CN106179396B - A kind of composite catalyst for decomposing ozone and preparation method thereof - Google Patents
A kind of composite catalyst for decomposing ozone and preparation method thereof Download PDFInfo
- Publication number
- CN106179396B CN106179396B CN201610543720.1A CN201610543720A CN106179396B CN 106179396 B CN106179396 B CN 106179396B CN 201610543720 A CN201610543720 A CN 201610543720A CN 106179396 B CN106179396 B CN 106179396B
- Authority
- CN
- China
- Prior art keywords
- composite catalyst
- preparation
- ozone decomposition
- decomposition according
- ozone
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 239000002131 composite material Substances 0.000 title claims abstract description 68
- 239000003054 catalyst Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 29
- 238000000227 grinding Methods 0.000 claims abstract description 26
- 239000000725 suspension Substances 0.000 claims abstract description 24
- 239000007788 liquid Substances 0.000 claims abstract description 15
- 238000006479 redox reaction Methods 0.000 claims abstract description 10
- 229910002476 CuII Inorganic materials 0.000 claims abstract description 8
- 229910003177 MnII Inorganic materials 0.000 claims abstract description 8
- 238000004140 cleaning Methods 0.000 claims abstract description 7
- 238000012545 processing Methods 0.000 claims abstract description 7
- 238000004108 freeze drying Methods 0.000 claims abstract description 6
- 150000003839 salts Chemical class 0.000 claims abstract description 6
- 238000009938 salting Methods 0.000 claims abstract description 5
- 238000001914 filtration Methods 0.000 claims abstract description 3
- 238000004090 dissolution Methods 0.000 claims abstract 2
- 239000007787 solid Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- 239000011656 manganese carbonate Substances 0.000 claims description 2
- 235000006748 manganese carbonate Nutrition 0.000 claims description 2
- 229940093474 manganese carbonate Drugs 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 229940099607 manganese chloride Drugs 0.000 claims description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 2
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 2
- 239000005864 Sulphur Substances 0.000 claims 2
- 230000035484 reaction time Effects 0.000 claims 2
- OQVYMXCRDHDTTH-UHFFFAOYSA-N 4-(diethoxyphosphorylmethyl)-2-[4-(diethoxyphosphorylmethyl)pyridin-2-yl]pyridine Chemical compound CCOP(=O)(OCC)CC1=CC=NC(C=2N=CC=C(CP(=O)(OCC)OCC)C=2)=C1 OQVYMXCRDHDTTH-UHFFFAOYSA-N 0.000 claims 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims 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 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 17
- 239000006185 dispersion Substances 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 11
- 230000008569 process Effects 0.000 abstract description 9
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 16
- 150000001875 compounds Chemical class 0.000 description 10
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 8
- 238000003421 catalytic decomposition reaction Methods 0.000 description 8
- 238000006555 catalytic reaction Methods 0.000 description 8
- 239000012286 potassium permanganate Substances 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 229940099596 manganese sulfate Drugs 0.000 description 4
- 239000011702 manganese sulphate Substances 0.000 description 4
- 235000007079 manganese sulphate Nutrition 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 238000005367 electrostatic precipitation Methods 0.000 description 3
- 230000036541 health Effects 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- CNFDGXZLMLFIJV-UHFFFAOYSA-L manganese(II) chloride tetrahydrate Chemical compound O.O.O.O.[Cl-].[Cl-].[Mn+2] CNFDGXZLMLFIJV-UHFFFAOYSA-L 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 208000032170 Congenital Abnormalities Diseases 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- 206010047571 Visual impairment Diseases 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004887 air purification Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- QRJOYPHTNNOAOJ-UHFFFAOYSA-N copper gold Chemical compound [Cu].[Au] QRJOYPHTNNOAOJ-UHFFFAOYSA-N 0.000 description 1
- IYRDVAUFQZOLSB-UHFFFAOYSA-N copper iron Chemical compound [Fe].[Cu] IYRDVAUFQZOLSB-UHFFFAOYSA-N 0.000 description 1
- 229910000431 copper oxide Inorganic materials 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
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 210000004072 lung Anatomy 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- BZDIAFGKSAYYFC-UHFFFAOYSA-N manganese;hydrate Chemical compound O.[Mn] BZDIAFGKSAYYFC-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 210000005036 nerve Anatomy 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical compound [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 description 1
