CN113101923A - Mn-Zr-La-Ce catalyst for degrading VOCs (volatile organic compounds), preparation method and low-temperature plasma concerted catalysis application thereof - Google Patents
Mn-Zr-La-Ce catalyst for degrading VOCs (volatile organic compounds), preparation method and low-temperature plasma concerted catalysis application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 92
- 229910020785 La—Ce Inorganic materials 0.000 title claims abstract description 41
- 239000012855 volatile organic compound Substances 0.000 title claims abstract description 35
- 230000000593 degrading effect Effects 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 238000006555 catalytic reaction Methods 0.000 title description 6
- 230000002153 concerted effect Effects 0.000 title description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims abstract description 99
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 claims abstract description 78
- 230000015556 catabolic process Effects 0.000 claims abstract description 51
- 238000006731 degradation reaction Methods 0.000 claims abstract description 51
- 230000002195 synergetic effect Effects 0.000 claims abstract description 14
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 9
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 9
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 9
- 230000003197 catalytic effect Effects 0.000 claims abstract description 8
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 7
- 239000002131 composite material Substances 0.000 claims abstract description 4
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- 238000001035 drying Methods 0.000 claims description 16
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- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 6
- 239000011572 manganese Substances 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- 239000012495 reaction gas Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
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- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
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- 238000007598 dipping method Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
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- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
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- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
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- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
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- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
-
- 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
-
- 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
- B01D53/8678—Removing components of undefined structure
- B01D53/8687—Organic components
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- B01J35/615—
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- 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
- B01J37/03—Precipitation; Co-precipitation
- B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2259/00—Type of treatment
- B01D2259/80—Employing electric, magnetic, electromagnetic or wave energy, or particle radiation
- B01D2259/818—Employing electrical discharges or the generation of a plasma
Abstract
The invention discloses a Mn-Zr-La-Ce catalyst for degrading VOCs (volatile organic compounds), which comprises the active components of Mn, Zr, La and Ce, wherein the molar ratio of Mn to Zr to La to Ce is 1-2:0.5-2, and the composite catalystThe specific surface area of the agent is 100-300m2(ii) in terms of/g. The Mn-Zr-La-Ce composite catalyst has higher catalytic activity and stability. The invention also discloses a preparation method of the Mn-Zr-La-Ce catalyst for degrading VOCs, which is simple, green and pollution-free. The invention also discloses application of the Mn-Zr-La-Ce catalyst for degrading the VOCs waste gas under the synergistic effect of low-temperature plasma to catalytic degradation of ethyl acetate and m-xylene respectively, and the application has higher degradation rate on the ethyl acetate and the m-xylene.
Description
Technical Field
The invention relates to the technical field of volatile organic waste gas treatment, in particular to a Mn-Zr-La-Ce catalyst for degrading VOCs (volatile organic compounds), a preparation method and a low-temperature plasma concerted catalysis application thereof.
Background
Volatile Organic pollutants (VOCs) are important precursors to today's atmospheric pollution. It can directly or indirectly cause pollution such as haze, photochemical smog, global warming and the like. VOCs have complex components and strong toxic and peculiar smell, not only can affect the atmospheric environment, but also can harm human health. With the development of economy, the treatment of the discharge of VOCs is urgent. The industrial use of organic solvents in large quantities is a key source of atmospheric VOCs. Further divided into 8 classes according to the chemical structure of volatile organic compounds, alkanes, aromatic hydrocarbons, alkenes, halocarbons, esters, aldehydes, ketones and other compounds. The main sources of the VOCs pollutants comprise an industrial fixed emission source, a motor vehicle exhaust emission source, a daily life emission source and the like. Industrial stationary sources are their primary emissions sources. Major industries for discharging VOCs mainly include petrochemical, chemical, industrial coating, printing and other industries.
Firstly, the effect of separation and recycling is achieved by a physical or chemical method, and the method mainly comprises membrane separation, adsorption, absorption and condensation; the other is that the molecular structure is destroyed by combustion, catalysis and other methods to achieve the effect of degradation, which mainly comprises biological treatment, photocatalysis and other technologies. However, these conventional treatment techniques have some disadvantages, such as high cost and difficulty in removing low concentrations of VOCs. In recent years, low temperature plasma technology has become a research focus of researchers. Researches show that the low-temperature plasma technology can degrade and convert VOCs into carbon dioxide, water and the like at normal temperature, and particularly has a unique removing effect on large-air-volume low-concentration waste gas; it can also degrade one or more mixed VOCs. It is considered to be a potentially effective way of treating industrial waste gases. However, VOCs degraded by single low-temperature plasma (NTP) are not easy to be completely mineralized, and have poor selectivity, and harmful byproducts can be generated, so that compounds with stronger toxicity are formed. The addition of a suitable catalyst to the NTP reaction system can improve the degradation effect and reduce the concentration of by-products such as ozone.
