CN110560059B - Preparation method of noble metal ozone removal catalyst - Google Patents
Preparation method of noble metal ozone removal catalyst Download PDFInfo
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- CN110560059B CN110560059B CN201910895018.5A CN201910895018A CN110560059B CN 110560059 B CN110560059 B CN 110560059B CN 201910895018 A CN201910895018 A CN 201910895018A CN 110560059 B CN110560059 B CN 110560059B
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- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 70
- 239000003054 catalyst Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- AQCHWTWZEMGIFD-UHFFFAOYSA-N metolazone Chemical compound CC1NC2=CC(Cl)=C(S(N)(=O)=O)C=C2C(=O)N1C1=CC=CC=C1C AQCHWTWZEMGIFD-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims abstract description 23
- 239000000243 solution Substances 0.000 claims abstract description 21
- 239000008139 complexing agent Substances 0.000 claims abstract description 20
- 239000004094 surface-active agent Substances 0.000 claims abstract description 18
- 238000009835 boiling Methods 0.000 claims abstract description 17
- 238000001816 cooling Methods 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 239000012266 salt solution Substances 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 5
- 239000002253 acid Substances 0.000 claims description 20
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 18
- 239000011258 core-shell material Substances 0.000 claims description 16
- 239000002105 nanoparticle Substances 0.000 claims description 14
- 150000002500 ions Chemical class 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 11
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 10
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 claims description 6
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- 229960002303 citric acid monohydrate Drugs 0.000 claims description 6
- 235000006408 oxalic acid Nutrition 0.000 claims description 6
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 6
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 5
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 5
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 5
- 239000008103 glucose Substances 0.000 claims description 5
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 5
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 4
- 229910021645 metal ion Inorganic materials 0.000 claims description 4
- 239000010970 precious metal Substances 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 3
- 239000001110 calcium chloride Substances 0.000 claims description 3
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 3
- -1 ion salt Chemical class 0.000 claims description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 229920000428 triblock copolymer Polymers 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims description 2
- 238000007865 diluting Methods 0.000 abstract description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052710 silicon Inorganic materials 0.000 abstract description 4
- 239000010703 silicon Substances 0.000 abstract description 4
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 22
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 21
- 229910052737 gold Inorganic materials 0.000 description 21
- 239000010931 gold Substances 0.000 description 21
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 14
- 229910052697 platinum Inorganic materials 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000011068 loading method Methods 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 3
- 230000009931 harmful effect Effects 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- JUWSSMXCCAMYGX-UHFFFAOYSA-N gold platinum Chemical compound [Pt].[Au] JUWSSMXCCAMYGX-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 206010011224 Cough Diseases 0.000 description 1
- 206010019233 Headaches Diseases 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 206010068319 Oropharyngeal pain Diseases 0.000 description 1
- 201000007100 Pharyngitis Diseases 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 231100000869 headache Toxicity 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 210000004877 mucosa Anatomy 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 239000005437 stratosphere Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
Classifications
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- 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
- B01D53/8671—Removing components of defined structure not provided for in B01D53/8603 - B01D53/8668
- B01D53/8675—Ozone
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a preparation method of a noble metal ozone removal catalyst, which is characterized by comprising the following steps: (1) heating the first noble metal ion salt solution to boiling, adding a complexing agent, heating to boil and cooling to obtain a noble metal sol core; (2) diluting the noble metal sol core, heating to boil, adding a second noble metal ion salt solution, boiling again, adding a complexing agent, performing ultrasonic treatment, and keeping boiling for 1-2 h; (3) and adding a demulsifier and a surfactant, stirring until the surfactant is completely dissolved, dropwise adding an inorganic silicon source, pouring the solution into a reaction kettle, standing for 12-16h at 110 ℃, cooling to room temperature, filtering, washing, drying for 10-12h, and roasting for 4-6h at 600 ℃ in the presence of 500-.
Description
Technical Field
The invention relates to a catalyst for removing ozone, in particular to a preparation method of a noble metal catalyst for removing ozone.