- 230000035755 proliferation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000029058 respiratory gaseous exchange Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 208000029257 vision disease Diseases 0.000 description 1
- 230000004393 visual impairment Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—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
- B01D53/8671—Removing components of defined structure not provided for in B01D53/8603 - B01D53/8668
- B01D53/8675—Ozone
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Environmental & Geological Engineering (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
Abstract
A kind of preparation method of the composite catalyst of ozone decomposition, the described method comprises the following steps: by permanganate, MnIISalt and CuIIRespectively dissolution obtains three kinds of salting liquids to salt respectively；These three salting liquids are mixed and stirred for rapidly to carry out redox reaction, then obtain the filter residue of composite oxides by filtering, cleaning；Filter residue addition water is mixed, the suspension of filter residue and water is formed, Ultrafine Grinding processing is carried out to the suspension, is fully ground the composite catalyst for arriving the ozone decomposition after the suspension using freeze drying process.Method synthesis step of the invention is few, and synthesis condition is simple, and Ultrafine Grinding treatment process is simple, and dispersion effect is good, and the various material mixings doping in composite catalyst obtained sufficiently, significantly improves catalytic effect.
Description
Technical field
It is decomposed the present invention relates to the preparation method more particularly to a kind of catalysis ozone of a kind of environmental protection and material for air purification
Composite catalyst and preparation method thereof.
Background technique
Ozone (O3) a kind of light blue gas for having off-odor, it is primarily present in smelly away from 20-35 kilometers of earth surface
In oxygen layer, the ultraviolet light direct irradiation earth is kept out.Under normal conditions, sucking is beneficial to human body on a small quantity, however sucks excessive to people
Body health has certain harm.Ozone concentration must not exceed 0.08mg/m in regulation room air in national standard3, the highest of ozone permits
Perhaps concentration is 0.16mg/m3, can be caused harm to the human body if being more than this concentration.The ozone of excessive concentrations can stimulate breathing
Road causes the damage of throat, tracheae and lung etc., and visual impairment can be caused when situation is serious, causes fetal anomaly youngster, nerve
Phenomena such as poisoning.
Since with strong oxidizing property, ozone is normally used for playing disinfection in the industries such as food, health care and water process
Effect.However, being difficult to region that is fully erased and being directly discharged to our work and lifes after usage；In addition, coming
Atmospheric environment has been entered from what the ozone of the other equipment such as duplicator, the electrion etc. of nature was all difficult to avoid that
In.In addition, the application of electrostatic precipitation product is also more and more extensive with the rapid proliferation of air clearing product, however in high pressure
Electrostatic precipitation module work during, voltage is higher, generate ozone it is more, it is excessive smelly if be not pocessed
Oxygen just inevitably enters in air, and excessive ozone enters into air not only generate offending odor impact ring
The health of human body is also seriously damaged in border.Since the ozone of generation is difficult to handle, electrostatic precipitation air purifier is also limited
Using.
Currently, there are many methods of removal ozone pollution, wherein representative mainly have medical fluid absorption process, solid absorption
Method, photocatalytic method and constant temperature catalyzing method.Its herb liquid absorption method is using liquid absorption, it is difficult to is widely applied to smelly in air
The removal of oxygen；Solid absorption method is usually to carry out physical absorption using inorganic porous material, to achieve the purpose that remove ozone, so
And the adsorption capacity of its material is limited, reach saturation after cannot be used continuously but also exist release secondary pollution
Risk, nor solving the problems, such as the very wise move of ozone pollution；Photocatalytic method is usually using the material for having catalyticing decomposition action to ozone
Material, since it needs the catalytic condition of light, it is difficult to be applied in the environment such as interior；Constant temperature catalyzing method mainly utilizes catalyst to exist
Any additional condition catalysis ozone is not needed under room temperature to decompose to achieve the purpose that removal, is a kind of permanently effective and practical
Method.
