CN108686650B - Cryptomelane type manganese dioxide, preparation method and application thereof - Google Patents
Cryptomelane type manganese dioxide, preparation method and application thereof Download PDFInfo
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- CN108686650B CN108686650B CN201810495659.7A CN201810495659A CN108686650B CN 108686650 B CN108686650 B CN 108686650B CN 201810495659 A CN201810495659 A CN 201810495659A CN 108686650 B CN108686650 B CN 108686650B
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- manganese dioxide
- type manganese
- cryptomelane
- potassium permanganate
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- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 title claims abstract description 210
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims abstract description 63
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 51
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 50
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 38
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000004202 carbamide Substances 0.000 claims abstract description 17
- 239000002904 solvent Substances 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 13
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N alpha-methyl toluene Natural products CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002244 precipitate Substances 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims description 61
- 238000000034 method Methods 0.000 claims description 40
- 239000012855 volatile organic compound Substances 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 238000004519 manufacturing process Methods 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 12
- 238000007084 catalytic combustion reaction Methods 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 6
- 239000007795 chemical reaction product Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 5
- 238000005949 ozonolysis reaction Methods 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 238000010304 firing Methods 0.000 claims 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 abstract description 24
- 239000002994 raw material Substances 0.000 abstract description 5
- 239000000243 solution Substances 0.000 description 28
- 239000000463 material Substances 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 17
- 238000011156 evaluation Methods 0.000 description 17
- 238000001027 hydrothermal synthesis Methods 0.000 description 15
- 230000000694 effects Effects 0.000 description 12
- 238000001556 precipitation Methods 0.000 description 12
- 229910000510 noble metal Inorganic materials 0.000 description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 10
- 238000004364 calculation method Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 238000002347 injection Methods 0.000 description 8
- 239000007924 injection Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 239000001569 carbon dioxide Substances 0.000 description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 5
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 230000036541 health Effects 0.000 description 4
- 229940071125 manganese acetate Drugs 0.000 description 4
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- 229920006221 acetate fiber Polymers 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 239000000443 aerosol Substances 0.000 description 2
- 238000003915 air pollution Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- -1 coatings Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
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- 230000000630 rising effect Effects 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000000809 air pollutant Substances 0.000 description 1
- 231100001243 air pollutant Toxicity 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 210000000349 chromosome Anatomy 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 1
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
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- 238000004817 gas chromatography Methods 0.000 description 1
- 230000036737 immune function Effects 0.000 description 1
- 239000004434 industrial solvent Substances 0.000 description 1
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 description 1
- 230000003902 lesion Effects 0.000 description 1
- 210000004698 lymphocyte Anatomy 0.000 description 1
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical class [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 210000000653 nervous system Anatomy 0.000 description 1
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- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
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- 239000005437 stratosphere Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- 231100000378 teratogenic Toxicity 0.000 description 1
- 230000003390 teratogenic effect Effects 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 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
- B01D53/76—Gas phase processes, e.g. by using aerosols
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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
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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
- B01D53/8659—Removing halogens or halogen compounds
- B01D53/8662—Organic halogen compounds
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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
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8671—Removing components of defined structure not provided for in B01D53/8603 - B01D53/8668
- B01D53/8675—Ozone
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- B01J35/31—
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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
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
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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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- 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 provides cryptomelane type manganese dioxide, a preparation method and application thereof, wherein the preparation method comprises the following steps: mixing potassium permanganate with a solvent, then mixing with urea for reaction to obtain a precipitate, and roasting the precipitate to obtain cryptomelane type manganese dioxide; wherein the usage amount of the potassium permanganate is more than the solubility of the potassium permanganate in the solvent. The preparation method of the cryptomelane type manganese dioxide is simple, raw materials are easy to obtain, the obtained cryptomelane type manganese dioxide is high in crystallinity, high in yield and high in density, volatile organic matters such as ethyl acetate, benzene and dichloromethane can be catalytically combusted under the high-temperature condition (200-500 ℃), ozone can be decomposed under the room-temperature high-humidity condition, and the cryptomelane type manganese dioxide has a good application prospect and wide environmental-protection application.
Description
Technical Field
The invention belongs to the technical field of catalysts, and relates to cryptomelane type manganese dioxide, a preparation method and application thereof.
Background
As the intensity of human industrial activities increases, a large amount of Volatile Organic Compounds (VOCs) are emitted into the atmospheric environment, causing environmental pollution through a series of chemical reactions. For example, some highly reactive VOCs may react photochemically with another atmospheric pollutant, nitrogen oxide (NOx), causing an increase in surface ozone concentration, forming photochemical smog pollution; some VOCs with low vapor pressure can also form secondary organic aerosol through nucleation and growth in a complex process, and the secondary organic aerosol is just an important component of the fine particulate matter PM 2.5. VOCs are seen as important precursors for the formation of photochemical pollution and atmospheric haze. In addition, VOCs themselves can pose a significant threat to human health. For example, the common VOCs such as formaldehyde, benzene, toluene and the like have carcinogenic and teratogenic hazards. Therefore, to remove photochemical smog, reduce particulate pollution, improve urban air quality, and protect the health of people, emission control and removal of VOCs are imperative.
