CN108295866B - Nano flower spinel CoMn for catalytic oxidation of VOCs (volatile organic compounds)2O4Catalyst, preparation method and application - Google Patents
Nano flower spinel CoMn for catalytic oxidation of VOCs (volatile organic compounds)2O4Catalyst, preparation method and application Download PDFInfo
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- 239000011029 spinel Substances 0.000 title claims abstract description 37
- 229910052596 spinel Inorganic materials 0.000 title claims abstract description 37
- 239000012855 volatile organic compound Substances 0.000 title claims abstract description 32
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 22
- 229910002521 CoMn Inorganic materials 0.000 title claims abstract description 21
- 230000003647 oxidation Effects 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 17
- 239000002057 nanoflower Substances 0.000 title claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 62
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 230000000694 effects Effects 0.000 claims abstract description 14
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 14
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- 239000011572 manganese Substances 0.000 claims description 7
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- 239000000126 substance Substances 0.000 claims description 7
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 6
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000012360 testing method Methods 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 229940071125 manganese acetate Drugs 0.000 claims description 4
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 4
- 239000012495 reaction gas Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract description 37
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 abstract description 10
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 abstract description 9
- 229910016978 MnOx Inorganic materials 0.000 abstract description 8
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- 230000010718 Oxidation Activity Effects 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000002957 persistent organic pollutant Substances 0.000 description 4
- 229910000314 transition metal oxide Inorganic materials 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
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- 239000010941 cobalt Substances 0.000 description 2
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- 238000011156 evaluation Methods 0.000 description 2
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- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 description 2
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910020647 Co-O Inorganic materials 0.000 description 1
- 229910002518 CoFe2O4 Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910020704 Co—O Inorganic materials 0.000 description 1
- 229910016506 CuCo2O4 Inorganic materials 0.000 description 1
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- 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 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
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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
- B01D53/8678—Removing components of undefined structure
- B01D53/8687—Organic components
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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
- B01J23/005—Spinels
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- 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
- B01J37/082—Decomposition and pyrolysis
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- 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
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- 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 belongs to the technical field of environmental catalytic purification, and provides a nano flower spinel CoMn for catalytic oxidation of VOCs (volatile organic compounds)2O4Catalyst, preparation method and application thereof. Oxalic acid is used as a precipitator, and washing, drying and calcining are carried out to obtain spinel CoMn2O4A catalyst. CoMn prepared by the invention2O4The catalyst exhibits self-assembly of the nanosheets to form a nanoflower-like structure. Phase contrast oxide Co3O4、MnOxAnd mixed phase Co3O4/MnOxAnd spinel CoMn reported in the literature at present2O4Catalyst, spinel CoMn prepared by the invention2O4The catalyst shows better activity and stability in VOCs removal, can reach 99% of toluene removal rate at 220 ℃, realizes 100% conversion of formaldehyde at 90 ℃, can reach 100% of acetone removal rate at 170 ℃, and has better industrial application prospect.
Description
Technical Field
The invention relates to spinel CoMn2O4A catalyst for efficiently removing VOCs and a preparation method thereof, belonging to the technical field of environmental catalytic purification.
Background
With the continuous development of the related chemical industry, the emission of volatile organic pollutants in the air is increased. The volatile organic pollutants are widely available and mainly come from organic solvents, water-containing coatings, paints and the like used in interior decoration materials, industrial waste gas and motor vehicle tail gas. In the face of the increasing of volatile organic pollutants and the adverse effects on human beings, animals and plants, the emission of the volatile organic pollutants is controlled unsuccessfully. The method for removing VOCs by catalytic oxidation is widely applied as an efficient removal method, and the research and development of efficient and stable catalysts have very important significance.
Researches find that the transition metal oxide has lower cost, better stability and good oxygen storage and release capacity, can be converted between different valence states so as to realize rapid oxidation-reduction reaction, and shows better catalytic activity in a plurality of catalytic oxidation reactions. In recent years, a great deal of research is carried out on manganese-based catalysts, and other transition metals are doped and added to change the internal structure of a single-component transition metal oxide, generate some structural defects and the like, so that the oxygen adsorption, oxygen activation and oxygen transmission capacity of the catalyst is improved, and finally the catalytic oxidation activity of the transition metal oxide is improved. Manganese, copper and cobalt catalysts possess relatively better activity in the catalytic oxidation of VOCs than the remaining transition metal oxide catalysts and are referred to as "environmentally friendly catalysts".
