CN115555018B - Catalyst for low-temperature ozone catalytic oxidation of VOCs and preparation method thereof - Google Patents
Catalyst for low-temperature ozone catalytic oxidation of VOCs and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 61
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 239000012855 volatile organic compound Substances 0.000 title claims abstract description 32
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 28
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 28
- 230000003647 oxidation Effects 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000002245 particle Substances 0.000 claims abstract description 23
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 19
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 12
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 10
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(iii) oxide Chemical compound O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 50
- 239000000243 solution Substances 0.000 claims description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- 239000011572 manganese Substances 0.000 claims description 31
- 239000000843 powder Substances 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 21
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 12
- 229910002651 NO3 Inorganic materials 0.000 claims description 11
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 239000002105 nanoparticle Substances 0.000 claims description 8
- 235000019441 ethanol Nutrition 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 6
- 239000012266 salt solution Substances 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 238000000354 decomposition reaction Methods 0.000 claims description 5
- 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 5
- 238000001816 cooling Methods 0.000 claims description 4
- TYTHZVVGVFAQHF-UHFFFAOYSA-N manganese(3+);oxygen(2-) Chemical group [O-2].[O-2].[O-2].[Mn+3].[Mn+3] TYTHZVVGVFAQHF-UHFFFAOYSA-N 0.000 claims description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- 230000009467 reduction Effects 0.000 claims description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 32
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 23
- 238000006243 chemical reaction Methods 0.000 description 18
- 238000005470 impregnation Methods 0.000 description 11
- 229910052697 platinum Inorganic materials 0.000 description 6
- 230000009977 dual effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000643 oven drying Methods 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000809 air pollutant Substances 0.000 description 1
- 231100001243 air pollutant Toxicity 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000005949 ozonolysis reaction Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 229910003446 platinum oxide Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—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
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/656—Manganese, technetium or rhenium
- B01J23/6562—Manganese
-
- 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
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
-
- B01J35/23—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/708—Volatile organic compounds V.O.C.'s
-
- 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 relates to a preparation method of a catalyst for low-temperature ozone catalytic oxidation of VOCs, which takes manganese trioxide as a carrier, wherein a first active component is noble metal Pt particles, a second active component is rare earth metal oxide cerium oxide, and a synergistic catalytic effect exists between the two active components, so that the ozone catalytic oxidation efficiency of the VOCs can be promoted. The catalyst can be combined with ozone to realize high-efficiency removal of VOCs at room temperature, the removal rate reaches more than 95%, and meanwhile, the catalyst has the advantages of simple preparation method, long catalytic life and the like, and has good application prospect.
Description
Technical Field
The invention belongs to the technical field of waste gas treatment, and particularly relates to a preparation method of a catalyst for low-temperature ozone catalytic oxidation of VOCs.
Background
Volatile organic compounds (Volatile Organic Compounds, VOCs) are PM 2.5 (fine particulate matter) and ozone (O) 3 ) The important precursor is a main air pollutant, which can be generated in the discharge of industrial production process or in the human living environment, and comprises: release of house finishing materials, paint spraying for vehicles, catering oil smoke and the like. Whichever mode of generation constitutes a great hazard to humans and the environment. The current VOCs treatment methods mainly comprise two main types: one type is recovery, which is generally directed to organic materials of medium, high concentration and relatively single composition, including: absorption, condensation, adsorption, membrane separation, and the like. The other is decomposition, i.e. oxidative decomposition of VOCs into CO 2 、H 2 Cleaning of O and the likeThe gas discharge is the main treatment method of the low-concentration VOCs. Mainly comprises the following steps: thermal decomposition method, photocatalytic oxidation method, ozone catalytic oxidation method, low-temperature plasma method, etc. Among them, the ozone catalytic oxidation method is regarded as a promising low-concentration VOCs treatment method with the advantages of low energy consumption, low-temperature reaction, clean products and the like.
It has been found that a combination of ozone and catalytic oxidation techniques can effectively remove VOCs. The ozone catalytic oxidation technology is to generate ozone by an ozone generator, oxidize organic pollutants on the surface of a catalyst into non-toxic CO at normal temperature and normal pressure 2 、H 2 O or other inorganic matters, has the advantages of low reaction temperature, wide pollutant degradation range and the like. The metal, metal oxide and metal salt are generally used as catalysts, and the combination of catalysis and ozone oxidation ensures that ozone generates more intermediate products with strong oxidizing ability under the action of the catalysts so as to achieve the improvement
The purpose of ozone oxidizing ability is to promote the oxidation reaction of ozone, and to enable low-temperature catalytic oxidation of gaseous pollutants.
