged that the content of Lacking oxygen can promote the yield of hydroxyl radical free radical (OH), calcination atmosphere CO or
H2Equal selective reductions atmosphere can promote the content of Lacking oxygen effectively to promote the yield of hydroxyl radical free radical (OH).
Catalyst of the invention can not only promote the oxygenation efficiency of NOx, and be able to achieve the decomposition to ozone, prevent in tail gas
Secondary pollution caused by the residual of ozone.The present invention also provides a kind of catalyst of the present invention in ozone Oxidation Treatment NOx
Application in exhaust gas, technical solution are as follows:
A kind of processing method of NOx exhaust gas, comprising the following steps:
(1) NOx exhaust gas is reacted with ozone by catalyst layer progress catalytic ozonation；
(2) the exhaust gas continuation that step (1) obtains reacts generation inorganic salts with specific components in catalyst and is stored in catalyst
In, clean gas emptying.
In processing method of the present invention, in the step (1), the reaction condition of the catalytic ozonation includes: reaction
10~200 DEG C of temperature, preferably 20~50 DEG C, 400~2000h of air speed-1, preferably 500~900h-1, step mainly occurs in (1)
Two kinds of reactions, first is that ozone is main and NO reaction generates NO2, second is that ozone degrade on a catalyst generate hydroxyl radical free radical (
OH) continue and NO and NO2Reaction generates higher nitrogen oxides.The mixed gas and catalyst of NOx and ozone connects in step (1)
The touching time determines the efficiency of the efficiency that ozone decomposes and catalysis oxidation, and in general, time of contact is longer, reacts more thorough,
When air speed is reduced to certain value, NOx removal rate tends to definite value.
In processing method of the present invention, the step (1) can be to carry out, preferably in any reactor known in the art
Using tower.In order to improve the mixed effect of NOx and ozone, air-spreading disk is equipped in tower.
In processing method of the present invention, in the step (2), the specific components of the catalyst are the oxide of calcium, calcium
Oxide and NO2And higher nitrogen oxides react, and generate in nitrate storage catalyst, clean gas emptying, it is high
The consumption of valence nitrogen oxides promotes NO and NO2Oxidation.
The positive effect of the present invention is:
(1) present invention synthesizes ozone catalytic oxidation catalyst using flyash, improves the added value of flyash, simultaneously also
With distinct economic；Use ultraviolet radioactive and the modified flyash of Gd-F as carrier, not only increases to NOx exhaust gas
Adsorption effect catalyst activity component load factor and dispersibility are not only improved by the modification of Gd-F, while enhancing catalysis
The catalytic activity and stability of agent.
(2) present invention processing NOx exhaust gas simple process, is not necessarily to rear end higher nitrogen oxides caustic scrubbing step, saves tower
Investment and alkali-wash waste water secondary treatment problem.
(3) ozone catalyst used in the present invention improves the adsorption effect to NOx, while urging by particular procedure
Under agent effect, ozone can be rapidly converted into a large amount of OH, react with the NOx of absorption and generate higher nitrogen oxides, high price nitrogen oxygen
Generation nitrate is reacted in compound continuation with the calcium oxide component of catalyst, promotes the removal rate of NOx, while ozone catalyst can be with
Unreacted ozone is decomposed completely, not will cause secondary pollution, integration ofTechnology degree is high.
Specific embodiment
Technical solution of the present invention and its effect are described further below by way of specific embodiment.Following embodiment is only used
In illustrating the contents of the present invention, the protection scope that is not intended to restrict the invention.A variety of different embodiments of the invention it
Between can also carry out any combination, as long as it does not violate the idea of the present invention, equally should be considered as it is disclosed in this invention in
Hold.
Oxygen source ozone generator, model C F-G-2 are purchased from Qingdao state woods environmental protection Science and Technology Co., Ltd.；
Catalysis oxidizing tower and absorption tower are purchased from Hua Da Medical Devices Co., Ltd.；
Flyash comes from Huaneng Group Yantai illiciumverum Thermal Power Co., Ltd；
NOx exhaust gas, collected from ten thousand magnificent Yantai industry park nitre benzene devices；
The V-Sorb 2800S type specific surface area measuring instrument measurement that specific surface area is produced by Beijing Jin Aipu scientific & technical corporation；
NOx exhaust gas is detected using flue gas analyzer moral Figure 35 0.