In the low-temperature plasma synergistic catalyst degradation technology, the catalyst is the core of good or no degradation effect, and the quality of the catalyst performance has decisive influence on the degradation efficiency and the reduction of the operation cost. The low-temperature plasma synergistic catalyst belongs to a solid catalyst and generally comprises a carrier, an active component, a cocatalyst and the like. The catalysts can be classified into noble metal catalysts and metal oxide catalysts (non-noble metal catalysts) according to the active components used in the catalysts. The noble metal catalyst mainly takes Pt, Au, Pd, Ag and the like as active substances, has the characteristic of high activity at low temperature, but has higher cost. In recent years, the catalytic combustion of VOCs by non-noble metal catalysts is one of the research hotspots in the field of environmental catalysis, and the catalysts have the characteristics of high catalytic oxidation activity, good stability, low price and the like, so that the catalysts are widely researched, and mainly comprise non-noble metal oxides such as Cu, Mn, Cr, La, Ce, Zr and the like.
Chinese patent publication No. CN104607172A discloses degradation of toluene by a Ce-doped plasma catalyst, wherein when the applied voltage is 17kV, the degradation rates of toluene by an empty tube, a titanium dioxide catalyst alone and a cerium-doped catalyst are 25.4%, 62.3% and 70.3%, respectively. The catalyst disclosed in the patent literature has low catalytic degradation rate, and has low degradation rate on other VOCs gases such as m-xylene and ethyl acetate.
Disclosure of Invention
The invention provides a Mn-Zr-La-Ce catalyst with higher degradation activity and stability for degrading VOCs (volatile organic compounds), a preparation method thereof and application of the Mn-Zr-La-Ce catalyst in low-temperature plasma concerted catalysis of ethyl acetate and m-xylene.
The active components of the catalyst are Mn, Zr, La and Ce, and the molar ratio of Mn to Zr to La to Ce is 1-2:0.5-2:0.5-2: 0.5-2; the specific surface area of the catalyst is 100-300m2/g。
The catalyst has higher specific surface area, active components Mn, Zr, La and Ce in the catalyst are uniformly and orderly distributed on the surface of the catalyst, and a large number of anion defects exist on the surface of the catalyst to provide proper activation positions for molecular oxygen, so that the catalyst has higher catalytic performance and stability.
The invention also provides a preparation method of the Mn-Zr-La-Ce catalyst for degrading VOCs, which comprises the following steps:
(1) preparing precursor solutions according to the atomic molar ratio of Mn, Zr, La and Ce of 1-2:0.5-2:0.5-2:0.5-2, mixing to obtain a mixed salt solution, and ultrasonically stirring uniformly;
(2) adding a nano alumina carrier into the mixed salt solution, stirring, and drying in the shade at room temperature for 24-26h to form gel;
(3) and drying the gel for 1-2h, and calcining for 3-5h to obtain the Mn-Zr-La-Ce composite catalyst.
The active component of the catalyst is firmly and uniformly loaded on the nano alumina rich in the defect sites in a nano particle state, so that the Mn-Zr-La-Ce catalyst loaded with the nano alumina has higher catalytic activity and stability.
Based on active components (manganese, zirconium, lanthanum and cerium), dipping the active components into a nano alumina carrier in a nitrate solution form and permeating the carrier into the inner surface, drying the carrier after the dipping balance, evaporating and overflowing water to leave salts of the active components on the inner surface of the carrier, uniformly distributing the metal salts in pores of the carrier, and heating and decomposing the metal salts to obtain the highly dispersed catalyst.
In the step (1), the ultrasonic stirring conditions are that the ultrasonic stirring time is 20-30min and the ultrasonic stirring speed is 0-2400 r/min.
In the step (2), the nano alumina carrier is gamma-phase alumina, and the average grain diameter is 20 nm.
