CN108295866A - A kind of nano flower spinelle CoMn for VOCs catalysis oxidations2O4Catalyst, preparation method and application - Google Patents
A kind of nano flower spinelle CoMn for VOCs catalysis oxidations2O4Catalyst, preparation method and application Download PDFInfo
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- CN108295866A CN108295866A CN201810255389.2A CN201810255389A CN108295866A CN 108295866 A CN108295866 A CN 108295866A CN 201810255389 A CN201810255389 A CN 201810255389A CN 108295866 A CN108295866 A CN 108295866A
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- 229910002521 CoMn Inorganic materials 0.000 title claims abstract description 26
- 239000012855 volatile organic compound Substances 0.000 title claims abstract description 25
- 239000002057 nanoflower Substances 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 61
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 14
- 238000001354 calcination Methods 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 6
- 238000001338 self-assembly Methods 0.000 claims abstract description 3
- 230000003647 oxidation Effects 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000012360 testing method Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000011572 manganese Substances 0.000 claims description 6
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 5
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 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
- 238000003756 stirring Methods 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 239000004615 ingredient Substances 0.000 claims description 2
- 229940071125 manganese acetate Drugs 0.000 claims description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract description 40
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract description 18
- 230000000694 effects Effects 0.000 abstract description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 abstract description 10
- 229910016978 MnOx Inorganic materials 0.000 abstract description 9
- 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 8
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract description 2
- 239000003153 chemical reaction reagent Substances 0.000 abstract 1
- 230000001376 precipitating effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 229910052596 spinel Inorganic materials 0.000 description 7
- 239000011029 spinel Substances 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 230000010718 Oxidation Activity Effects 0.000 description 4
- 230000008569 process Effects 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
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000000356 contaminant Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000008246 gaseous mixture Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 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
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000000713 high-energy ball milling Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000010189 synthetic method Methods 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
- 229910017816 Cu—Co Inorganic materials 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 229910003168 MnCo2O4 Inorganic materials 0.000 description 1
- 229910003119 ZnCo2O4 Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 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
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
-
- 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
-
- 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
-
- B01J35/23—
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- B01J35/393—
-
- B01J35/615—
-
- 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
-
- 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
-
- 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 belongs to environmental catalysis purification techniques fields, provide a kind of nano flower spinelle CoMn for VOCs catalysis oxidations2O4Catalyst, preparation method and applications.Oxalic acid obtains spinelle CoMn as precipitating reagent, washing, dry, calcining2O4Catalyst.CoMn prepared by the present invention2O4Catalyst shows nanometer sheet and is self-assembly of nano flower-like structure.Compared to oxide Co3O4、MnOxWith mixed phase Co3O4/MnOxAnd current spinelle CoMn reported in the literature2O4Catalyst, the spinelle CoMn that the present invention prepares2O4Catalyst shows preferable activity and stability in VOCs removals, 99% toluene removal rate can be reached at 220 DEG C, 100% conversion of formaldehyde is realized at 90 DEG C, while can reach 100% to the removal rate of acetone at 170 DEG C, and there is preferable prospects for commercial application.
Description
Technical field
The present invention relates to a kind of spinelle CoMn2O4The efficiently catalyst and preparation method of removal VOCs, belongs to environmental catalysis
Purification techniques field.
Background technology
As related chemical engineering industry continues to develop, the volatile organic contaminant given off in air is on the increase.Volatilization
Property organic pollution derives from a wealth of sources, and is mainly derived from the used organic solvent of interior decoration ornament materials, aqueous coating, paint etc.
And industrial waste gas and motor vehicle tailstock gas.In face of being continuously increased and to the mankind, animals and plants band for volatile organic contaminant
The adverse effect come, the discharge for controlling volatile organic contaminant are very urgent.Catalytic oxidation removes VOCs as a kind of high
The minimizing technology of effect and be widely used, the research and development of efficient stable catalyst have very important significance.
Research finds that transition metal oxide possesses lower cost and preferable stability, and has good storage
Oxygen ability can be converted to realize quick redox reaction between different valence state, the table in multiple catalytic oxidations
Reveal preferable catalytic activity.In recent years, numerous studies are expanded to manganese-based catalyst, adulterates, adds other transition metal, changes
The internal structure for becoming one-component transition metal oxide generates some faults of construction etc., and then improves Catalyst Adsorption oxygen, work
Change oxygen and transmits the ability of oxygen, it is final to improve transition metal oxide catalytic oxidation activity.Compared to remaining transition metal oxide
Catalyst, manganese, copper and Co catalysts possess relatively good activity in the catalytic oxidation of VOCs and are referred to as " environment friend
Good type catalyst ".