Background
Ozone absorbs harmful ultraviolet radiation in the stratosphere, but ozone is generated on the surface layer because volatile organic compounds and nitrogen oxides generate complex photochemical reaction, and non-thermal plasma technology and negative ion purification technology can also generate ozone while removing indoor pollutants; in addition, air conditioners, printers and copiers can release ozone in the using process; the strong oxidizing property of ozone makes the ozone be applied to the treatment of industrial wastewater and the desulfurization and denitrification of flue gas, but the tail gas still contains a large amount of ozone. The air quality standard of the people's republic of China strictly regulates the concentration of ozone indoors and outdoors: the concentration of the ozone in the room is not more than 0.08ppm (0.16mg/m3) within 1 hour, the concentration of the ozone in the room is not more than 0.1ppm (0.2mg/m3) within 1 hour, and the ozone can have harmful effects on human bodies, such as headache, cough, sore throat and mucosa injury, and simultaneously weaken the resistance of the human bodies to diseases such as cold and the like. In addition, ozone reacts with other harmful gases to generate substances such as ultrafine particles, peroxide, carboxylic acid and the like, which causes more harm to human bodies. Therefore, removal of ozone is very necessary. The noble metal catalyst has higher catalytic decomposition effect on ozone, the noble metal loading capacity of the existing noble metal ozone removal catalyst is larger, the noble metal is loaded on the surface of the carrier by a simple impregnation method, but the noble metal loading capacity is larger, so that the cost of the catalyst is improved; noble metal ions are easy to aggregate to form large particles to influence the activity of the catalyst; chloride ions and water vapor have great influence on the catalytic activity of the noble metal catalyst, and meanwhile, the active components of the noble metal are easy to run off in the reaction process, so that the activity of the catalyst is reduced.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a preparation method of a noble metal ozone removal catalyst, which can effectively improve the specific surface area of the catalyst and improve the activity of the catalyst.
The technical scheme adopted by the invention for solving the technical problems is as follows: a preparation method of a noble metal ozone removal catalyst comprises the following steps:
(1) preparing a noble metal sol core: heating the first noble metal ion salt solution to boiling, adding a complexing agent, performing ultrasonic treatment for 20-40min, heating again to boiling, keeping boiling for 10-20min, and naturally cooling to obtain a noble metal sol core;
(2) preparing noble metal sol core-shell nano particles: taking the noble metal sol core prepared in the step (1), adding water to dilute by 8-10 times, heating to boil, adding a second noble metal ion salt solution, heating to boil, adding a complexing agent, performing ultrasound for 20-40min, keeping boiling for 1-2h again, and naturally cooling to obtain the noble metal sol core-shell nanoparticles;
(3) preparing a finished product of the noble metal ozone-removing catalyst: and (3) adding a demulsifier and a surfactant into the noble metal sol core-shell nanoparticles prepared in the step (2), heating to 40-50 ℃, stirring until the surfactant is completely dissolved, dropwise adding an inorganic silicon source, stirring for 22-26h, pouring the solution into a reaction kettle, standing for 12-16h at 110 ℃, cooling to room temperature, filtering, washing, drying for 10-12h at 90-100 ℃, and roasting for 4-6h at 600 ℃ in a muffle furnace to obtain the noble metal ozone removal catalyst finished product.
The first precious metal ion salt in the step (1) is chloroauric acid, palladium chloride, chloroplatinic acid or silver nitrate; the second precious metal ion salt in the step (2) is chloroauric acid, palladium chloride, chloroplatinic acid or silver nitrate;
the complexing agent in the step (1) is citric acid monohydrate, oxalic acid, EDTA or glucose; the molar ratio of the first noble metal ion salt to the complexing agent is 1: 1.5-3.
The complexing agent in the step (2) is citric acid monohydrate, oxalic acid, EDTA or glucose; the molar ratio of the noble metal ions to the complexing agent in the noble metal sol core-shell nano particles is 1: 1.5-3;
the surfactant in the step (3) is a triblock copolymer P123 or hexadecyl trimethyl ammonium bromide, the demulsifier is sodium chloride, calcium chloride or magnesium chloride, and the inorganic silicon source is tetraethyl orthosilicate.
The molar ratio of the noble metal ions to the surfactant in the noble metal sol core-shell nanoparticles is 1: 2-5; the molar ratio of the surfactant to the inorganic silicon source is 1: 3-5; the mass ratio of the demulsifier to the complexing agent in the step (2) is 20-40: 1.
the temperature rise rate of the roasting in the step (3) is 1-2 ℃/min.
Compared with the prior art, the invention has the advantages that:
(1) the noble metal sol is prepared by adopting a gel method, so that the problem of reduction of catalytic activity caused by material agglomeration is avoided, the noble metal core-shell structure is prepared, the reduction of catalytic activity caused by loss of active components is avoided, the specific surface area of the catalyst is effectively improved, and the activity of the catalyst is improved.
(2) Chloride is added as a demulsifier in the loading process, and the activity of the catalyst is promoted by the synergistic action of chloride ions and noble metals, and the catalyst also has the function of resisting chloride ion poisoning.
(3) The noble metal has small loading capacity, and the cost of the catalyst is greatly saved.