Embodiment 1
The present embodiment is used to illustrate the preparation method of ozone catalytic oxidation catalyst of the present invention and passes through this method
The ozone catalytic oxidation catalyst being prepared, the present embodiment prepare the catalyst with the following method:
(1), collected flyash is ground into fine powder, after crossing 80 meshes, takes 200g fine powder to be placed in Muffle furnace, In
After roasting 4h at 600 DEG C, washing and drying, addition concentration is 5wt% nitric acid solution 6g, and extrusion forming then roasts at 500 DEG C
3h obtains pretreated carrier；
(2), the manganese nitrate aqueous solution 11.8mL of the cobalt nitrate aqueous solution 8.2mL, the 0.5g/mL containing manganese of the 0.5g/mL containing cobalt are taken,
The iron nitrate aqueous solution 14.4mL of the copper nitrate aqueous solution 13.6mL of cupric 0.5g/mL, iron content 0.5g/mL, calcic 0.2g/mL's
Calcium nitrate aqueous solution 212.3mL, is added in pure water, is configured to the maceration extract that total volume is 347.0mL.Above-mentioned maceration extract is added
Enter into the pretreated carrier, carry out incipient impregnation, then dip time 10h does obtained solid in 80 DEG C of dryings
Dry time 5h, then in 500 DEG C of roasting 3h, calcination atmosphere is air, obtains catalyst 1#, the physico-chemical property of catalyst 1# and work
Property component element load capacity is as shown in table 1.
Embodiment 2
The present embodiment is used to illustrate the preparation method of ozone catalytic oxidation catalyst of the present invention and passes through this method
The ozone catalytic oxidation catalyst being prepared, the present embodiment prepare the catalyst with the following method:
(1), collected flyash is ground into fine powder, after crossing 200 meshes, takes 200g fine powder to be placed in Muffle furnace, In
After roasting 5h at 700 DEG C, washing and drying, addition concentration is 5wt% nitric acid solution 8g, and extrusion forming then roasts at 550 DEG C
4h obtains pretreated carrier；
(2), using the ultraviolet modified above-mentioned pretreated carrier of lamp radiation treatment, ultraviolet modified lamp power 250W, dominant wavelength
365nm, irradiation time 6h obtain the modified carrier of ultraviolet radioactive；
(3), the manganese nitrate aqueous solution of the cobalt nitrate aqueous solution 10.4mL, the 0.5g/mL containing manganese of the 0.5g/mL containing cobalt are taken
The iron nitrate aqueous solution 16.6mL of the copper nitrate aqueous solution 12.6mL of 10.2mL, cupric 0.5g/mL, iron content 0.5g/mL, calcic
The calcium nitrate aqueous solution 245.0mL of 0.2g/mL, is added in pure water, is configured to the maceration extract that total volume is 347.0mL.It will be upper
It states maceration extract to be added in the ultraviolet radioactive modified support, carries out incipient impregnation, dip time 10h, then by gained
Solid is in 100 DEG C of dryings, drying time 4h, then in 550 DEG C of roasting 4h, calcination atmosphere is air, obtains catalyst 2#, the catalysis
The physico-chemical property and active component element load capacity of agent 2# is as shown in table 1.
Embodiment 3
The present embodiment is used to illustrate the preparation method of ozone catalytic oxidation catalyst of the present invention and passes through this method
The ozone catalytic oxidation catalyst being prepared, the present embodiment prepare the catalyst with the following method:
(1), collected flyash is ground into fine powder, after crossing 200 meshes, takes 200g fine powder to be placed in Muffle furnace, In
After roasting 5h at 700 DEG C, washing and drying, addition concentration is 5wt% nitric acid solution 10g, and extrusion forming then roasts at 500 DEG C
3h is burnt, pretreated carrier is obtained；
(2), using the ultraviolet modified above-mentioned pretreated carrier of lamp radiation treatment, ultraviolet modified lamp power 500W, dominant wavelength
365nm, irradiation time 12h obtain the modified carrier of ultraviolet radioactive；
(3), the manganese nitrate aqueous solution of the cobalt nitrate aqueous solution 11.6mL, the 0.5g/mL containing manganese of the 0.5g/mL containing cobalt are taken
The iron nitrate aqueous solution 19.2mL of the copper nitrate aqueous solution 15.2mL of 11.6mL, cupric 0.5g/mL, iron content 0.5g/mL, calcic
The calcium nitrate aqueous solution 259.0mL of 0.2g/mL, is added in pure water, is configured to the maceration extract that total volume is 347.0mL.It will be upper
It states maceration extract to be added in the ultraviolet radioactive modified support, carries out incipient impregnation, dip time 10h, then by gained
Solid is in 120 DEG C of dryings, drying time 6h, then obtains catalyst 3# in 600 DEG C of roastings 5h, calcination atmosphere CO, the catalyst
The physico-chemical property and active component element load capacity of 3# is as shown in table 1.