For this technology, the key to deep oxidation is a highly efficient catalyst. However, most of the catalysts currently available for the catalytic oxidation of VOCs use transition metal oxides or noble metals alone as the active component. Catalysts based on individual transition metal oxides as active components are generally subject to incomplete ozonolysis and CO 2 Low selectivity, etc. The noble metal is used as an active component, so that the low-temperature reducibility of the catalyst can be greatly improved, but the supported noble metal catalyst has the defects of high preparation cost, easiness in sintering at high temperature and the like, and the catalytic activity and stability are still to be further improved.
In view of the above, the present invention has chosen to incorporate a rare earth metal into platinum nanoparticles to reduce the amount of noble metal platinum and to improve its thermal stability. And the cerium-based material has good oxygen storage and release capacity, so that the catalytic activity of the catalyst is improved. The preparation process is simple and quick, the content of Pt active components can be effectively controlled below 0.25 and wt%, the application cost is greatly reduced, and the method can almost realize complete conversion of VOCs at room temperature when the method is applied to deep treatment of low-concentration VOCs.
Disclosure of Invention
The invention aims to solve the technical problems of overcoming the defects of the prior art and providing a preparation method of a catalyst for catalyzing and oxidizing VOCs by low-temperature ozone.
In order to solve the technical problems, the invention adopts the following technical scheme:
the catalyst comprises a carrier, a first active component and a second active component, wherein the carrier is manganese sesquioxide, the first active component is noble metal Pt particles, and the second active component is rare earth metal oxide cerium oxide.
Preferably, the optimum mass ratio of the first and second active components of the catalyst is 0.2:15.
Preferably, the catalyst comprises the following components in proportion: the mass percentage of noble metal Pt particles in the catalyst is 0.2 to 0.25 percent by weight based on the mass of the catalyst being 100 wt percent; the rare earth metal oxide cerium oxide accounts for 5-20 wt% of the total mass of the catalyst. The precursor of the manganese sesquioxide is nitrate of element Mn.
Preferably, the precursor of the rare earth metal oxide cerium oxide is a nitrate of element Ce; the Pt particles are obtained by a glycol reduction method of chloroplatinic acid.
The preparation method of the multi-metal catalyst for low-temperature ozone catalytic oxidation of VOCs comprises the following steps of:
1) Dissolving 4.0-5.0 g of 1,3, 5-benzene tricarboxylic acid in absolute ethyl alcohol, adding 10.0-11.0 g of nitrate precursor of Mn element, stirring at room temperature, slowly adding 4.0-5.0 mL triethylamine solution in the stirring process, grinding the dried solid into nano-scale particles, and further roasting to obtain brownish black Mn2O3 powder; the roasting temperature is as follows: 400. the temperature is lower than the temperature; the firing time was 4 h.
2) Mixing the brownish black Mn2O3 powder obtained in the step 1) with nitrate precursors of Ce elements with different masses, dissolving in absolute ethyl alcohol, standing at room temperature for 24 h, and drying and roasting to obtain w% Ce/Mn2O3 powder, wherein w% is 5%, 10%, 15% and 20% respectively;
3) Weighing 800-900 mg polyvinylpyrrolidone and 100 mL glycol solution, mixing, adding 20 mL noble metal salt solution with the concentration of 10 g/L to obtain yellow solution, magnetically stirring 1 h under the condition of 120 ℃ oil bath until the yellow solution becomes dark brown solution, cooling, adding acetone to extract Pt particles, centrifuging, washing, and dispersing in ethanol to obtain Pt particle solution;
4) Mixing the powder obtained in the step 2) of 1.0 g with the Pt particle solution obtained in the step 3) of 7 mL, dissolving in absolute ethyl alcohol, stirring for 8-12 h, and centrifuging, drying, roasting and the like to obtain the catalyst for the catalytic oxidation of VOCs by ozone.
In the above method, in step 1), the nitrate precursor of Mn element is: manganese nitrate solution with the mass percentage concentration of 50 percent.
In the above method, in step 3), the noble metal salt solution is H 2 PtCl 6 。
In the method, in the loading process of the first active component and the second active component, drying is carried out in a vacuum drying oven.
In the method, the stirring rotation speed is as follows: 300-400 r/min.
The invention selects double active components, wherein the rare earth oxide cerium oxide surface is rich in electrons, and O is easy to be adsorbed 3 In (2) providing an electron to O 3 Thereby forming O 3 - A group that can promote the decomposition of VOCs; at the same time, the interaction between cerium oxide and Pt can reduce the activation energy of the reaction, thereby
The low-temperature catalytic activity of the catalyst is improved in one step, and the O can be synchronously decomposed 3 And the effect of VOCs.