The sources of the VOCs are wide, and mainly include petroleum, chemical industry, medicine, packaging, printing, coating and the like, and the emission of the VOCs is approximately 700 ten thousand tons/year, which accounts for 1/3 of the total emission of the VOCs. In the field of eliminating and purifying VOCs in the coating industry, the advanced countries in the west and Japan begin earlier. In 1955, the United states has issued the air pollution control Law, which provides detailed regulation of the category and total amount of air pollutants, and later the clean air Law, which was revised twice in 1970 and 1990; in 1966, special regulations, namely '66 regulations', are specially established for the emission of VOCs in the coating industry. Under the compelling constraints of law and the impetus of business interest, various techniques for eliminating VOCs have been developed and used.
At present, the pollution problem of VOCs is highly emphasized in China, and the emission reduction of the VOCs in the whole process from raw materials to products and from production to consumption is basically realized as long as 2020 is required. Therefore, the technology for reducing the emission of the VOCs is widely researched and explored. The catalytic combustion technology has a good application prospect, and the development of a novel catalyst is a hotspot and frontier of research.
Ethyl acetate is a widely used fine chemical product, has excellent solubility and quick-drying property, has wide application, is a very important organic chemical raw material and an excellent industrial solvent, and is widely used in the production processes of acetate fibers, ethyl fibers, chlorinated rubber, vinyl resin, acetate fiber resin, synthetic rubber, coatings, paints and the like. According to estimates, about 130 million tons of ethyl acetate are used annually in a large worldwide dating, the vast majority of which are used as solvents. It is statistical that about 77% of ethyl acetate solvent is discharged into the atmosphere to cause air pollution, which affects the environmental quality and health of people.
Ozone pollution is now becoming a more and more popular concern. Ozone (O)3) With oxygen (O)2) Is an allotrope of oxygen element, and has double-edged sword function for human living environment. In the atmosphere stratosphere, ozone is beneficial to our living environment, and can resist harmful ultraviolet rays; however, near the surface, ozone is an invisible killer, which can affect the skin and nervous system of human body to different degrees and also damage the immune function of human body, so that the lymphocyte can generate chromosome lesion, thus accelerating the aging of human body and increasing the birth rate of malformed infants. The world health organization stipulates that the concentration of ozone in an environment of 8 hours of continuous operation cannot exceed 0.1 ppm. At present, the ozone pollution problem exists in indoor houses, office places, large-scale entertainment places and the like, and the ozone removing equipment with excellent development and practical effects has better market prospect.
The current methods for treating ozone mainly comprise: heat treatment method, active carbon adsorption method, electromagnetic wave radiation decomposition method, liquid medicine absorption method and catalytic method, wherein the catalytic decomposition method is one of the most ideal methods for eliminating ozone at present. Catalyst development is a very active area of research, where increasing the resistance of a catalyst to water vapor attack (activity under high humidity conditions) is an important link for the catalyst to be practical.
In the field of VOCs catalytic combustion, a noble metal-supported catalyst is one of candidate materials widely used at present, but the noble metal is high in cost, so that the catalyst is not suitable for large-scale popularization and application. Therefore, the development of non-noble metal catalysts with activity comparable to that of noble metals but with lower cost has better prospect.