Embodiment 4
The present embodiment is used to illustrate the preparation method of ozone catalytic oxidation catalyst of the present invention and passes through this method
The ozone catalytic oxidation catalyst being prepared, the present embodiment prepare the catalyst with the following method:
(1), collected flyash is ground into fine powder, after crossing 200 meshes, takes 200g fine powder to be placed in Muffle furnace, In
After roasting 5h at 700 DEG C, washing and drying, addition concentration is 5wt% nitric acid solution 8g, and extrusion forming then roasts at 500 DEG C
4h obtains pretreated carrier；
(2), using the ultraviolet modified above-mentioned pretreated carrier of lamp radiation treatment, ultraviolet modified lamp power 1000W, dominant wavelength
365nm, irradiation time 8h obtain the modified carrier of ultraviolet radioactive；
(3), the gadolinium nitrate aqueous solution 30.0mL of the 0.01g/mL containing gadolinium, the ammonium fluoride aqueous solution of fluorine-containing 0.01g/mL are taken
140.0mL is added in pure water, is configured to the maceration extract that total volume is 347.0mL, above-mentioned maceration extract is added to described ultraviolet
In radiation modification carrier, incipient impregnation, dip time 10h, then by obtained solid in 120 DEG C of dryings, then 550 are carried out
DEG C roasting 5h, obtains the modified carrier of ultraviolet radioactive and Gd-F；
(3), the manganese nitrate aqueous solution of the cobalt nitrate aqueous solution 12.6mL, the 0.5g/mL containing manganese of the 0.5g/mL containing cobalt are taken
The iron nitrate aqueous solution 20.6mL of the copper nitrate aqueous solution 16.6mL of 16.0mL, cupric 0.5g/mL, iron content 0.5g/mL, calcic
The calcium nitrate aqueous solution 196.7mL of 0.3g/mL, is added in pure water, is configured to the maceration extract that total volume is 347.0mL.It will be upper
It states maceration extract to be added in the ultraviolet radioactive and Gd-F modified support, progress incipient impregnation, dip time 10h, then
By obtained solid in 120 DEG C of dryings, drying time 4h, then in 600 DEG C of roastings 5h, calcination atmosphere H2, catalyst 4# is obtained, it should
The physico-chemical property and active component element load capacity of catalyst 4# is as shown in table 1.
Embodiment 5
The present embodiment is used to illustrate the preparation method of ozone catalytic oxidation catalyst of the present invention and passes through this method
The ozone catalytic oxidation catalyst being prepared, the present embodiment prepare the catalyst with the following method:
(1), collected flyash is ground into fine powder, after crossing 200 meshes, takes 200g fine powder to be placed in Muffle furnace, In
After roasting 5h at 700 DEG C, washing and drying, addition concentration is 5wt% nitric acid solution 8g, and extrusion forming then roasts at 500 DEG C
4h obtains pretreated carrier；
(2), using the ultraviolet modified above-mentioned pretreated carrier of lamp radiation treatment, ultraviolet modified lamp power 200W, dominant wavelength
365nm, irradiation time 12h obtain the modified carrier of ultraviolet radioactive；
(3), the gadolinium nitrate aqueous solution 50.0mL of the 0.01g/mL containing gadolinium, the ammonium fluoride aqueous solution of fluorine-containing 0.01g/mL are taken
160.0mL is added in pure water, is configured to the maceration extract that total volume is 347.0mL, above-mentioned maceration extract is added to described ultraviolet
In radiation modification carrier, incipient impregnation, dip time 10h, then by obtained solid in 120 DEG C of dryings, then 550 are carried out
DEG C roasting 5h, obtains the modified carrier of ultraviolet radioactive and Gd-F；
(3), the manganese nitrate aqueous solution of the cobalt nitrate aqueous solution 14.8mL, the 0.5g/mL containing manganese of the 0.5g/mL containing cobalt are taken
The iron nitrate aqueous solution 24.0mL of the copper nitrate aqueous solution 19.6mL of 14.2mL, cupric 0.5g/mL, iron content 0.5g/mL, calcic
The calcium nitrate aqueous solution 183.3mL of 0.3g/mL, is added in pure water, is configured to the maceration extract that total volume is 347.0mL.It will be upper
It states maceration extract to be added in the ultraviolet radioactive and Gd-F modified support, progress incipient impregnation, dip time 10h, then
By obtained solid in 120 DEG C of dryings, drying time 5h, then catalyst 5# is obtained in 600 DEG C of roastings 5h, calcination atmosphere CO, it should
The physico-chemical property and active component element load capacity of catalyst 5# is as shown in table 1.