Further preferably, the first active component Pt element accounts for 0.2% wt% of the mass of the catalyst, the second active component accounts for 5-20 wt% of the mass of the catalyst, when the mass ratio of the first active component to the second active component is 0.2:15, the catalytic activity is the highest, and the synergistic catalytic effect of platinum and cerium oxide is the most remarkable. The degradation rate of the catalyst to toluene at normal temperature is over 95 percent.
With respect to the active component, most preferably, the noble metal comprises 0.2. 0.2 wt% of the total mass of the catalyst and the rare earth oxide comprises 15. 15 wt% of the total mass of the catalyst.
Preferably, the noble metal is Pt.
Preferably, the rare earth metal oxide is an oxide of Ce. It can effectively adsorb ozone and provide electrons to make O 3 - The radicals further decompose VOCs, while decomposing O 3 。
Compared with the prior art, the invention has the beneficial effects that:
(1) The method adopts the impregnation method to prepare the catalyst, has simple preparation process and is easy to realize industrialization;
(2) According to the catalyst, pt and cerium oxide are introduced as active components, so that the conversion rate of VOCs at low temperature is facilitated, and meanwhile, the dispersity of noble metal Pt on the surface of the catalyst is improved, so that the possibility of reducing the activity of the catalyst due to sintering is reduced, the conversion rate is ensured, and the reaction temperature and the high temperature tolerance capability of the catalyst are reduced;
(3) The active component of the invention adopts noble metal and rare earth metal to combine, thereby reducing the reaction temperature, improving the activity and the service life of the catalyst;
(4) The invention can complete the reaction at normal temperature without complex reaction conditions such as high-temperature heating, high pressure and the like, and has higher safety;
(5) The invention greatly improves the utilization rate of ozone, and can realize the advanced oxidation treatment of VOCs with less ozone under the same condition;
(6) The method has good stability, can still maintain the toluene conversion rate of more than 85% after long-time reaction, and greatly reduces the cost of VOCs treatment;
drawings
FIG. 1 is a graph comparing the conversion of p-toluene ozone catalyzed oxidation of a dual active component catalyst at different temperatures at a mass percent of 5-20-wt% platinum and a different second active component.
FIG. 2 is a graph showing the ozone catalyzed oxidation of CO to toluene at various temperatures with a dual active component catalyst at a platinum and different second active component mass percent of 5-20 wt% 2 Selective comparison.
FIG. 3 shows the ozone catalyzed oxidation of p-toluene with a dual active component catalyst at different temperatures at a mass percent of 5-20-wt% platinum and a different second active component 3 Comparison of decomposition rates.
FIG. 4 shows Pt-0.15Ce/Mn at a temperature of 50℃for a mass ratio of platinum to cerium oxide of 0.2:15 2 O 3 And (3) evaluating the stability of the catalyst for catalytic oxidation of toluene by ozone.
Detailed Description
The following description of the embodiments of the present invention will clearly and fully describe the technical solutions of the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. The following examples are only for more clearly illustrating the technical aspects of the present invention, and are not intended to limit the scope of the present invention.
Example 1
The method is an impregnation method, and the preparation process is as follows:
dissolving 4.20 g of 1,3, 5-benzene tricarboxylic acid in 100 mL absolute ethanol, adding 10.74 g of nitrate precursor of Mn element, stirring at room temperature at medium speed for 6 h, slowly adding 4.0 mL triethylamine solution during stirring, oven drying at 120deg.C for 12 h, grinding the solid into nano-sized particles, and calcining at 400deg.C in muffle furnace for 4 h to obtain brownish black Mn 2 O 3 And (3) powder.
Example 2
The method is an impregnation method, and the preparation process is as follows:
1) Dissolving 4.20 g of 1,3, 5-benzene tricarboxylic acid in 100 mL absolute ethanol, adding 10.74 g manganese nitrate solution (with mass percentage concentration of 50%), stirring at room temperature at medium speed for 6 h, and slowly adding 4.0 mL three during stirringDrying the ethylamine solution at 120 ℃ for 12 h, grinding the solid into nano-sized particles, and then placing the nano-sized particles in a muffle furnace for roasting at 400 ℃ for 4 h to obtain brown-black Mn 2 O 3 A powder;
2) Taking 2.0 g and 0.310 g Ce (NO) of the powder obtained in the step 1) 3 ) 3 •6H 2 O is mixed and dissolved in 30 mL absolute ethyl alcohol, and is kept stand at room temperature for 24 h, then is dried in a vacuum drying oven at 40 ℃, and is baked at 300 ℃ for 2 h to obtain 0.05Ce/Mn 2 O 3 A powder;
example 3
The method is an impregnation method, and the preparation process is as follows:
removing Ce (NO) 3 ) 3 •6H 2 The amount of O was 0.620. 0.620 g, and the final catalyst became 0.10Ce/Mn 2 O 3 The procedure of example 2 was repeated except for the powder.