Spinel structure oxide AB2O4Has some unique properties, and is widely applied in various fields. Chinese patent net CN 102000576A adopts high temperature ball milling method to prepare bi-component Cu-Co-O composite oxide, which uses spinel CuCo2O4And a Cu-Co solid solution exists, the complete oxidation of toluene is realized at 250 ℃, but the high-temperature ball milling method needs to carry out high-temperature treatment on the precursor, so that the preparation cost of the catalyst is increased. In order to solve the problems, the spinel preparation technology is developed by a sol-gel method, a precipitation method, a hydrothermal/solvothermal method and the like, so that the temperature of the synthesis method is reduced. Wang et al prepared three-dimensional mesoporous ZnCo by hard template method2O4And CoFe2O4Spinel catalysts that achieve 90% benzene removal at 236 ℃ and 261 ℃, respectively (acscatal, 2017.7, 1626-. Liang et al obtained hercynite by a coprecipitation process, which completely mineralized formaldehyde at 250 ℃ (j. hazard. mater.,2016.306,305-312). The method for respectively preparing CoMn by using sol-gel and coprecipitation methods by using Seyed Ali Hosseini and the like2O4Spinel, and the defect of spinel structure is sensitive to synthesis method and condition, and its crystal phase structure contains mixed-phase CoMn2O4And MnCo2O4Two structures, 80% conversion of p-toluene and 2-propanol at 320 ℃ and 260 ℃ respectively, the ratioThe surface area is only 31m2g-1. (J.environ. Sci.health, Part A.,2011.46,291-297). Although the prior literature of preparing spinel catalysts is available, the preparation of single-phase spinel catalysts under mild conditions is still difficult to control, the specific surface area is relatively low, the low-temperature oxidation activity of VOCs is still to be improved, the energy consumption for removing VOCs is relatively high, and the application cost is increased.
In view of the above, the invention adopts oxalic acid sol-gel method to prepare spinel CoMn2O4The synthesized catalyst has large specific surface area, good reduction performance and high oxygen flow performance, can remove VOCs at lower temperature, and has better stability and wide application prospect.
Disclosure of Invention
The invention aims to provide nanoflower spinel CoMn2O4A catalyst and a preparation method thereof, and is used as a catalyst for oxidizing VOCs. The catalyst has the characteristics of good activity, high stability, good repeatability and the like, is simple in preparation method, relatively low in synthesis temperature, and shows good low-temperature activity in the catalytic oxidation reaction of VOCs.
The technical scheme of the invention is as follows:
nano flower spinel CoMn for catalytic oxidation of VOCs (volatile organic compounds)2O4Catalyst, said nanoflower spinel CoMn2O4The catalyst comprises a single crystal phase CoMn2O4The nano flower is formed by self-assembling nano sheets, the grain size is 7.9nm, and the specific surface area is 124.4m2g-1(ii) a The spinel catalyst has good VOCs oxidation activity, and can effectively remove VOCs at 30-300 ℃.
Nano flower spinel CoMn for catalytic oxidation of VOCs (volatile organic compounds)2O4The preparation method of the catalyst adopts an oxalic acid sol-gel method and comprises the following steps:
dissolving and dispersing manganese acetate and cobalt nitrate in an ethanol solution, and placing the solution in a heat collection type constant-temperature magnetic stirrer at the temperature of 60-80 ℃ for violent stirring; then, 0.24mol/L oxalic acid solution is rapidly added, the molar ratio of metal to oxalic acid is controlled to be 1:1.2, the molar ratio of Mn/Co is controlled to be 2:1, and the reaction is continued at 60-80Stirring for 0.5-4h in a heat collection type constant-temperature magnetic stirrer; centrifugally washing the obtained substance, drying in a drying oven at 60-100 ℃ for 12-24h, calcining in a muffle furnace at 350-550 ℃ for 3-5h at a heating rate of 1 ℃/min to obtain spinel CoMn with a single crystal phase2O4A catalyst.
CoMn of the invention2O4The catalyst is used for the catalytic oxidation of VOCs: the reaction gas is 100-1000ppm VOCs, Ar is used as the balance gas, and the balance gas comprises 20 percent of O2The flow rate of the mixed reaction gas is 30-100mL/min, the dosage of the catalyst is 0.05-0.2g, and the activity test is continuously operated on a self-built micro-reaction device.
CoMn of the invention2O4The catalyst can realize the complete oxidation of VOCs at a lower temperature and simultaneously can keep good stability. In addition, the catalyst has better activity in denitration, ammonia SCO elimination and the like.