Embodiment 6
The present embodiment is used to illustrate the preparation method of ozone catalytic oxidation catalyst of the present invention and passes through this method
The ozone catalytic oxidation catalyst being prepared, the present embodiment prepare the catalyst with the following method:
(1), collected flyash is ground into fine powder, after crossing 200 meshes, takes 200g fine powder to be placed in Muffle furnace, In
After roasting 5h at 700 DEG C, washing and drying, addition concentration is 5wt% nitric acid solution 10g, and extrusion forming then roasts at 500 DEG C
4h is burnt, pretreated carrier is obtained；
(2), using the ultraviolet modified above-mentioned pretreated carrier of lamp radiation treatment, ultraviolet modified lamp power 1000W, dominant wavelength
365nm, irradiation time 12h obtain the modified carrier of ultraviolet radioactive；
(3), the gadolinium nitrate aqueous solution 40.0mL of the 0.01g/mL containing gadolinium, the ammonium fluoride aqueous solution of fluorine-containing 0.01g/mL are taken
200.0mL is added in pure water, is configured to the maceration extract that total volume is 347.0mL, above-mentioned maceration extract is added to described ultraviolet
In radiation modification carrier, incipient impregnation, dip time 10h, then by obtained solid in 120 DEG C of dryings, then 550 are carried out
DEG C roasting 5h, obtains the modified carrier of ultraviolet radioactive and Gd-F；
(3), the manganese nitrate aqueous solution of the cobalt nitrate aqueous solution 16.0mL, the 0.5g/mL containing manganese of the 0.5g/mL containing cobalt are taken
The iron nitrate aqueous solution 25.8mL of the copper nitrate aqueous solution 18.4mL of 12.2mL, cupric 0.5g/mL, iron content 0.5g/mL, calcic
The calcium nitrate aqueous solution 180.2mL of 0.3g/mL, is added in pure water, is configured to the maceration extract that total volume is 347.0mL.It will be upper
It states maceration extract to be added in the ultraviolet radioactive and Gd-F modified support, progress incipient impregnation, dip time 10h, then
By obtained solid in 120 DEG C of dryings, drying time 6h, then catalyst 6# is obtained in 550 DEG C of roastings 5h, calcination atmosphere CO, it should
The physico-chemical property and active component element load capacity of catalyst 6# is as shown in table 1.
Table 1
Application examples 1
The application example carries out activity rating to the catalyst being prepared in above-described embodiment using following experiment condition.
The ozone catalytic oxidation catalyst of preparation is put into catalysis oxidizing tower, NOx exhaust gas is derived from ten thousand magnificent Yantai industry parks
Nitre benzene device, NOx exhaust gas are passed through catalytic ozonation reaction tower together with ozone, flow 1.5L/min, 30 DEG C of reaction temperature,
Air speed 800h-1、O3(mg/Nm3): NOx (mg/Nm3)=1.0, with flue gas analyzer to NO in gas and NO2Concentration is detected,
The treatment effect of catalyst 1#~6# is as shown in table 2.
Table 2
Application examples 2
The cycle life for taking the above-mentioned catalyst 6# by test case 1 to carry out catalyst is evaluated, and experiment condition is as follows:
Catalysis oxidizing tower exit NOx concentration is monitored, when NOx concentration is more than 100mg/m3When start to roast catalyst
Regeneration, calcination atmosphere select CO, and maturing temperature selects 600 DEG C, and calcining time selects 5h, the catalyst recycled by 5 times
Catalytic activity is as shown in table 3.
Table 3
The catalyst that preparation method it can be seen from the evaluation data of above-mentioned test case through the invention is prepared
Catalytic activity is high, and recyclable regenerative, and the catalyst activity after regeneration restores good.
Comparative example 1
This comparative example is carried out using method identical with application examples 1, except that being filled out in catalysis oxidizing tower using inertia
Material replaces catalyst, and the NOx exhaust gas of simultaneous reactions tower outlet introduces absorption tower, and pure water is respectively adopted in absorbing liquid, and 1%NaOH is molten
Liquid, 1%Ca (OH)2Solution, liquid-gas ratio setting 10, with flue gas analyzer to NO and NO in the exit gas of absorption tower2Concentration is examined
It surveys, treatment effect is as shown in table 4.