Manganese oxides are the most promising non-noble metal catalysts, especially cryptomelane-type manganese dioxide. The conventional preparation method for cryptomelane type manganese dioxide comprises a hydrothermal method, a heating reflux method and the like, and the preparation method of the hydrothermal method comprises the following steps: (1) preparing a solution 1: weighing 20.54g of potassium permanganate, putting the solution in 800mL of water, and stirring strongly for later use; preparing a solution 2: weighing 39.86g of manganese acetate, dissolving in 400mL of water, adding 25mL of glacial acetic acid, sealing, and magnetically stirring; (2) under the condition that the solution 2 is sealed, dropwise adding the solution 1 into the solution 2 by using an injection pump, wherein the injection rate is 2.4mL/min, magnetically stirring in the injection process, and obtaining a mixed solution of the solution 1 and the solution 2 after the injection is finished; (3) and transferring the mixed solution of the solution 1 and the solution 2 into a 2L hydrothermal reaction kettle, placing the reaction kettle into an oven for hydrothermal reaction, keeping the temperature of the hydrothermal reaction kettle constant for 24 hours at 150 ℃, naturally cooling to room temperature after the reaction is finished, washing and filtering a crystallized product until a filtrate is neutral, drying, placing the filtrate into a muffle furnace for roasting treatment, wherein the roasting condition is that the temperature rising rate is 5 ℃/min, the temperature rises to 500 ℃, and keeping the temperature for 3 hours to obtain the cryptomelane type manganese dioxide catalyst. A reflux process such as that disclosed in CN101711990B for the preparation of a metal oxide supported molecular sieve catalyst comprising: firstly, preparing a potassium permanganate solution; secondly, preparing a manganese acetate solution; thirdly, adding the solution obtained in the step one into a three-neck flask, heating, condensing and refluxing; fourthly, adding the solution obtained in the second step into the flask obtained in the third step, condensing and refluxing the solution, and performing suction filtration and drying on the obtained black slurry-like precipitate; roasting to obtain octahedral manganese oxide molecular sieve catalyst (OMS-2) solid; fifthly, adding cerium ammonium nitrate, cobalt nitrate hexahydrate, copper nitrate trihydrate, ferric nitrate nonahydrate or yttrium nitrate into deionized water to form a solution; sixthly, mixing the solid measured in the fourth step with the solution in the fifth step, dipping cerium on the octahedral manganese oxide molecular sieve catalyst (OMS-2) solid, drying the obtained solid, and roasting. However, the hydrothermal method requires high temperature which is more than 100 ℃, the heating reflux method requires long time which is more than 24 hours. Further, the yield of manganese dioxide obtained by the above method is relatively low, about 50%, and many crystallized particles are suspended in a solvent and cannot be recovered. Causing material waste and increased energy consumption.
Therefore, there is a need in the art to develop a method for preparing cryptomelane-type manganese dioxide with wide sources of raw materials, simple preparation process and high yield.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide cryptomelane type manganese dioxide, a preparation method and application thereof, wherein the preparation method of the cryptomelane type manganese dioxide is simple, the obtained cryptomelane type manganese dioxide has high crystallinity, high yield and high density, can catalyze and combust volatile organic matters such as ethyl acetate, benzene and dichloromethane under the high temperature condition (200-.
In order to achieve the purpose, the invention adopts the following technical scheme:
one of the purposes of the invention is to provide a preparation method of cryptomelane type manganese dioxide, which comprises the following steps:
mixing potassium permanganate with a solvent, then mixing with urea for reaction to obtain a precipitate, and roasting the precipitate to obtain cryptomelane type manganese dioxide;
wherein the usage amount of the potassium permanganate is more than the solubility of the potassium permanganate in the solvent.
The cryptomelane type manganese dioxide catalyst can be obtained in high yield by a simple precipitation method, and compared with a hydrothermal method and a reflux method in the prior art, the cryptomelane type manganese dioxide catalyst has the advantages of simple, convenient and simple raw materials, mild reaction conditions, high product yield and easiness in separation and recovery.
In the preparation method, potassium permanganate and/or urea are replaced by other substances, so cryptomelane type manganese dioxide cannot be obtained. When the addition amount of the potassium permanganate is not more than the solubility of the potassium permanganate in the solvent, the catalytic activity of the obtained cryptomelane type manganese dioxide is poor.
The mixing temperature of the potassium permanganate and the solvent is 10-35 ℃, such as 15 ℃, 20 ℃, 23 ℃, 28 ℃, 30 ℃ or 32 ℃.
Preferably, the solvent is selected from deionized water.
Preferably, the molar ratio of potassium permanganate to water is 0.007 to 0.04:1, such as 0.008:1, 0.009:1, 0.010:1, 0.015:1, 0.02:1, or 0.03:1, etc., preferably (0.01 to 0.04): 1. .
Mixing potassium permanganate with a solvent, and then mixing with excessive urea for reaction. The excessive urea is slowly hydrolyzed in the aqueous solution along with the rise of the temperature, and OH is gradually released-And CO3 2-Ions. The process does not change the concentration of metal ions in the solution, and is more favorable for uniform precipitation of particles compared with other precipitants such as ammonia water and ammonium bicarbonate. The molar weight of the urea is 3-5 times of potassium permanganate ions, such as 3.2 times, 3.5 times, 4.0 times or 4.5 times.
Preferably, the molar ratio of potassium permanganate to urea is 0.2-1:1, such as 0.3:1, 0.4:1, 0.5:1, 0.6:1, 0.7:1, or 0.8:1, etc.
The reaction temperature is 70-100 deg.C, such as 70 deg.C, 78 deg.C, 83 deg.C, 88 deg.C or 96 deg.C.
Preferably, the reaction time is 1-24h, such as 2h, 3h, 5h, 8h, 10h, 15h, 18h or 23h, etc., preferably 9-24 h.
Preferably, stirring is performed during the reaction.