The gamma-phase alumina carrier has the main function of dispersing active components on the surface of the carrier to form a stable structure and simultaneously plays a supporting role.
In the step (2), the volume ratio of the nano alumina carrier to the mixed solution is 1-1.05: 1. The proper volume ratio of the nano alumina carrier to the mixed solution ensures that the moisture in the mixed solution is absorbed by the nano alumina carrier in a large amount, and the mixed solution is in an anhydrous paste state, so that the carrier can be completely impregnated with a metal salt solution, excessive redundant impregnating solution is saved, the content of active components in the catalyst is convenient to control, and the active components are saved.
In the step (3), the drying condition is drying for 1.5-2h at the temperature of 105-120 ℃.
In the step (3), the calcination condition is that the calcination is carried out for 3-5h at the temperature of 300-500 ℃.
The invention also provides application of the Mn-Zr-La-Ce catalyst in respectively catalyzing and degrading ethyl acetate or m-xylene under the synergistic action of low-temperature plasma.
The mass concentration ranges of the ethyl acetate and the m-xylene are respectively 800-1100mg/m3、100-400mg/m3。
The degradation rate of the ethyl acetate is up to more than 91.0%, and the degradation rate of the m-xylene is up to more than 90.0%.
Compared with the prior art, the invention has the beneficial effects that:
(1) the preparation method provided by the invention is simple, the industrial application and mass production of the catalyst can be realized, the catalyst has a very high-efficiency removal effect on m-xylene and ethyl acetate, the catalyst provided by the invention has very good high-efficiency low-temperature plasma synergistic catalytic efficiency on the m-xylene and the ethyl acetate, and the degradation efficiency can reach more than 90% when the applied voltage is 44 kV.
(2) The low-temperature plasma synergistic Mn-Zr-La-Ce catalyst provided by the invention has high degradation efficiency in degrading benzene organic matters, can obtain the catalyst suitable for synergistic low-temperature plasma degradation through different atomic ratios of manganese, zirconium, lanthanum and cerium, and has wide application prospect.
(3) The Mn-Zr-La-Ce catalyst provided by the invention takes deionized water as a solvent in the preparation process, and has no environmental pollution. Meanwhile, the raw materials of the active components of the catalyst are cheap and easy to obtain, and the cost is low.
Drawings
FIG. 1 is a graph showing the removal efficiency of M-xylene by the electrolytic degradation under empty tube conditions in the presence of a Mn-Zr-La-Ce (molar ratio 1:1:1) catalyst obtained in example 1;
FIG. 2 shows the removal efficiency of the Mn-Zr-La-Ce (molar ratio 1:1:1:1) catalyst obtained in example 1 for ethyl acetate degradation under discharge;
FIG. 3 shows the CO2 selectivity of Mn-Zr-La-Ce (molar ratio 1:1:1) catalyst obtained in example 1 for the degradation of meta-xylene under discharge.
FIG. 4 is a graph showing the comparison of the removal efficiency of the Mn-Zr-La-Ce (molar ratio 1:1:2:2) catalyst obtained in example 2 and the removal efficiency of the electrically degraded metaxylene under the empty tube condition;
FIG. 5 shows the removal efficiency of the Mn-Zr-La-Ce (molar ratio 1:1:2:2) catalyst obtained in example 2 for ethyl acetate degradation under discharge;
FIG. 6 is a photograph of a catalyst embodiment obtained in example 2.
Detailed Description
The present invention is further illustrated by the following specific examples, in which all reagents used are analytical reagents. However, the present invention is not limited to the following examples.
Example 1
The preparation method of the low-temperature plasma synergistic Mn-Zr-La-Ce catalyst comprises the following steps:
(1) 11.65mL of manganese nitrate solution with the density of 1.536g/mL is weighed, and 21.466g of zirconium nitrate, 21.6505g of lanthanum nitrate and 21.711g of cerium nitrate are respectively weighed. Respectively dissolving the four solutions in deionized water to prepare aqueous solution with the concentration of 0.2mol/L, respectively measuring and mixing the four solutions by 9mL, and then carrying out ultrasonic stirring for 30min under the condition that the stirring speed is 1200r/min for later use;
(2) subjecting gamma-Al having an average particle diameter of 20nm to heat treatment2O3Drying the powder in a drying oven at 105 ℃ for 1.5h for later use;
(3) adding 20g of the mixed metal aqueous solution obtained in the step (1) into the gamma-Al with the average grain diameter of 20nm obtained in the step (2)2O3Uniformly stirring the powder to fully soak the powder, and drying the powder in the shade for 24 hours at the room temperature of 20 ℃;
(4) placing the mixture obtained in the step (3) in an oven, and drying for 2h at the temperature of 120 ℃;
(5) placing the mixture obtained in the step (4) in a muffle furnace, calcining at 500 ℃ for 3h to obtain the loaded gamma-Al2O3Mn-Zr-La-Ce (molar ratio 1:1:1: 1).