The invention has the beneficial effects that: nanometer flower CoMn2O4The catalyst is prepared by an oxalic acid sol-gel method, and has good low-temperature activity and stability. Simple preparation steps, low cost, economy, environmental protection, good repeatability and the prepared nanoflower CoMn2O4The catalyst has high specific surface area, good low-temperature reduction performance and high oxygen flow performance. Prepared CoMn2O4The catalyst can realize the complete oxidation of VOCs at a lower temperature, and has good industrial application prospect.
Drawings
FIG. 1 is a graph showing toluene activity of catalysts prepared in example 1 of the present invention and comparative example 1.
FIG. 2 is a graph of toluene stability activity of the spinel catalyst of example 1 of the present invention.
Figure 3 is an XRD pattern of the catalyst prepared in example 1 of the present invention and comparative example 1.
FIG. 4 is a graph of the oxidation activity of VOCs for the catalyst prepared in example 1 of the present invention.
Detailed Description
Specific examples of the present invention are described in detail below. The invention takes manganese and cobalt as active components, adopts oxalic acid sol-gel method for preparation, does not need organic solvent and surfactant, and has the advantages of low cost, simple preparation process and good repeatability.
Example 1:
spinel CoMn2O4The preparation of (1):
0.04mol of manganese acetate and 0.02mol of cobalt nitrate are dissolved and dispersed in 10mL of ethanol solution, and the solution is placed in a heat collection type constant temperature magnetic stirrer at the temperature of 80 ℃ for intensive stirring. Then, 0.24mol/L oxalic acid solution is quickly added, the ratio of metal to oxalic acid is controlled to be 1:1.2, and the mixture is continuously stirred in a heat collection type constant temperature magnetic stirrer at the temperature of 80 ℃ for 30 min. Centrifugally washing the obtained substance, drying in a 60-100 ℃ oven for 12-24h, calcining in a muffle furnace at 400 ℃ for 3h at a heating rate of 1 ℃/min to obtain spinel CoMn2O4A catalyst.
Comparative example 1:
MnOxthe preparation of (1): 0.03mol of manganese acetate is dissolved and dispersed in 10mL of ethanol solution, and the mixture is vigorously stirred to form a uniform solution. Then, 0.24mol/L oxalic acid solution is rapidly added, and the mixture is vigorously stirred for 30min in a heat collection type constant temperature magnetic stirrer at the temperature of 80 ℃. Centrifugally washing the obtained substance, drying in a 60-100 ℃ oven for 12-24h, calcining in a muffle furnace at 400 ℃ for 3h at a heating rate of 1 ℃/min to obtain MnOxA catalyst.
Co3O4The preparation of (1): 0.03mol of cobalt nitrate is dissolved and dispersed in 10mL of ethanol solution, and the mixture is vigorously stirred to form a uniform solution. Then, 0.24mol/L oxalic acid solution is rapidly added, and the mixture is vigorously stirred for 30min in a heat collection type constant temperature magnetic stirrer at the temperature of 80 ℃. Centrifugally washing the obtained substance, drying in a 60-100 ℃ oven for 12-24h, calcining in a muffle furnace at 400 ℃ for 3h at a heating rate of 1 ℃/min to obtain Co3O4A catalyst.
Composite oxide Co3O4/MnOxThe preparation of (1): adopting equal-volume impregnation, weighing a proper amount of cobalt nitrate, dissolving the cobalt nitrate in 1mL of deionized water, adding a proper amount of prepared MnOx, controlling the Mn/Co molar ratio to be 2:1, uniformly stirring, drying at room temperature, drying in an oven at 60-100 ℃ for 12-24h, and finally drying at 400 ℃ in a muffle furnaceCalcining for 3h at the heating rate of 1 ℃/min to obtain Co3O4/MnOxA catalyst.
Example 2:
the test of the oxidation performance of the 4 catalysts prepared in the example 1 and the comparative example 1 on toluene is carried out continuously on a self-built micro-reaction device, argon is used as balance gas, and a gas chromatography GC2014 is used for configuring TCD and FID detectors to detect the gaseous substance toluene molecules and the product CO after the reaction on line2A molecule.
The reaction conditions are specifically as follows: the toluene concentration was 500ppm, the flow rate of the mixed gas was 75mL/min, and the reaction space velocity was 22500mL/g h. Toluene oxidation conversion rate calculation formula: percent conversion of toluene [ (initial concentration of toluene-concentration after toluene reaction)/initial concentration of toluene%]*100. The reactivity is shown in FIG. 1, in which spinel CoMn2O4The catalyst activity is best, and 90% toluene conversion is achieved at 210 ℃.