Preferably, the reaction is carried out under water bath conditions.
The precipitate is also washed and dried before calcination.
Preferably, the drying temperature is 80-120 deg.C, such as 85 deg.C, 90 deg.C, 95 deg.C, 100 deg.C, 105 deg.C or 115 deg.C, preferably 100 deg.C.
Preferably, the drying time is 10-48h, such as 12h, 15h, 18h, 20h, 28h, 32h, 38h or 42h, etc., preferably 18 h.
The temperature of the calcination is 400-700 deg.C, such as 420 deg.C, 450 deg.C, 480 deg.C, 510 deg.C, 550 deg.C, 590 deg.C, 620 deg.C, 650 deg.C or 680 deg.C, preferably 500 deg.C.
Preferably, the roasting time is 1-10h, such as 2h, 5h, 8h or 9h, etc., preferably 3 h.
Preferably, the atmosphere of the calcination is an oxidizing atmosphere.
As a preferred technical scheme, the preparation method of cryptomelane type manganese dioxide comprises the following steps:
(1) stirring and mixing potassium permanganate and water at the temperature of 10-35 ℃, wherein the molar ratio of potassium permanganate to water is (0.007-0.04):1, so as to obtain a mixture;
(2) adding excessive urea into the mixture, wherein the molar weight of the urea is 3-5 times of that of potassium permanganate ions, heating the mixture to 70-100 ℃ in a water bath, and continuously stirring the mixture for 1-24 hours to obtain a reaction product; wherein the molar ratio of potassium permanganate to urea is 0.5-1.25: 1;
(3) carrying out solid-liquid separation on the reaction product, washing, and drying at 80-120 ℃ for 10-48h to obtain a dried substance;
(4) and roasting the dried substance for 1-10h in the air atmosphere at the temperature of 400-700 ℃ to obtain the cryptomelane type manganese dioxide.
The invention also provides cryptomelane type manganese dioxide obtained by the preparation method. The cryptomelane type manganese dioxide has the advantages of high crystallinity, high yield (the yield of the method is more than 90 percent, and the yield of the hydrothermal method is about 50 percent at most), high density ((the bulk density of 40-60-mesh particles is 0.6-0.8g/mL, and the density is twice of the bulk density of the 40-60-mesh particles obtained by the hydrothermal method), and the like.
The invention also provides the application of the cryptomelane type manganese dioxide as a catalyst for catalyzing and combusting VOCs. Namely, the invention also provides a method for improving the efficiency of catalytic combustion of VOCs, and the method uses the cryptomelane type manganese dioxide.
Preferably, the VOCs comprise any one or a combination of at least two of ethyl acetate, benzene or dichloromethane, typically but not limited to a combination of ethyl acetate and benzene, benzene and dichloromethane, dichloromethane and ethyl acetate, benzene and dichloromethane.
The cryptomelane type manganese dioxide can catalyze and combust volatile organic compounds such as ethyl acetate, benzene and dichloromethane under the high temperature condition (200-500 ℃). Compared with the conventional noble metal catalyst, the performance of catalyzing and combusting the ethyl diacid is better (the noble metal catalyst needs a reaction temperature of about 300 ℃ under the same condition, but only needs a reaction temperature of 200 ℃ when the cryptomelane type manganese dioxide provided by the invention is used), the cost is lower, the excellent catalytic performance can still be shown under a high airspeed environment, the catalyst can be widely applied to the field of purification treatment of ethyl acetate, benzene and dichloromethane, a small reactor is convenient to manufacture, and the fixed investment cost is reduced.
The invention also provides another application of cryptomelane type manganese dioxide which is used as a catalyst for ozonolysis. Namely, the invention also provides a method for improving the ozonolysis efficiency, which uses the cryptomelane type manganese dioxide. The cryptomelane type manganese dioxide can be used for completely catalytically decomposing ozone at room temperature (20-30 ℃) and high humidity (relative humidity is 45% -95%), namely the decomposition rate of ozone is 100%, and excellent catalytic performance can still be shown in a high airspeed environment, so that a small reactor is convenient to manufacture, and the cost of fixed investment is reduced.
The recitation of numerical ranges herein includes not only the above-recited numerical values, but also any numerical values between non-recited numerical ranges, and is not intended to be exhaustive or to limit the invention to the precise numerical values encompassed within the range for brevity and clarity.