The reasons for selecting alumina are mainly: 1. the pore volume of the alumina is larger, and the specific surface area is larger; 2. the mechanical property is good, and the cracking and the pulverization are not easy (which is very important in the market of industrial production); 3. it is used as a carrier, and has better activity; 4. the adsorption property is better, the impregnation property is better, and the loaded metal solution is easier to load.
Performance testing
The test method comprises the following steps: 1000mg of the catalyst obtained in example 1 was placed in a self-made low-temperature plasma generator. At the room temperature of 20 ℃, the concentrations of the meta-xylene and the ethyl acetate at the gas inlet end and the gas outlet end of the low-temperature plasma generator are continuously and respectively detected by GC1690, the concentrations of the meta-xylene and the ethyl acetate at the gas inlet end and the gas outlet end of the low-temperature plasma reactor are also the concentrations of the meta-xylene and the ethyl acetate before and after degradation, and the degradation rate can be obtained by calculating the concentrations before and after degradation.
Wherein the reaction gas comprises the following components:
and (3) degrading m-xylene: the concentration of the m-xylene is 300mg/m321% oxygen and 79% nitrogen, wherein nitrogen is used as carrier gas, reaction gasThe flow rate was 300 mL/min. The applied voltage is 28-44 kV. The degradation efficiency can reach 93.12% under the condition that the applied voltage is 44 kV.
And (3) degrading ethyl acetate: the concentration of ethyl acetate is 1000mg/m321% oxygen and 79% nitrogen, wherein nitrogen is used as a carrier gas, and the flow rate of the reaction gas is 300 mL/min. The applied voltage is 28-44 kV. The degradation efficiency can reach 92.02% under the condition that the applied voltage is 44 kV.
As can be seen from FIG. 1, the Mn-Zr-La-Ce (molar ratio 1:1:1) catalyst obtained in example 1 has a degradation rate of m-xylene increased from 29.52% to 93.13% at an applied voltage of 28kV to 44kV, while the degradation rate of m-xylene increased from 33.33% to 67.25% at an applied voltage of 28kV to 44kV without the catalyst, and the degradation rate is significantly higher in the case of the catalyst than in the case of the catalyst without the catalyst. Therefore, the catalyst has better degradation effect on m-xylene under the condition of cooperating with low-temperature plasma, and simultaneously, the catalyst has better synergistic effect.
As can be seen from FIG. 2, the Mn-Zr-La-Ce (molar ratio 1:1:1) catalyst obtained in example 1 has a better effect on the degradation of ethyl acetate, wherein the degradation rate of ethyl acetate is increased from 42.20% to 92.02% under the applied voltage of 28kV to 44 kV.
As can be seen from FIG. 3, the Mn-Zr-La-Ce catalyst obtained in example 1 (molar ratio 1:1:1:1) was used for the degradation of meta-xylene CO at an applied voltage of 28kV to 44kV2The selectivity is improved from 27.36 percent to 100.00 percent, and the catalyst can be seen to be used for degrading the CO of m-xylene2The selectivity is better
After the Mn-Zr-La-Ce (molar ratio is 1:1:1) catalyst obtained in example 1 is placed for 72 hours, the degradation rate of ethyl acetate and m-xylene can still reach more than 90% under the condition of applied voltage of 44kV, and the stability is good.