Example 4
The method is an impregnation method, and the preparation process is as follows:
removing Ce (NO) 3 ) 3 •6H 2 The amount of O was 0.930 and g, and the finally obtained catalyst became 0.15Ce/Mn 2 O 3 The procedure of example 2 was repeated except for the powder.
Example 5
The method is an impregnation method, and the preparation process is as follows:
removing Ce (NO) 3 ) 3 •6H 2 The amount of O was 1.240. 1.240 g, and the finally obtained catalyst became 0.20Ce/Mn 2 O 3 The procedure of example 2 was repeated except for the powder.
Example 6
The method is an impregnation method, and the preparation process is as follows:
1) Dissolving 4.20 g of 1,3, 5-benzene tricarboxylic acid in 100 mL absolute ethanol, adding 10.74 g manganese nitrate solution (the mass percentage concentration is 50%), stirring at room temperature at medium speed for 6 h, slowly adding 4.0 mL triethylamine solution during stirring, drying at 120deg.C for 12 h, grinding the solid into nano-sized particles, and roasting at 400deg.C in a muffle furnace for 4 h to obtain brownish-black Mn 2 O 3 A powder;
2) Taking 2.0 g and 0.310 g Ce (NO) of the powder obtained in the step 1) 3 ) 3 •6H 2 O is mixed and dissolved in 30 mL absolute ethyl alcohol, and is kept stand at room temperature for 24 h, then is dried in a vacuum drying oven at 40 ℃, and is baked at 300 ℃ for 2 h to obtain 0.05Ce/Mn 2 O 3 A powder;
3) Weighing 880 and mg polyvinylpyrrolidone, mixing with 100 mL glycol solution, adding 20 mL noble metal salt solution with concentration of 10 g/L to obtain yellow solution, magnetically stirring 1 h at 120deg.C under oil bath condition until the yellow solution becomes dark brown solution, cooling, adding acetone to extract Pt particles, centrifuging, washing, and dispersing in ethanol to obtain Pt particle solution;
4) Mixing the powder obtained in step 2) of 1.0 g with the Pt particle solution obtained in step 3) of 7 mL, dissolving in absolute ethanol, stirring for 10 h, centrifuging ethanol for 3 times, drying in a vacuum drying oven, and roasting at 300 ℃ for 4 h to obtain catalyst for ozone catalytic oxidation of VOCs, pt-0.05Ce/Mn 2 O 3 。
Example 7
The method is an impregnation method, and the preparation process is as follows:
except that the powder added in step 4) became 0.10Ce/Mn 2 O 3 The final catalyst was changed to Pt-0.10Ce/Mn 2 O 3 The procedure of example 6 was repeated except that the other components were the same.
Example 8
The method is an impregnation method, and the preparation process is as follows:
except that the powder added in step 4) became 0.15Ce/Mn 2 O 3 The final catalyst was changed to Pt-0.15Ce/Mn 2 O 3 The procedure of example 6 was repeated except that the other components were the same.
As can be seen from FIG. 1, the catalyst can reach more than 95% conversion rate under the condition of room temperature, and has optimal catalytic performance; under the same conditions, the worst Pt-0.05Ce/Mn 2 O 3 The conversion of the catalyst is only 75%;
as can be seen from FIG. 2, the sample with the best performance has CO 2 Selectivity also performs best, 1Almost complete mineralization of toluene can be achieved at 10 ℃.
As can be seen from FIG. 3, all four catalysts showed good ozone conversion, except Pt-0.05Ce/Mn 2 O 3 Besides the samples, the other three samples can realize complete decomposition of ozone at room temperature.
As can be seen from FIG. 4, pt-0.05Ce/Mn 2 O 3 The sample has excellent stability, the toluene conversion rate is slightly reduced by adsorption in the first 15 hours, and the toluene is stable after the adsorption, and the catalyst still has the conversion rate of more than 85 percent after the test of 95 h.
Example 9
The method is an impregnation method, and the preparation process is as follows:
except that the powder added in step 4) became 0.20Ce/Mn 2 O 3 The final catalyst was changed to Pt-0.20Ce/Mn 2 O 3 The procedure of example 6 was repeated except that the other components were the same.