Compared with the prior art, the invention has the beneficial effects that:
the preparation method of the cryptomelane type manganese dioxide provided by the invention is simple, the required raw materials are few, the operation is simple and convenient, and the reaction conditions are mild;
the cryptomelane type manganese dioxide provided by the invention has high crystallinity, high yield (the yield is more than 99%), small volume and high density (the bulk density of 40-60-mesh particles is 0.6-0.8 g/mL);
the cryptomelane type manganese dioxide provided by the invention can catalyze and combust volatile organic compounds such as ethyl acetate, benzene and dichloromethane under a high temperature condition (200-500 ℃), and has better performance than that of catalyzing and combusting diacid ethyl ester by a conventional precious metal catalyst (the precious metal catalyst needs a reaction temperature of about 300 ℃ under the same condition, but the cryptomelane type manganese dioxide provided by the invention only needs a reaction temperature of 200 ℃), and the cost is lower; can be widely applied to the field of purification treatment of VOCs;
the cryptomelane type manganese dioxide provided by the invention can be used for efficiently decomposing ozone under the condition of room temperature and high humidity, and the cryptomelane type manganese dioxide can be used for catalytically decomposing all ozone under the condition of room temperature (20-30 ℃) and high humidity (the relative humidity is 45% -95%), namely the decomposition rate of ozone is 100%, and excellent catalytic performance can still be shown under the environment at a high space velocity (such as 840L/(g.h));
the cryptomelane type manganese dioxide provided by the invention has excellent catalytic activity, is a very high-efficiency catalyst, can be conveniently used for manufacturing a small reactor, can reduce the fixed investment cost, has a wide application range, and has a good application prospect and wide environmental protection application.
Drawings
Fig. 1 is an XRD test pattern of the catalyst obtained in comparative example 2 and some examples.
Fig. 2 is an XRD test pattern of the catalysts obtained in comparative example 2 and some examples.
Fig. 3 is an XRD test pattern of the catalysts obtained in example 1 and comparative examples 2 to 5.
FIG. 4 is a graph showing the ethyl acetate conversion of the catalysts prepared in examples 1-4 and comparative example 1.
FIG. 5 is a graph showing the ethyl acetate conversion of the catalysts prepared in examples 1, 6-7 and comparative example 1.
FIG. 6 is a graph showing the ethyl acetate conversion of the catalysts prepared in examples 1, 8-10 and comparative example 1.
FIG. 7 is a graph showing the ethyl acetate conversion rates of the catalysts obtained in examples 1, 11 to 13 and comparative examples 1 to 2.
FIG. 8 is a graph showing the methylene chloride conversion of the catalysts obtained in examples 1 and 3 and comparative examples 1 and 2.
FIG. 9 is a graph showing benzene conversion efficiency and carbon dioxide yield of the catalyst prepared in example 1.
FIG. 10 is a graph showing the ozonolysis efficiency of the catalysts obtained in examples 1, 3, 5 to 7 and comparative examples 1 to 2.
Wherein the examples in the figures refer to embodiments.
Detailed Description
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings.
Example 1
A preparation method of cryptomelane type manganese dioxide comprises the following steps:
(1) under the condition that the temperature is 20 ℃, 0.3mol of potassium permanganate is added into 273mL of deionized water to obtain a mixture;
(2) adding 63g of excessive urea into the mixture, putting the mixture into a water bath device, heating the mixture to 90 ℃, and continuously stirring the mixture for reacting for 18 hours to obtain a reaction product;
(3) carrying out suction filtration and washing on a reaction product, and drying at 100 ℃ for 12h to obtain a dried substance;
(4) and roasting the dried substance for 3 hours at the temperature of 500 ℃ in the air atmosphere to obtain the cryptomelane type manganese dioxide. The tablets are sieved into 40-60 meshes for evaluation and are ready for use.
The final yield of the cryptomelane type manganese dioxide is 99 percent by calculation, materials are completely and successfully trapped through precipitation reaction, no material loss exists, and the bulk density of the cryptomelane type manganese dioxide is 0.8 g/mL.
Example 2
A process for preparing cryptomelane type manganese dioxide, the conditions being the same as in example 1 except that the temperature of the water bath is 70 ℃. The obtained cryptomelane type manganese dioxide pressed sheet is sieved into 40-60 meshes for evaluation and standby.
The final yield of the cryptomelane type manganese dioxide is 90% by calculation, materials are completely and successfully trapped through precipitation reaction, no material loss exists, and the bulk density of the cryptomelane type manganese dioxide is 0.6 g/mL.
Example 3
A process for preparing cryptomelane type manganese dioxide, the conditions being the same as in example 1 except that the temperature of the water bath is 80 ℃. The obtained cryptomelane type manganese dioxide pressed sheet is sieved into 40-60 meshes for evaluation and standby.
The final yield of the cryptomelane type manganese dioxide is 92% by calculation, materials are completely and successfully trapped through precipitation reaction, no material loss exists, and the bulk density of the cryptomelane type manganese dioxide is 0.75 g/mL.
Example 4
A process for preparing cryptomelane type manganese dioxide, the conditions being the same as in example 1 except that the temperature of the aqueous bath is 100 ℃. The obtained cryptomelane type manganese dioxide pressed sheet is sieved into 40-60 meshes for evaluation and standby.