Example 2
The preparation method of the low-temperature plasma synergistic Mn-Zr-La-Ce catalyst comprises the following steps:
(1) 11.65mL of manganese nitrate solution with the density of 1.536g/mL is weighed, and 21.466g of zirconium nitrate, 21.6505g of lanthanum nitrate and 21.711g of cerium nitrate are respectively weighed. Dissolving them in deionized water respectively to prepare aqueous solution with the concentration of 0.2 mol/L. Weighing 6mL of each of manganese nitrate and zirconium nitrate aqueous solutions with the concentration of 0.2mol/L and 12mL of each of lanthanum nitrate and cerium nitrate aqueous solutions, mixing, and carrying out ultrasonic stirring for 30min under the condition that the stirring speed is 1200 r/min;
(2) gamma-Al with a particle size of 20nm2O3Drying the powder in an oven at 105 deg.C for 1.5h for later use
(3) Adding 15g of the mixed metal aqueous solution obtained in the step (1) into the gamma-Al with the particle size of 20nm obtained in the step (2)2O3Uniformly stirring the powder to fully soak the powder, and drying the powder in the shade for 24 hours at the room temperature of 20 ℃;
(4) placing the mixture obtained in the step (3) in an oven, and drying for 2h at the temperature of 120 ℃;
(5) placing the mixture obtained in the step (4) in a muffle furnace, calcining at 500 ℃ for 3h to obtain the loaded gamma-Al2O3Mn-Zr-La-Ce (molar ratio 1:1:2: 2).
Performance testing
The test method was to place 1000mg of the catalyst obtained in example 2 in a home-made low temperature plasma generator. At the room temperature of 20 ℃, the concentrations of the meta-xylene and the ethyl acetate between the air inlet end and the air outlet end of the low-temperature plasma generator are continuously detected by GC1690, the concentrations of the meta-xylene and the ethyl acetate between the air inlet end and the air outlet end of the low-temperature plasma generator are also the concentrations of the meta-xylene and the ethyl acetate before and after degradation, and the degradation rates of the meta-xylene and the ethyl acetate can be obtained by calculating the concentrations of the meta-xylene and the meta-xylene before and after degradation. Wherein the reaction gas comprises the following components:
and (3) degrading m-xylene: the concentration of the m-xylene is 250mg/m321% oxygen and 79% nitrogen, wherein nitrogen is used as a carrier gas, and the flow rate of the reaction gas is 300 mL/min. The applied voltage is 28-44 kV. Under the condition that the applied voltage is 44kV, the degradation efficiency can reach 90.73 percent.
And (3) degrading ethyl acetate: the concentration of ethyl acetate is 1050mg/m321% oxygen andand 79% nitrogen gas, wherein the nitrogen gas is used as a carrier gas, and the flow rate of the reaction gas is 300 mL/min. The applied voltage is 28-44 kV. Under the condition that the applied voltage is 44kV, the degradation efficiency can reach 91.74 percent.
As can be seen from FIG. 4, the Mn-Zr-La-Ce (molar ratio 1:1:2:2) catalyst obtained in example 2 has a degradation rate of m-xylene increased from 25.26% to 90.73% at an applied voltage of 28kV to 44kV, while the degradation rate of m-xylene increased from 33.33% to 67.25% at an applied voltage of 28kV to 44kV without the catalyst, and the degradation rate is significantly higher in the case of the catalyst than in the case of the catalyst without the degradation. Therefore, the catalyst has better degradation effect on m-xylene under the condition of cooperating with low-temperature plasma, and simultaneously, the catalyst has better synergistic effect.
As can be seen from FIG. 5, the Mn-Zr-La-Ce (molar ratio 1:1:2:2) catalyst obtained in example 2 has a better effect on the degradation of ethyl acetate, as the degradation rate of ethyl acetate is increased from 28.36% to 91.74% under the applied voltage of 28kV to 44 kV.
After the Mn-Zr-La-Ce (molar ratio is 1:1:2:2) catalyst obtained in example 2 is placed for 72 hours, the degradation rate of ethyl acetate and m-xylene can still reach more than 90% under the condition of applied voltage of 44kV, and the stability is good.
FIG. 6 is a photograph showing a real catalyst prepared in example 2, and it can be seen from FIG. 6 that the catalyst is not aggregated and dispersed on the surface of the carrier.
Claims (10)
1. The Mn-Zr-La-Ce catalyst for degrading VOCs is characterized in that active components of the catalyst are Mn, Zr, La and Ce, the molar ratio of Mn to Zr to La to Ce is 1-2:0.5-2:0.5-2, and the specific surface area of the catalyst is 300 m-2/g。
2. The method of claim 1 for preparing a Mn-Zr-La-Ce catalyst for degrading VOCs, comprising:
(1) preparing precursor solutions according to the atomic molar ratio of Mn, Zr, La and Ce of 1-2:0.5-2:0.5-2:0.5-2, mixing to obtain a mixed salt solution, and ultrasonically stirring uniformly;
(2) adding a nano alumina carrier into the mixed salt solution, stirring, and drying in the shade at room temperature for 24-26h to form gel;
(3) and drying the gel for 1-2h, and calcining for 3-5h to obtain the Mn-Zr-La-Ce composite catalyst.