Example 10
The method is an impregnation method, and the preparation process is as follows:
1) Dissolving 4.20 g of 1,3, 5-benzene tricarboxylic acid in 100 mL absolute ethanol, adding 10.74 g manganese nitrate solution (the mass percentage concentration is 50%), stirring at room temperature at medium speed for 6 h, slowly adding 4.0 mL triethylamine solution during stirring, drying at 120deg.C for 12 h, grinding the solid into nano-sized particles, and roasting at 400deg.C in a muffle furnace for 4 h to obtain brown black Mn 2 O 3 A powder;
2) Weighing 880 and mg polyvinylpyrrolidone, mixing with 100 mL glycol solution, adding 20 mL noble metal salt solution with concentration of 10 g/L to obtain yellow solution, magnetically stirring 1 h at 120deg.C under oil bath condition until the yellow solution becomes dark brown solution, cooling, adding acetone to extract Pt particles, centrifuging, washing, and dispersing in ethanol to obtain Pt particle solution;
3) Mixing the powder obtained in step 1) of 1.0 g with the Pt granule solution obtained in step 2) of 7 mL, dissolving in absolute ethanol, stirring for 10 h, centrifuging with ethanol for 3 times, oven drying in vacuum drying oven, and calcining at 300 deg.C for 4 h to obtain the final productCatalyst for catalytic oxidation of VOCs by ozone-Pt/Mn 2 O 3 。
Claims (1)
1. The catalyst for low-temperature ozone catalytic oxidation of VOCs is characterized in that the catalyst is used for ozone catalytic oxidation of VOCs at room temperature and complete decomposition of ozone at room temperature is realized; the catalyst comprises a carrier, a first active component and a second active component, wherein the carrier is manganese sesquioxide, the first active component is noble metal Pt particles, and the second active component is rare earth metal oxide cerium oxide;
the mass ratio of the first active component to the second active component of the catalyst is 0.2:15;
the catalyst comprises the following components in percentage by weight: the mass percentage of noble metal Pt particles in the catalyst is 0.2 to 0.25 percent by weight based on the mass of the catalyst being 100 wt percent; the rare earth metal oxide cerium oxide accounts for 5-20 wt% of the total mass of the catalyst;
the precursor of the manganese sesquioxide is nitrate of element Mn;
the precursor of the rare earth metal oxide cerium oxide is nitrate of element Ce; pt particles are obtained by a chloroplatinic acid through a glycol reduction method;
the preparation method of the catalyst for low-temperature ozone catalytic oxidation of VOCs comprises the following steps:
1) Dissolving 4.0-5.0 g of 1,3, 5-benzene tricarboxylic acid in absolute ethanol, adding 10.0-11.0. 11.0 g of nitrate precursor of Mn element, stirring at room temperature, slowly adding 4.0-5.0 mL triethylamine solution in the stirring process, grinding the dried solid into nano-scale particles, and roasting to obtain brownish-black Mn 2 O 3 A powder; the roasting temperature is as follows: 400. the temperature is lower than the temperature; the roasting time is 4 h;
2) The brown-black Mn obtained in step 1) is reacted with 2 O 3 Mixing the powder with nitrate precursors of Ce elements with different masses, dissolving in absolute ethyl alcohol, standing at room temperature, and drying and roasting to obtain w% Ce/Mn 2 O 3 Powder, wherein w% is 5%, 10%, 15%, 20%, respectively;
3) Weighing 800-900 mg polyvinylpyrrolidone and 100 mL glycol solution, mixing, adding 20 mL noble metal salt solution with the concentration of 10 g/L to obtain yellow solution, magnetically stirring 1 h under the condition of 120 ℃ oil bath until the yellow solution becomes dark brown solution, cooling, adding acetone to extract Pt particles, centrifuging, washing, and dispersing in ethanol to obtain Pt particle solution;
4) Mixing the powder obtained in the step 1.0 g and the Pt particle solution obtained in the step 7 mL) and dissolving in absolute ethyl alcohol, stirring the mixture for 8 to 12 h, and centrifuging, drying and roasting the mixture to obtain the catalyst for ozone catalytic oxidation of VOCs;
in step 1), the nitrate precursor of the Mn element is: manganese nitrate solution with the mass percentage concentration of 50%;
in the step 3), the noble metal salt solution is H 2 PtCl 6；
In the loading process of the first active component and the second active component, drying is carried out in a vacuum drying oven;
the stirring rotating speed is as follows: 300-400 r/min.
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