Spinel strucutre oxides AB2O4Due to having some peculiar properties, it is widely used in numerous areas.It is Chinese special
Profit net 102000576 A of CN are prepared for bi-component Cu-Co-O composite oxides using high energy ball milling method, with spinelle CuCo2O4
And Cu-Co solid solution thereofs exist, at 250 DEG C realize toluene complete oxidation, but high energy ball milling method must by presoma into
Row high-temperature process will increase the manufacturing cost of catalyst.In view of the above-mentioned problems, development spinelle technology of preparing has colloidal sol solidifying at present
Glue method, the precipitation method and the hot method of hydrothermal/solvent etc., to reduce synthetic method temperature.Wang etc. is prepared for three using hard template method
Tie up mesoporous ZnCo2O4And CoFe2O4Spinel catalyst reaches 90% benzene removal rate (ACS at 236 DEG C and 261 DEG C respectively
Catal.,2017.7, 1626-1636).Liang etc. obtains jakobsite using coprecipitation, at 250 DEG C by formaldehyde
Permineralization (J.Hazard.Mater., 2016.306,305-312).Seyed Ali Hosseini etc. using collosol and gel with
Coprecipitation is prepared for CoMn respectively2O4Spinelle, and propose that spinel structure defect is more sensitive to synthetic method and condition,
Its crystal phase structure includes the CoMn of mixed phase2O4And MnCo2O4Two kinds of structures, respectively in 320 DEG C and 260 DEG C to toluene and 2- propyl alcohol
Reach 80% conversion ratio, specific surface area only has 31m2g-1。(J.Environ. Sci.Health,Part A.,2011.46,
291-297).Although having the forward position document that correlation prepares spinel catalyst, the point of single-phase is prepared in a mild condition
Spinel catalysts remain difficult to control, while its specific surface area is relatively low, and VOCs low-temperature oxidation activities need to be improved, and VOCs removes energy
It consumes larger, increases its application cost.
In consideration of it, the present invention prepares spinelle CoMn using oxalic acid sol-gal process2O4, the catalyst specific surface of synthesis
Product is big, reducing property is good and oxygen mobility can be high, can realize that VOCs is removed at a lower temperature, have preferable stability,
It has a extensive future.
Invention content
The purpose of the present invention is to provide nano flower spinelle CoMn2O4Catalyst and preparation method, and as VOCs oxygen
The catalyst of change.The features such as catalyst is active good, and stability is high and reproducible, preparation method is simple, synthesis
Temperature is relatively low, and preferable low temperature active is shown in VOCs catalytic oxidations.
Technical scheme of the present invention：
A kind of nano flower spinelle CoMn for VOCs catalysis oxidations2O4Catalyst, the nano flower spinelle
CoMn2O4The ingredient of catalyst is single crystalline phase CoMn2O4, nano flower is self-assembly of by nanometer sheet, crystallite dimension is
7.9nm, specific surface area 124.4m2g-1；The spinel catalyst possesses preferable VOCs oxidation activities, can be in 30-300
DEG C realize VOCs effectively remove.
A kind of nano flower spinelle CoMn for VOCs catalysis oxidations2O4The preparation method of catalyst, using oxalic acid colloidal sol
Gel method, steps are as follows：
Manganese acetate and cobalt nitrate dissolving are scattered in ethanol solution, are placed in 60-80 DEG C of heat collecting type constant temperature blender with magnetic force
It is vigorously stirred；0.24mol/L oxalic acid solutions are then rapidly joined, control metal is 1 with oxalic acid molar ratio:1.2, Mn/Co moles
Than being 2:1, it continues at and stirs 0.5-4 h in 60-80 DEG C of heat collecting type constant temperature blender with magnetic force；The substance centrifuge washing that will be obtained,
Dry 12-24h is positioned in 60-100 DEG C of baking oven, finally the 350-550 DEG C of calcining 3-5h in Muffle furnace, 1 DEG C of heating rate/
Min obtains the single spinelle CoMn of crystalline phase2O4Catalyst.