A kind of ozone decomposition catalyst and preparation method thereof is disclosed in 103127942 A of CN, with iron copper composite oxides
For main active component, gold prepares out iron/copper-gold composite catalyst, the catalyst pair using Precipitation method to help active component
Ozone in room air decomposes catalytic activity and stability with higher.However since noble metal is on the high side, it is difficult to
To being widely applied.A kind of room-temperature efficient ozone decomposition catalyst and preparation method thereof is disclosed in 102513106 B of CN,
It is middle, using potassium chlorate as oxidant, to precipitate using potassium carbonate and/or saleratus as precipitating reagent using the precipitation method and active group is made
Point, then it is added N, N- diethyl ethanamine, crystallization under the conditions of 180 DEG C -220 DEG C, is passing through high-temperature roasting technique in a kettle
It is made.The preparation process is many and diverse, and the hazardous agents used are more, is unfavorable for realizing safe production, therefore is difficult to carry out industrializing
Production；And reunion is easily caused in last high-temperature roasting technique, reduce the catalytic activity of catalyst.
Summary of the invention
For above-mentioned related problem, the object of the present invention is to provide the systems that a kind of catalysis ozone decomposes composite catalyst
Preparation Method, this preparation method is safe and simple, and has polymolecularity, can efficient catalytic ozone decomposition.The material is dioxy
Change the catalytic composite material of manganese and copper oxide, and various compounding ingredients realize the compound of lattice level, have very high urge
Change activity；The composite catalyst has polymolecularity and sufficiently small partial size, provides enough skies for the catalysis reaction of ozone
Between.
To achieve the goals above, the present invention be adopt the following technical scheme that realization a kind of catalysis ozone decompose it is compound
The synthetic method of catalyst, using manganese and copper carry out it is effectively compound obtain Copper-cladding Aluminum Bar composite oxides, first by solution
Oxidation-reduction method obtains the manganese dioxide and oxidation carbon/carbon-copper composite material, then passes through the above-mentioned composite catalyst of Ultrafine Grinding process
Obtain the very high catalytic composite material of dispersion degree.
The preparation process of the catalytic composite material of the ozone decomposition mainly includes the preparation of metal salt solution and oxide
Redox reaction and Ultrafine Grinding dispersing technology in technique, solution, specific as follows: catalysis ozone of the present invention decomposes compound
Catalyst material is prepared via a method which: by permanganate, MnIISalt and CuIISalt, which respectively dissolves, obtains salting liquid；By this
Three kinds of solution are mixed and stirred for carrying out redox reaction rapidly, obtain composite oxides precipitating, then by filtering, cleaning
To filter residue；Finally filter residue addition water is mixed, forms the suspension of filter residue and water, the suspension is carried out ultra-fine
Mill processing is fully ground after suspension using freeze drying process to get the compound of the high degree of dispersion mixed to molecular level
Oxide catalyst.
Preferably, the permanganate can select potassium permanganate；
Preferably, the MnIISalt can select manganese sulfate, manganese nitrate, manganese carbonate, in manganese chloride any one or
It is a variety of；
Preferably, the CuIISalt can be selected one or more in copper sulphate, copper nitrate and copper chloride.
Preferably, the permanganate solution compound concentration is 10-30wt%, preferably 10-25wt%；
Preferably, the MnIISalting liquid compound concentration is 5-30wt%, preferably 10-20wt%；
Preferably, the CuIISalting liquid compound concentration is 3-30wt%, preferably 8-20wt%；
Preferably, the MnIISalt, permanganate and CuIIThe molar ratio of salt is 1:(2.1-4): (0.05-
1), wherein optimum ratio is 1:(2.2-3.5): (0.2-1).
Preferably, the temperature range of the redox reaction is -10-99 DEG C, preferably 10-90 DEG C；
Preferably, the time range of the redox reaction is 0.5-30h, preferably 0.5-20h；
Preferably, spherolite diameter is 0.2-0.5mm, revolving speed 1000-2100r/min in the Ultrafine Grinding processing:
Preferably, solid content is 5wt%-50wt% in the suspension；
Preferably, the sufficient time is 30-600min, wherein preferably 60-480min；
Preferably, the suspension freeze-drying temperature is no more than room temperature；
Preferably, the suspension sublimation drying is 5-48h；
Compared with prior art, it has the advantages that
1, the synthesis step of catalytic composite material is few, and each raw material is co-precipitated by redox reaction, realizes
It is compound on molecular level；
2, the synthesis condition of catalytic composite material is simple；
3, Ultrafine Grinding treatment process is simple, and dispersion effect is good；
4, the various material mixings doping in composite catalyst sufficiently, significantly improves catalytic effect.