In conclusion, according to the preparation method of the noble metal ozone removal catalyst, the noble metal active component is prepared by using the sol method, so that the noble metal can be uniformly dispersed in the colloid, and the loss of the catalytic active component is avoided by preparing the core-shell structure during loading; chloride is added in the loading process to form a synergistic effect with the noble metal of the active component of the catalyst, so that the catalytic activity is improved, and the influence of chloride ions on the catalyst is effectively resisted.
Detailed Description
The present invention will be described in further detail with reference to examples.
Example 1
A preparation method of a noble metal ozone removal catalyst comprises the following steps:
(1) preparing a gold sol core: preparation of 5X 10-3measuring 200mL of a chloroauric acid solution in mol/L, mechanically stirring (vortex is not required to be formed too quickly), heating to boil (hydrogen chloride gas in the solution escapes), adding 0.315g of citric acid monohydrate, carrying out ultrasonic treatment for 20min, heating again to boil, keeping for 10min, and naturally cooling to obtain a gold sol core;
(2) preparing gold/platinum sol core-shell nanoparticles: the preparation concentration is 5 multiplied by 10-2measuring 40mL of gold sol prepared in the step (1) by using a mol/L chloroplatinic acid solution, diluting the gold sol to 400mL by using deionized water, heating the diluted gold sol to boiling, and adding 8mL of 5 multiplied by 10- 2And (3) boiling the chloroplatinic acid solution in mol/L, adding 0.13g of citric acid monohydrate, performing ultrasonic treatment for 20min, keeping boiling for 1h, and naturally cooling to obtain the gold-platinum stoichiometric ratio of 1:2 gold/platinum sol core-shell nanoparticles;
(3) preparation of finished gold/platinum @ silica catalyst: weighing 150mL of gold/platinum sol prepared in the step (2), adding 3.78g of sodium chloride, adding 2.55g of surfactant P123, heating to 40 ℃, stirring until the surfactant is completely dissolved, dropwise adding 7.656g of tetraethyl orthosilicate (TEOS), stirring for 24h, pouring the solution into a reaction kettle, standing for 12h at 110 ℃, cooling to room temperature, filtering, washing, drying at 90 ℃ for 12h, roasting the sample in a muffle furnace at 500 ℃ for 4h at the heating rate of 1 ℃/min, and thus obtaining the finished gold/platinum @ silicon dioxide catalyst. Under the condition of room temperature, the ozone removal rate reaches 96 percent.
Example 2
A preparation method of a noble metal ozone removal catalyst comprises the following steps:
(1) preparing a gold sol core: preparation of 5X 10-3measuring 200mL of a chloroauric acid solution in mol/L, heating to boil, adding 0.27g of oxalic acid, carrying out ultrasonic treatment for 40min, heating to boil again, keeping for 15min, and naturally cooling to obtain a gold sol core;
(2) preparing gold/platinum sol core-shell nanoparticles: the preparation concentration is 5 multiplied by 10-2measuring 40mL of gold sol prepared in the step (1) by using a mol/L chloroplatinic acid solution, diluting the gold sol to 320mL by using deionized water, heating the diluted gold sol to boiling, and adding 16mL of 5 multiplied by 10- 2And (3) boiling the chloroplatinic acid solution in mol/L, adding 0.22g of oxalic acid, performing ultrasonic treatment for 40min, keeping boiling for 2h, and naturally cooling to obtain the gold-platinum stoichiometric ratio of 1: 4 gold/platinum sol core-shell nanoparticles;
(3) preparation of finished gold/platinum @ silica catalyst: weighing 150mL of gold/platinum sol prepared in the step (2), adding 10.8g of magnesium chloride, adding 0.81g of Cetyl Trimethyl Ammonium Bromide (CTAB) serving as a surfactant, heating to 40 ℃, stirring until the surfactant is completely dissolved, dropwise adding 4g of tetraethyl orthosilicate (TEOS), stirring for 24 hours, pouring the solution into a reaction kettle, standing for 16 hours at 110 ℃, cooling to room temperature, filtering, washing, drying for 10 hours at 100 ℃, roasting the sample for 6 hours at 600 ℃ in a muffle furnace at the heating rate of 2 ℃/min, and thus obtaining the finished gold/platinum @ silicon dioxide catalyst. Under the condition of room temperature, the ozone removal rate reaches 97 percent.
Comparative example 1
Preparation of 5X 10-3measuring 50mL of chloroauric acid solution in mol/L, diluting with deionized water to 200mL, weighing a proper amount of silicon dioxide, adding into the chloroauric acid solution to ensure that the liquid surface is just covered with solid silicon dioxide, standing for 2h, and drying. The sample was placed in a muffle furnace and calcined at 300 ℃ for 2h under a hydrogen atmosphere. Thus obtaining the ozone removing catalyst loaded with single noble metal. The ozone removal rate at room temperature was 70%.