The CoMn of the present invention2O4Catalyst is used for VOCs catalysis oxidations：Reaction gas is 100-1000ppm VOCs, Ar conducts
Balance Air, wherein including 20%O2, hybrid reaction gas velocity is 30-100mL/min, catalyst amount 0.05-0.2g, activity
Test operates continuously on self-built micro-reaction device.
The CoMn of the present invention2O4Catalyst can realize the complete oxidation of VOCs at a lower temperature, while can keep
Good stability.In addition, the catalyst also possesses preferable activity in denitration and ammonia SCO eliminations etc..
Beneficial effects of the present invention：Nano flower CoMn2O4Catalyst is prepared using oxalic acid sol-gal process, is had good
Low temperature active and stability.Preparation process is simple, and cost is relatively low, economic and environment-friendly, and repeatability is preferable, the nano flower of preparation
CoMn2O4Catalyst has higher specific surface area, preferable cryogenic reducting performance and higher oxygen mobility energy.It prepares
CoMn2O4Catalyst can realize the complete oxidation of VOCs at a lower temperature, have good prospects for commercial application.
Description of the drawings
Fig. 1 is catalyst toluene activity figure prepared by the embodiment of the present invention 1 and comparative example 1.
Fig. 2 is 1 spinel catalyst toluene stability activity figure of the embodiment of the present invention.
Fig. 3 is catalyst XRD diagram prepared by the embodiment of the present invention 1 and comparative example 1.
Fig. 4 is catalyst VOCs oxidation activity figures prepared by the embodiment of the present invention 1.
Specific implementation mode
It elaborates below to specific embodiments of the present invention.The present invention is using manganese and cobalt as active component, using oxalic acid
Prepared by sol-gal process, need not use organic solvent and surfactant, and cost is relatively low, and preparation flow is simple, repeatability
It is good.
Embodiment 1：
Spinelle CoMn2O4Preparation：
0.04mol manganese acetates and the dissolving of 0.02mol cobalt nitrates are scattered in 10mL ethanol solutions, are placed in 80 DEG C of heat collecting type perseverances
It is vigorously stirred in warm magnetic stirring apparatus.0.24mol/L oxalic acid solutions are then rapidly joined, control metal is 1 with oxalic acid ratio:1.2
It continues in 80 DEG C of heat collecting type constant temperature blender with magnetic force and stirs 30min.The substance centrifuge washing that will be obtained, is positioned over 60-100 DEG C
Dry 12-24h in baking oven, finally 400 DEG C of calcinings 3h, 1 DEG C/min of heating rate obtain spinelle CoMn in Muffle furnace2O4It urges
Agent.
Comparative example 1：
MnOxPreparation：0.03mol manganese acetates dissolving be scattered in 10mL ethanol solutions, be vigorously stirred to be formed it is uniform molten
Liquid.0.24mol/L oxalic acid solutions then are rapidly joined, 30min is vigorously stirred in 80 DEG C of heat collecting type constant temperature blender with magnetic force.It will
Obtained substance centrifuge washing is positioned in 60-100 DEG C of baking oven dry 12-24h, finally 400 DEG C of calcining 3h in Muffle furnace,
1 DEG C/min of heating rate, obtains MnOxCatalyst.
Co3O4Preparation：0.03mol cobalt nitrates dissolving be scattered in 10mL ethanol solutions, be vigorously stirred to be formed it is uniform molten
Liquid.0.24mol/L oxalic acid solutions then are rapidly joined, 30min is vigorously stirred in 80 DEG C of heat collecting type constant temperature blender with magnetic force.It will
Obtained substance centrifuge washing is positioned in 60-100 DEG C of baking oven dry 12-24h, finally 400 DEG C of calcining 3h in Muffle furnace,
1 DEG C/min of heating rate, obtains Co3O4Catalyst.
Composite oxides Co3O4/MnOxPreparation：Using incipient impregnation, weighs suitable cobalt nitrate and be dissolved in 1mL
In ionized water, the appropriate MnOx prepared is added, control Mn/Co molar ratios are 2:1, it stirs evenly, after drying at room temperature, in
Dry 12-24h in 60-100 DEG C of baking oven, finally 400 DEG C of calcinings 3h, 1 DEG C/min of heating rate obtain Co in Muffle furnace3O4/
MnOxCatalyst.
Embodiment 2：
4 kinds of catalyst prepared by embodiment 1 and comparative example 1 to toluene oxidation performance test micro- are answered self-built
Continuous operation carries out on device, and argon gas does Balance Air, is examined online using gas-chromatography GC2014 configuration TCD and fid detector
Survey gaseous material toluene molecule and product CO after reacting2Molecule.