3. The method for preparing the Mn-Zr-La-Ce catalyst for degrading VOCs according to claim 2, wherein in the step (1), the ultrasonic stirring conditions are that the ultrasonic stirring time is 20-30min and the ultrasonic stirring speed is 0-2400 r/min.
4. The method for preparing a Mn-Zr-La-Ce catalyst for degrading VOCs according to claim 2, wherein in the step (2), the nano alumina carrier is gamma phase alumina with an average particle size of 20 nm.
5. The method for preparing a Mn-Zr-La-Ce catalyst for degrading VOCs according to claim 2, wherein in the step (2), the volume ratio of the nano alumina carrier to the mixed solution is 1-1.05: 1.
6. The method for preparing a Mn-Zr-La-Ce catalyst for degrading VOCs according to claim 2, wherein in the step (3), the drying conditions are as follows: drying for 1.5-2h at the temperature of 105-120 ℃.
7. The method of claim 2, wherein the calcination conditions are as follows: calcining for 3-5h at the temperature of 300-500 ℃.
8. The use of the Mn-Zr-La-Ce catalyst for degrading VOCs according to claim 1 to catalyze the degradation of ethyl acetate and meta-xylene respectively under the synergistic effect of low-temperature plasma.
9. According toThe use of the Mn-Zr-La-Ce catalyst for degrading VOCs in claim 8 for the catalytic degradation of ethyl acetate and m-xylene respectively under the synergistic effect of low-temperature plasma, wherein the mass concentrations of the ethyl acetate and the m-xylene are respectively 800-1100mg/m3、100-400mg/m3。
10. The application of the Mn-Zr-La-Ce catalyst for degrading VOCs according to claim 9, wherein the catalyst is used for respectively catalyzing and degrading ethyl acetate and m-xylene under the synergistic effect of low-temperature plasma, and is characterized in that the degradation rate of ethyl acetate is more than 91.0%, and the degradation rate of m-xylene is more than 90.0%.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115400762A (en) * | 2022-08-25 | 2022-11-29 | 浙江工商大学 | Catalyst for catalyzing p-xylene in cooperation with low-temperature plasma, and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1990103A (en) * | 2005-12-26 | 2007-07-04 | 浙江师范大学 | Catalytic combustion catalyst |
| CN107754809A (en) * | 2017-10-23 | 2018-03-06 | 浙江工商大学 | The Cu Mn Zr composite catalysts and preparation method of degraded VOCs waste gas |
| CN109939689A (en) * | 2019-04-22 | 2019-06-28 | 内蒙古科技大学 | A kind of Rare Earth Mine monolithic catalyst, preparation method and applications |
-
2021
- 2021-04-26 CN CN202110453198.9A patent/CN113101923A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1990103A (en) * | 2005-12-26 | 2007-07-04 | 浙江师范大学 | Catalytic combustion catalyst |
| CN107754809A (en) * | 2017-10-23 | 2018-03-06 | 浙江工商大学 | The Cu Mn Zr composite catalysts and preparation method of degraded VOCs waste gas |
| CN109939689A (en) * | 2019-04-22 | 2019-06-28 | 内蒙古科技大学 | A kind of Rare Earth Mine monolithic catalyst, preparation method and applications |
Non-Patent Citations (2)
| Title |
|---|
| YUXIANG CAI等: "Plasma-catalytic decomposition of ethyl acetate over LaMO3 (M=Mn,Fe, and Co) perovskite catalysts", 《JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY》, 13 November 2018 (2018-11-13), pages 452 * |
| 许秀鑫等: "B位元素掺杂对La0.8Ce0.2MnxM1-xO3/γ-Al2O3催化剂催化VOCs燃烧性能的影响", 《石油学报（石油加工）》, 31 October 2013 (2013-10-31), pages 3 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115400762A (en) * | 2022-08-25 | 2022-11-29 | 浙江工商大学 | Catalyst for catalyzing p-xylene in cooperation with low-temperature plasma, and preparation method and application thereof |
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