The final yield of the cryptomelane type manganese dioxide is 98%, the materials are all successfully trapped through precipitation reaction, no material loss occurs, and the bulk density is 0.8 g/mL.
Example 5
A process for preparing cryptomelane type manganese dioxide, except that the reaction time in water bath is 9h, the other conditions are the same as in example 1. The obtained cryptomelane type manganese dioxide pressed sheet is sieved into 40-60 meshes for evaluation and standby.
The final yield of cryptomelane type manganese dioxide was calculated to be 98% and its bulk density was 0.7 g/mL.
Example 6
A process for preparing cryptomelane type manganese dioxide, except that the reaction time in water bath is 12h, the other conditions are the same as in example 1. The obtained cryptomelane type manganese dioxide pressed sheet is sieved into 40-60 meshes for evaluation and standby.
The final yield of the cryptomelane type manganese dioxide is 99 percent by calculation, materials are completely and successfully trapped through precipitation reaction, no material loss exists, and the bulk density of the cryptomelane type manganese dioxide is 0.8 g/mL.
Example 7
A process for preparing cryptomelane type manganese dioxide, except that the reaction time in water bath is 24h, the other conditions are the same as in example 1. The obtained cryptomelane type manganese dioxide pressed sheet is sieved into 40-60 meshes for evaluation and standby.
The final yield of the cryptomelane type manganese dioxide is 99 percent by calculation, materials are completely and successfully trapped through precipitation reaction, no material loss exists, and the bulk density of the cryptomelane type manganese dioxide is 0.8 g/mL.
Example 8
A cryptomelane type manganese dioxide was prepared in the same manner as in example 1, except that 0.11mol of potassium permanganate was added. The obtained cryptomelane type manganese dioxide pressed sheet is sieved into 40-60 meshes for evaluation and standby. The final yield of the cryptomelane type manganese dioxide is 99 percent by calculation, materials are completely and successfully trapped through precipitation reaction, no material is lost, and the bulk density of the cryptomelane type manganese dioxide is 0.68 g/mL.
Example 9
A cryptomelane type manganese dioxide was prepared in the same manner as in example 1, except that 0.4mol of potassium permanganate was added. The obtained cryptomelane type manganese dioxide pressed sheet is sieved into 40-60 meshes for evaluation and standby.
The final yield of the cryptomelane type manganese dioxide is 99 percent by calculation, materials are completely and successfully trapped through precipitation reaction, no material loss exists, and the bulk density of the cryptomelane type manganese dioxide is 0.8 g/mL.
Example 10
A cryptomelane type manganese dioxide was prepared in the same manner as in example 1, except that 0.6mol of potassium permanganate was added. The obtained cryptomelane type manganese dioxide pressed sheet is sieved into 40-60 meshes for evaluation and standby.
The final yield of the cryptomelane type manganese dioxide is 95% by calculation, materials are completely and successfully trapped through precipitation reaction, no material loss exists, and the bulk density of the cryptomelane type manganese dioxide is 0.7 g/mL.
Example 11
A cryptomelane type manganese dioxide is prepared under the same conditions as in example 1 except that the roasting temperature is 400 ℃ and the roasting time is 1 hour. The obtained cryptomelane type manganese dioxide pressed sheet is sieved into 40-60 meshes for evaluation and standby. The final yield of the cryptomelane type manganese dioxide is 99 percent by calculation, materials are completely and successfully trapped through precipitation reaction, no material loss exists, and the bulk density of the cryptomelane type manganese dioxide is 0.8 g/mL.
Example 12
A cryptomelane type manganese dioxide was prepared under the same conditions as in example 1 except that the calcination temperature was 600 ℃. The obtained cryptomelane type manganese dioxide pressed sheet is sieved into 40-60 meshes for evaluation and standby.
Example 13
A cryptomelane type manganese dioxide is prepared under the same conditions as in example 1 except that the roasting temperature is 700 ℃ and the roasting time is 1 hour. The obtained cryptomelane type manganese dioxide pressed sheet is sieved into 40-60 meshes for evaluation and standby.
Comparative example 1
Commercial noble metal catalyst 1 wt% Pt/Al2O3The powder particles are 40-60 meshes.