Detailed description of the invention
Fig. 1 is the composite catalyst synthesis process flow diagram of ozone decomposition.
Fig. 2 is the transmission electron microscope picture of the composite catalyst of the ozone decomposition.
Specific embodiment
Embodiment 1
19.8g tetrahydrate manganese chloride is completely dissolved in 100mL pure water, 34.76g potassium permanganate is completely dissolved in 200mL
In pure water, then 0.25g cupric sulfate pentahydrate is dissolved into 50mL pure water, above-mentioned three kinds of solution is sufficiently dissolved for use.It is quickly mixed
It closes and states three kinds of solution & stirs, above-mentioned mixed solution is stirred at room temperature to filter after reaction 10h and is cleaned, combined oxidation is obtained
Object filter residue.Filter residue obtained above is added in Ultrafine Grinding equipment, 19g water is added and obtains the suspension that solid content is 50%,
The zirconia ball for selecting 0.2mm, the revolving speed that Ultrafine Grinding is arranged is 2100r/min milled processed 10h.By the suspension after grinding
High degree of dispersion composite catalyst powder is obtained after being freeze-dried 20h under the conditions of -50 DEG C.
(see Fig. 2) is tested through SEM, shows that the composite catalyst of synthesized ozone decomposition is nanometer materials, partial size
Within the scope of 20-S0nm.
The divided catalytic ozone decomposition composite catalyst material of the above-mentioned preparation of 1.00g is taken to be placed in the glass tube that diameter is 2mm
Catalytic decomposition Performance Evaluation is carried out on interior sand core.The bottom of glass tube and air pump (gas outlet for being connected to ozone generator) phase
Even, top is connected with ultraviolet specrophotometer on-line detector.When the sky that generation ozone content is 100ppm in ozone generator
Be discharged after gas by its gas outlet, ozone-containing air additive amount be 800mL/min, then through air pump be transported in glass tube with it is compound
Catalysis material is reacted, and is finally spilled over in connected ultraviolet specrophotometer at the top of glass tube again, by detecting
Instrument measures the content of ozone in tail gas.Testing result shows the high degree of dispersion composite catalyst prepared in the present embodiment in room temperature
Under the conditions of to the ozone of 100ppm carry out catalytic decomposition efficiency be 90%.
Embodiment 2
Tetra- water manganese sulfate of 7.8g is completely dissolved in 100mL pure water, it is pure that 22.1g potassium permanganate is completely dissolved in 100mL
In water, then 6.03g copper chloride dihydrate is dissolved into 95mL pure water, above-mentioned three kinds of solution is sufficiently dissolved for use.Quickly mixing
Above-mentioned three kinds of solution & stirs filter cleaning after above-mentioned mixed solution to be stirred to react to 30h at 0 DEG C, obtain composite oxides
Filter residue.Filter residue obtained above is added in Ultrafine Grinding equipment, 36.4g water is added and obtains the suspension that solid content is 30%,
The alumina balls for selecting 0.3mm, the revolving speed that Ultrafine Grinding is arranged is 1500r/min milled processed 6h.By the suspension after grinding-
The composite catalyst powder of ozone decomposition is obtained after being freeze-dried 15h under the conditions of 20 DEG C.
For catalytic performance test with embodiment 1, testing result shows the high degree of dispersion composite catalyst prepared in the present embodiment
Carrying out catalytic decomposition efficiency to the ozone of 100ppm at room temperature is 92%.
Embodiment 3
Six water manganese nitrate of 14.35g is completely dissolved in 130mL pure water, 22.1g potassium permanganate is completely dissolved in 200mL
In pure water, 8.45g nitrate trihydrate copper is completely dissolved in 85mL pure water, above-mentioned three kinds of solution is sufficiently dissolved for use.Quickly
Above-mentioned three kinds of solution & stirs are mixed, cleaning is filtered after above-mentioned mixed solution to be stirred to react to 5h at 40 DEG C, obtains composite oxygen
Compound filter residue.Filter residue obtained above is added in Ultrafine Grinding equipment, be added 187.4g water obtain solid content be 10% it is outstanding
Turbid selects the alumina balls of 0.4mm, and the revolving speed that Ultrafine Grinding is arranged is 1800r/min milled processed 1h.It will be suspended after grinding
Liquid obtains the composite catalyst powder of ozone decomposition after being freeze-dried 30h under the conditions of 0 DEG C.