Comparative example 2
Preparation of 5X 10-3measuring 50mL of a chloroplatinic acid solution in mol/L, diluting with deionized water to 200mL to obtain a solution 1, measuring 0.1g of sodium borohydride to dissolve in 50mL of deionized water to obtain a solution 2, pouring the solution 2 into the solution 1 to obtain a solution 3, measuring a proper amount of titanium dioxide to add into the solution 3, covering the liquid surface with solid titanium dioxide, standing for 2h, and drying. Thus obtaining the ozone removing catalyst loaded with single noble metal. The ozone removal rate at room temperature was 69%.
In addition to the above embodiments, the complexing agent may be EDTA or glucose, and the noble metal ion salt may be palladium chloride, chloroplatinic acid, or silver nitrate; the demulsifier can also be calcium chloride; the molar ratio of the noble metal ions to the complexing agent in the step (1) can be any value within 1: 1.5-3; in the step (2), the molar ratio of the noble metal ions in the chloroplatinic acid, the palladium chloride or the chloroauric acid to the complexing agent can also be 1:1.5 to 3; the molar ratio of the noble metal ions in the gold/platinum sol in the step (3) to the surfactant can be any value of 1: 2-5; the molar ratio of the surfactant to the tetraethyl orthosilicate can be any value of 1: 3-5; the mass ratio of the demulsifier to the complexing agent in the step (2) can be any value of 20-40: 1.
The above description is not intended to limit the present invention, and the present invention is not limited to the above examples. Those skilled in the art should also realize that changes, modifications, additions and substitutions can be made without departing from the true spirit and scope of the invention.
Claims (6)
1. A preparation method of a noble metal ozone removal catalyst is characterized by comprising the following steps:
(1) preparing a noble metal sol core: heating the first noble metal ion salt solution to boiling, adding a complexing agent, performing ultrasonic treatment for 20-40min, heating again to boiling, keeping boiling for 10-20min, and naturally cooling to obtain a noble metal sol core;
(2) preparing noble metal sol core-shell nano particles: taking the noble metal sol core prepared in the step (1), adding water to dilute by 8-10 times, heating to boil, adding a second noble metal ion salt solution, heating to boil, adding a complexing agent, performing ultrasound for 20-40min, keeping boiling for 1-2h again, and naturally cooling to obtain the noble metal sol core-shell nanoparticles;
(3) preparing a finished product of the noble metal ozone-removing catalyst: and (3) adding a demulsifier and a surfactant into the noble metal sol core-shell nanoparticles prepared in the step (2), heating to 40-50 ℃, stirring until the surfactant is completely dissolved, dropwise adding tetraethyl orthosilicate, stirring for 22-26h, pouring the solution into a reaction kettle, standing for 12-16h at 110 ℃, cooling to room temperature, filtering, washing, drying for 10-12h at 90-100 ℃, placing in a muffle furnace, and roasting at 600 ℃ for 4-6h to obtain the noble metal ozone removal catalyst finished product, wherein the surfactant is a triblock copolymer P123 or hexadecyl trimethyl ammonium bromide, and the demulsifier is sodium chloride, calcium chloride or magnesium chloride.
2. The method for preparing a noble metal ozone removal catalyst according to claim 1, wherein: the first precious metal ion salt in the step (1) is chloroauric acid, palladium chloride, chloroplatinic acid or silver nitrate; the second precious metal ion salt in the step (2) is chloroauric acid, palladium chloride, chloroplatinic acid or silver nitrate.
3. The method for preparing a noble metal ozone removal catalyst according to claim 1, wherein: the complexing agent in the step (1) is citric acid monohydrate, oxalic acid, EDTA or glucose; the molar ratio of the first noble metal ion salt to the complexing agent is 1: 1.5-3.
4. The method for preparing a noble metal ozone removal catalyst according to claim 1, wherein: the complexing agent in the step (2) is citric acid monohydrate, oxalic acid, EDTA or glucose; the molar ratio of the noble metal ions to the complexing agent in the noble metal sol core-shell nano particles is 1: 1.5-3.
5. The method for preparing a noble metal ozone removal catalyst according to claim 4, wherein: the molar ratio of the noble metal ions to the surfactant in the noble metal sol core-shell nanoparticles is 1: 2-5; the molar ratio of the surfactant to the tetraethyl orthosilicate is 1: 3-5; the mass ratio of the demulsifier to the complexing agent in the step (2) is 20-40: 1.
6. the method for preparing a noble metal ozone removal catalyst according to claim 1, wherein: the temperature rise rate of the roasting in the step (3) is 1-2 ℃/min.
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