Reaction condition is specially：Toluene concentration is 500ppm, and the flow velocity of gaseous mixture is 75mL/min, and reaction velocity is
22500mL/g h.Toluene oxidation conversion rate calculation formula：Toluene conversion %=is [(after toluene initial concentration-toluene reaction
Concentration)/toluene initial concentration] * 100.Reactivity is as shown in Figure 1, wherein spinelle CoMn2O4Catalyst activity is best,
210 DEG C reach 90% toluene conversion.
Embodiment 3：
Spinelle CoMn prepared by embodiment 12O4Catalyst is continuous in 220 DEG C in the case where keeping 2 reaction condition of embodiment
The stability of operation test catalyst, stability is as shown in Fig. 2, conversion ratio is maintained at 98% or more in 700min.
Embodiment 4：
Spinelle CoMn prepared by embodiment 12O4Catalyst carries out oxidation of formaldehyde performance test, and reaction condition is：Formaldehyde
A concentration of 120-130ppm, gaseous mixture 20%O2/ Ar, flow velocity 60mL/min, catalyst amount 0.1g.Oxidation of formaldehyde is lived
Property test result is as shown in table 1, and the complete oxidation of formaldehyde can be realized at 90 DEG C.
1 catalyst activity evaluation result of table
Embodiment 5：
Spinelle CoMn prepared by embodiment 12O4Catalyst carries out acetone oxidation performance test, and reaction condition is：Acetone
A concentration of 800-1000ppm, gaseous mixture 20%O2/ Ar, flow velocity 50mL/min, catalyst amount 0.2g.Acetone oxidation
It is active as shown in table 2, the complete oxidation of acetone can be realized at 170 DEG C.
2 catalyst activity evaluation result of table
Embodiment 6：
4 kinds of catalyst prepared by embodiment 1 and comparative example 1 carry out X-ray diffraction (XRD) and analyze test, XRD
Spectrogram is as shown in Figure 3.The spinelle CoMn prepared using sol-gal process2O4Catalyst only there is CoMn2O4Object phase,
Sol-gal process prepares MnOxCatalyst shows as Mn5O8And Mn2O3Mixed phase, Co3O4Show Co3O4Pure phase, and use
Composite oxides Co prepared by infusion process3O4/MnOxShow oxide M n5O8、Mn2O3And Co3O4Mixture phase.
Embodiment 7：
4 kinds of catalyst prepared by embodiment 1 and comparative example 1 carry out nitrogen adsorption desorption test, and analysis data obtain
Its specific surface area finds the spinelle CoMn that bigger serface is successfully prepared using this method as shown in table 32O4Catalyst.
3 specific surface area of catalyst test result of table
Claims (3)
1. a kind of nano flower spinelle CoMn for VOCs catalysis oxidations2O4Catalyst, which is characterized in that the nano flower
Spinelle CoMn2O4The ingredient of catalyst is single crystalline phase CoMn2O4, nano flower, crystallite dimension are self-assembly of by nanometer sheet
For 7.9nm, specific surface area 124.4m2g-1。
2. a kind of nano flower spinelle CoMn for VOCs catalysis oxidations2O4The preparation method of catalyst, which is characterized in that adopt
Nano flower spinelle CoMn is prepared with oxalic acid sol-gal process2O4Catalyst, steps are as follows：
Manganese acetate and cobalt nitrate dissolving are scattered in ethanol solution, are placed in 60-80 DEG C and are vigorously stirred；Then rapidly join
0.24mol/L oxalic acid solutions, control metal are 1 with oxalic acid molar ratio:1.2, Mn with Co molar ratios be 2:1, continue at 60-80 DEG C
Middle stirring 0.5-4h；The substance centrifuge washing that will be obtained is positioned in 60-100 DEG C of baking oven dry 12-24h, finally in 350-
550 DEG C of calcinings 3-5h, 1 DEG C/min of heating rate, obtain the single nano flower spinelle CoMn of crystalline phase2O4Catalyst.
3. by nano flower spinelle CoMn described in claim 12O4Catalyst is used for VOCs catalysis oxidations：Reaction gas is 100-
1000ppm VOCs, Ar are as Balance Air, wherein including 20%O2, hybrid reaction gas velocity is 30-100mL/min, catalyst
Dosage is 0.05-0.2g, and active testing operates continuously on self-built micro-reaction device.
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