Table 4
This comparative example simulates method disclosed in CN104128079A and handles NOx exhaust gas, as seen from Table 4 NOx removal effect
Lower than method described in application examples 1.
Claims (12)
1. a kind of ozone catalytic oxidation catalyst, which is characterized in that the catalyst includes carrier and active component, the carrier
For flyash；The active component includes with cobalt, manganese existing for oxide form, copper, iron and calcium；Weight with the carrier is
Benchmark meter, the catalyst include:
1.0~5.5wt% of Co, preferably 2.0~4.0wt%；
Mn0.5~4.5wt%, preferably 2.5~4.0wt%；
1.5~6.5wt% of Cu, preferably 3.0~5.0wt%；
2.5~9.5wt% of Fe, preferably 3.0~6.5wt%；
10~50wt% of Ca, preferably 20~30wt%.
2. catalyst according to claim 1, which is characterized in that for the carrier by pretreatment molding, the carrier is pre-
Processing method roasts at a temperature of 600 DEG C -800 DEG C the following steps are included: flyash is ground into fine powder excessively after 60-200 mesh
After burning 4h-6h, binder is added in washing and drying, and extrusion forming obtains then in 500 DEG C of -600 DEG C of roasting temperature 3h-5h
Pretreated carrier.
3. catalyst according to claim 2, which is characterized in that the binder is nitric acid solution, and concentration of nitric acid is excellent
5%-10% is selected, is counted on the basis of carrier quality, the preferred 3wt%-5wt% of nitric acid solution dosage.
4. catalyst according to claim 2 or 3, which is characterized in that the pretreated carrier is modified by ultraviolet radioactive.
5. catalyst according to claim 4, which is characterized in that the modified method of the ultraviolet radioactive includes following step
Rapid: using pretreated carrier described in ultraviolet modified lamp radiation treatment, ultraviolet modified lamp uses high-pressure sodium lamp, power 200-1000W,
It is preferred that 1000W, dominant wavelength 365nm, irradiation time 6-12h, obtain the modified carrier of ultraviolet radioactive.
6. catalyst according to claim 5, which is characterized in that the modified carrier of the ultraviolet radioactive uses gadolinium and fluorine
It is modified.
7. catalyst according to claim 6, which is characterized in that it is counted on the basis of the vehicle weight modified by ultraviolet radioactive,
The content of gadolinium is 0.1%-0.5%, preferably 0.15%-0.25%, and the content of fluorine is 0.5~3.0wt%, preferably 0.7~
1.0wt%.
8. catalyst according to claim 7, which is characterized in that the gadolinium and fluorine carry out the modified carrier of ultraviolet radioactive
Modified method, comprising the following steps: gadolinium salt and ammonium fluoride are mixed in a certain ratio to form solution, and modified through ultraviolet radioactive
Carrier carries out incipient impregnation, and then obtained solid is dried and is roasted, and obtains the modified carrier of ultraviolet radioactive, Gd-F.
9. catalyst according to claim 8, which is characterized in that the dip time be 10-12h, drying temperature 80~
120 DEG C, drying time 4-6h, 500~600 DEG C of maturing temperature, calcining time is 3~5h.
10. a kind of method for preparing the described in any item catalyst of claim 1-9, comprising the following steps: cobalt salt, manganese will be contained
Salt, mantoquita, molysite and calcium salt solution be added in carrier, carry out incipient impregnation, dip time 10-12h, then by institute
Solid is obtained in 80~120 DEG C of dryings, 4~6h of drying time, then in 500~600 DEG C of 3~5h of roasting, preferably calcination atmosphere is CO
Or H2, obtain ozone catalytic oxidation catalyst.
11. application of the described in any item catalyst of claim 1-9 in ozone Oxidation Treatment NOx exhaust gas.
12. side's application according to claim 11, wherein 10~200 DEG C of reaction temperature, 400~2000h of air speed-1, O3
(mg/Nm3): NOx (mg/Nm3)=0.6~2；Preferably, 20~50 DEG C of reaction temperature, 500~900h of air speed-1, O3(mg/
Nm3): NOx (mg/Nm3)=0.8~1.2.
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| CN115739162A (en) * | 2022-12-15 | 2023-03-07 | 郑州大学 | Copper-iron bimetal composite carbon nitride Fenton catalyst and preparation method and application thereof |
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| CN114618295B (en) | 2023-05-30 |
| CN110449161B (en) | 2022-08-05 |
| CN114618295A (en) | 2022-06-14 |
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