Comparative example 2
A cryptomelane type manganese dioxide catalyst is prepared by the following steps:
(1) preparing a solution 1: weighing 20.54g of potassium permanganate, putting the solution in 800mL of water, and stirring strongly for later use; preparing a solution 2: weighing 39.86g of manganese acetate, dissolving in 400mL of water, adding 25mL of glacial acetic acid, sealing, and magnetically stirring;
(2) under the condition that the solution 2 is sealed, dropwise adding the solution 1 into the solution 2 by using an injection pump, wherein the injection rate is 2.4mL/min, magnetically stirring in the injection process, and obtaining a mixed solution of the solution 1 and the solution 2 after the injection is finished;
(3) and transferring the mixed solution of the solution 1 and the solution 2 into a 2L hydrothermal reaction kettle, placing the reaction kettle into an oven for hydrothermal reaction, keeping the temperature of the hydrothermal reaction kettle constant for 24 hours at 150 ℃, naturally cooling to room temperature after the reaction is finished, washing and filtering a crystallized product until a filtrate is neutral, drying, placing the filtrate into a muffle furnace for roasting treatment, wherein the roasting condition is that the temperature rising rate is 5 ℃/min, the temperature rises to 500 ℃, and keeping the temperature for 3 hours to obtain the cryptomelane type manganese dioxide catalyst.
The obtained catalyst is sieved by a tablet press to be evaluated into 40-60 meshes for later use.
The calculated yield of the cryptomelane type manganese dioxide catalyst is 50%, the materials are very fine and are not easy to be successfully trapped, the materials are greatly lost along with the filtrate, and the bulk density of the cryptomelane type manganese dioxide catalyst is 0.4 g/mL.
Comparative example 3
A cryptomelane type manganese dioxide was prepared in the same manner as in example 1, except that 0.08mol of potassium permanganate was added.
The obtained cryptomelane type manganese dioxide pressed sheet is sieved into 40-60 meshes for evaluation and standby.
Comparative example 4
A catalyst was prepared under the same conditions as in example 1 except that potassium permanganate was replaced with manganese acetate.
Comparative example 5
A process for preparing catalyst features that the urea is replaced by NH4HCO3Otherwise, the other conditions were the same as in example 1.
And (3) performance testing:
the XRD tests were performed on the products prepared in examples 1 to 13 and comparative examples 2 to 5, and the results are shown in fig. 1 to 3, which showed that: the products of examples 1-13 and comparative example 2 are cryptomelane type manganese dioxide, and comparative examples 3-5 can not obtain cryptomelane type manganese dioxide, wherein the parameter changes in examples 3, 5, 12 and 13 have obvious influence on the crystallization property.
And (3) carrying out volatile organic compound catalytic combustion activity evaluation on part of the prepared 40-60-mesh catalyst particles on a fixed bed reactor, wherein the catalyst evaluation conditions are as follows:
the composition of the reaction mixture gas is: ethyl acetate or benzene or dichloromethane [ C ]4H8O2]＝1500ppm， [O2]20% (volume percentage content))，N2As balance gas, the total flow of the gas is 300mL/min, the space velocity is 90L/(g.h), and the reaction temperature is 150-. The concentrations of benzene, carbon dioxide and oxygen were measured by gas chromatography (Agilent-7980B, FID and TCD).
The ethyl acetate conversion curves for the catalytic combustion of ethyl acetate are shown in FIGS. 4-7, from which it can be seen. The water bath reaction temperature, time, initial molar weight and roasting temperature have obvious influence on the performance of the formed cryptomelane manganese dioxide for catalyzing ethyl acetate. But the activity of the catalyst prepared by the method is superior to that of the conventional noble metal catalyst, and the cost is lower. The activity was superior compared to the samples prepared by the hydrothermal method. Moreover, the density is higher, the airspeed is higher under the same condition, and the method is more favorable for popularization and use.
The curve for the conversion of methylene chloride to catalytic combustion methylene chloride is shown in FIG. 8, from which it can be seen. The activity of cryptomelane manganese dioxide prepared by the method for catalyzing and combusting dichloromethane containing chlorine volatile organic compounds is far higher than that of a commercial noble metal catalyst, and the activity of a product optimized by preparation parameters is better than that of a sample prepared by a hydrothermal method.
The benzene conversion efficiency and carbon dioxide yield curves for catalytic combustion of benzene are shown in fig. 9, from which it can be seen. The catalyst provided by the invention has excellent performance of catalyzing and burning benzene, can completely convert benzene into harmless carbon dioxide at 250 ℃, and has no influence on activity by adding a certain amount of water vapor, which shows that the catalyst has excellent water resistance and is more favorable for being popularized to practical conditions for use.
The performance of the catalyst for catalytic combustion of VOCs obtained in the example 1 is optimal, and the conversion rate of dichloromethane in catalytic combustion of the catalyst obtained in the other examples is more than 70% at the reaction temperature of 400 ℃; the conversion efficiency and the yield of carbon dioxide of benzene catalytically combusted are both more than 95% at a reaction temperature of 250 ℃.
In conclusion, the catalyst prepared by the uniform coprecipitation method has the capability of obviously removing volatile organic matters such as ethyl acetate, dichloromethane and benzene, and the activity of the catalyst is higher than that of a commercial noble metal catalyst.