Example 3:
for spinel CoMn prepared in example 12O4The catalyst was tested for its stability by continuous operation at 220 ℃ under the reaction conditions of example 2, and the stability was as shown in FIG. 2, with the conversion rate being maintained above 98% within 700 min.
Example 4:
for spinel CoMn prepared in example 12O4The catalyst is used for formaldehyde oxidation performance test, and the reaction conditions are as follows: the concentration of formaldehyde is 120-130ppm, and the mixed gas is 20% O2Ar, flow rate 60mL/min, catalyst amount 0.1 g. The results of the formaldehyde oxidation activity test are shown in table 1, and complete oxidation of formaldehyde can be achieved at 90 ℃.
TABLE 1 evaluation results of catalyst Activity
Example 5:
for spinel CoMn prepared in example 12O4The catalyst is subjected to acetone oxidation performance test, and the reaction conditions are as follows: the acetone concentration is 800-1000ppm, 20% of mixed gas O2Ar, flow rate 50mL/min, catalyst amount 0.2 g. Acetone oxidation activity as shown in table 2, complete oxidation of acetone was achieved at 170 ℃.
TABLE 2 evaluation results of catalyst Activity
Example 6:
the 4 catalysts prepared in example 1 and comparative example 1 were subjected to X-ray diffraction (XRD) analysis and the XRD patterns thereof are shown in fig. 3. Spinel CoMn prepared by sol-gel method2O4Only the catalyst of (2) shows CoMn2O4Phase of (2), preparation of MnO by sol-gel methodxThe catalyst is represented by Mn5O8And Mn2O3Mixed phase of (2), Co3O4Exhibit Co3O4Is pure phase, and the composite oxide Co prepared by the dipping method3O4/MnOxShows the oxide Mn5O8、Mn2O3And Co3O4The mixture phase of (1).
Example 7:
the 4 catalysts prepared in example 1 and comparative example 1 were subjected to a nitrogen desorption test, and the data were analyzed to obtain specific surface areas thereof, and as shown in table 3, it was found that spinel CoMn having a large specific surface area was successfully prepared by the method2O4A catalyst.
TABLE 3 results of testing specific surface area of catalyst
Claims (3)
1. Nano flower spinel CoMn for catalytic oxidation of VOCs (volatile organic compounds)2O4The catalyst is characterized in that the nanoflower spinel CoMn2O4The catalyst comprises a single crystal phase CoMn2O4Which is composed ofThe nano-sheets are self-assembled to form nano-flowers, the grain size is 7.9nm, and the specific surface area is 124.4m2g-1。
2. Nano flower spinel CoMn for catalytic oxidation of VOCs (volatile organic compounds)2O4The preparation method of the catalyst is characterized in that the oxalic acid sol-gel method is adopted to prepare the nano flower spinel CoMn2O4The catalyst comprises the following steps:
dissolving and dispersing manganese acetate and cobalt nitrate in an ethanol solution, and placing the mixture in a temperature of between 60 and 80 ℃ to stir violently; then quickly adding 0.24mol/L oxalic acid solution, controlling the molar ratio of metal to oxalic acid to be 1:1.2 and the molar ratio of Mn to Co to be 2:1, and continuously stirring for 0.5-4h at 60-80 ℃; centrifugally washing the obtained substance, drying in a drying oven at 60-100 ℃ for 12-24h, and finally calcining at 350-550 ℃ for 3-5h at the heating rate of 1 ℃/min to obtain the nano flower spinel CoMn with single crystal phase2O4A catalyst.
3. The nanoflower spinel CoMn of claim 12O4The catalyst is used for the catalytic oxidation of VOCs: the reaction gas is 100-1000ppm VOCs, Ar is used as the balance gas, and the balance gas comprises 20 percent of O2The flow rate of the mixed reaction gas is 30-100mL/min, the dosage of the catalyst is 0.05-0.2g, and the activity test is continuously operated on a self-built micro-reaction device.
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| CN110193368B (en) * | 2019-06-21 | 2022-01-28 | 河北科技大学 | Preparation method of spinel type catalytic material |
| CN110404543B (en) * | 2019-07-12 | 2022-06-14 | 上海大学 | VOC catalyst with characteristic of ordered arrangement of composite metal oxide and ferroferric oxide and preparation method thereof |
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| CN110975870A (en) * | 2019-12-12 | 2020-04-10 | 重庆工商大学 | Preparation method and application of copper-cobalt composite oxide catalyst |
| CN112742416A (en) * | 2021-01-20 | 2021-05-04 | 中国石油大学胜利学院 | Spinel type composite oxide MnCo2O4Novel preparation method of |
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