Will be prepared intoThe catalyst particles of 40-60 meshes are subjected to an ozone purification catalyst activity evaluation test under the following test conditions: ozone concentration 40ppm, O2: 20% (volume percentage content), relative humidity 65%, N2As a balance gas, the reaction temperature was controlled by a thermostatic bath at 25 ℃ and the space velocity was 840L/(g.h), and the ozone concentration was measured by a U.S. 2B ozone analyzer.
The test results are shown in fig. 10, which shows that the catalyst prepared by the method has a remarkable ozone decomposing capability, and has better performance than the conventional noble metal catalyst and the manganese dioxide prepared by the hydrothermal method. It is noted that the relative humidity is 65% under the test condition, and therefore, the ozone decomposition performance is excellent under the high humidity condition, and the application potential is good.
The catalyst obtained in example 1 has the best ozone catalytic performance, and the catalysts obtained in other examples have the capability of catalyzing the decomposition of ozone under the same conditions of more than 60 percent.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (20)
1. A preparation method of cryptomelane type manganese dioxide is characterized by comprising the following steps:
mixing potassium permanganate with a solvent, then mixing with urea for reaction to obtain a precipitate, and roasting the precipitate to obtain cryptomelane type manganese dioxide;
wherein the using amount of the potassium permanganate is more than the solubility of the potassium permanganate in a solvent;
the molar weight of the urea is 3-5 times of that of potassium permanganate ions;
the solvent is selected from deionized water;
the molar ratio of the potassium permanganate to the deionized water is (0.007-0.04) to 1;
the reaction temperature is 70-100 ℃;
the reaction time is 1-24 h;
the roasting temperature is 400-700 ℃;
the roasting time is 1-10 h.
2. The preparation method according to claim 1, wherein the temperature of mixing the potassium permanganate with the solvent is 10-35 ℃.
3. The preparation method according to claim 1, wherein the molar ratio of potassium permanganate to deionized water is (0.01-0.04): 1.
4. The preparation method according to claim 1 or 2, wherein the molar ratio of potassium permanganate to urea is (0.2-0.3): 1.
5. The method according to claim 1, wherein the reaction time is 9 to 24 hours.
6. The production method according to claim 1 or 2, wherein stirring is performed during the reaction.
7. The method of claim 1 or 2, wherein the reaction is carried out under water bath conditions.
8. A method according to claim 1 or 2, characterized in that the precipitate is further washed and dried before calcination.
9. The method according to claim 8, wherein the drying temperature is 80 to 120 ℃.
10. The method according to claim 9, wherein the drying temperature is 100 ℃.
11. The method of claim 8, wherein the drying time is 10-48 hours.
12. The method of claim 11, wherein the drying time is 18 hours.
13. The method of claim 1, wherein the firing temperature is 500 ℃.
14. The method of claim 1, wherein the firing time is 3 hours.
15. The production method according to claim 1 or 2, characterized in that the atmosphere of the calcination is an oxidizing atmosphere.
16. The method of claim 1, comprising the steps of:
(1) stirring and mixing potassium permanganate and water at the temperature of 10-35 ℃, wherein the molar ratio of potassium permanganate to water is (0.007-0.04):1, so as to obtain a mixture;
(2) adding excessive urea into the mixture, heating to 70-100 ℃ in a water bath, and continuously stirring for 1-24h to obtain a reaction product; wherein the molar ratio of potassium permanganate to urea is (0.2-0.3) to 1;
(3) carrying out solid-liquid separation on the reaction product, washing, and drying at 80-120 ℃ for 10-48h to obtain a dried substance;
(4) and roasting the dried substance for 1-10h in the air atmosphere at the temperature of 400-700 ℃ to obtain the cryptomelane type manganese dioxide.
17. Cryptomelane-type manganese dioxide obtained by the production method according to one of claims 1 to 16;
the cryptomelane type manganese dioxide particle with 40-60 meshes has the bulk density of 0.6-0.8 g/mL.
18. Use of cryptomelane-type manganese dioxide according to claim 17 as a catalyst for the catalytic combustion of VOCs.
19. The use of cryptomelane-type manganese dioxide according to claim 18, the VOCs comprising any one of ethyl acetate, benzene or dichloromethane, or a combination of at least two thereof.
20. Use of cryptomelane-type manganese dioxide according to claim 17 as a catalyst for ozonolysis.
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| CN114733514A (en) * | 2022-03-01 | 2022-07-12 | 沈阳师范大学 | Monolithic catalyst containing cryptomelane type potassium-manganese composite oxides with different morphologies as well as preparation method and application of monolithic catalyst |
| CN114700032B (en) * | 2022-03-17 | 2023-06-16 | 中南大学 | Hidden potassium manganese ore whisker and preparation and application thereof |
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