For catalytic performance test with embodiment 1, testing result shows the high degree of dispersion composite catalyst prepared in the present embodiment
Carrying out catalytic decomposition efficiency to the ozone of 100ppm at room temperature is 93%.
Embodiment 4
Tetra- water manganese sulfate of 15g is completely dissolved in 150mL pure water, 26.9g potassium permanganate is completely dissolved in 200mL pure water
In, 5g cupric sulfate pentahydrate is completely dissolved in 50mL pure water, above-mentioned three kinds of solution is sufficiently dissolved for use.It quickly mixes above-mentioned
Three kinds of solution & stirs filter cleaning after above-mentioned mixed solution to be stirred to react to 20h at 30 DEG C, obtain composite oxides filter
Slag.Filter residue obtained above is added in Ultrafine Grinding equipment, 407g water is added and obtains the suspension that solid content is 5%, selects
The zirconia ball of 0.5mm, the revolving speed that Ultrafine Grinding is arranged is 1200r/min milled processed 1h.By the suspension after grinding in 2 DEG C of items
The composite catalyst powder of ozone decomposition is obtained after being freeze-dried 5h under part.
For catalytic performance test with embodiment 1, testing result shows the high degree of dispersion composite catalyst prepared in the present embodiment
Carrying out catalytic decomposition efficiency to the ozone of 100ppm at room temperature is 91%.
Embodiment 5
Tetra- water manganese sulfate of 14.35g is completely dissolved in 150mL pure water, 23.7g potassium permanganate is completely dissolved in 200mL
In pure water, 7.5g cupric sulfate pentahydrate is completely dissolved in 50mL pure water, above-mentioned three kinds of solution is sufficiently dissolved for use.It is quickly mixed
It closes and states three kinds of solution & stirs, filter cleaning after above-mentioned mixed solution to be stirred to react to 2h at 50 DEG C, obtain combined oxidation
Object filter residue.Filter residue obtained above is added in Ultrafine Grinding equipment, 69g water is added and obtains the suspension that solid content is 25%,
The zirconia ball for selecting 0.2mm, the revolving speed that Ultrafine Grinding is arranged is 1500r/min milled processed 2h.By the suspension after grinding 5
The composite catalyst powder of ozone decomposition is obtained after being freeze-dried 8h under the conditions of DEG C.
For catalytic performance test with embodiment 1, testing result shows the high degree of dispersion composite catalyst prepared in the present embodiment
Carrying out catalytic decomposition efficiency to the ozone of 100ppm at room temperature is 94%.
Comparative example 1
19.8g tetrahydrate manganese chloride is completely dissolved in 100mL pure water, 34.76g potassium permanganate is completely dissolved in 200mL
In pure water, then 0.25g cupric sulfate pentahydrate is dissolved into 50mL pure water, above-mentioned three kinds of solution is sufficiently dissolved for use.It is quickly mixed
It closes and states three kinds of solution & stirs, above-mentioned mixed solution is stirred at room temperature to filter after reaction 10h and is cleaned, combined oxidation is obtained
Object filter residue.Filter residue obtained above is added in general milling equipment, be added 19g water obtain solid content be 50% it is suspended
Liquid selects the zirconia ball of 0.2mm, handles 10h using general milling.Suspension after grinding is freezed under the conditions of -50 DEG C
Catalysis ozone, which is obtained, after dry 20h decomposes composite powder.
For catalytic performance test with embodiment 1, testing result shows the composite catalyst prepared in this comparative example in room temperature item
Carrying out catalytic decomposition efficiency to the ozone of 100ppm under part is 45%.
Through the foregoing embodiment with comparative example 1 as can be seen that the composite catalyst by Ultrafine Grinding processing urges ozone
Change capacity of decomposition to be noticeably greater than without the composite catalyst by Ultrafine Grinding processing.This may be because in Ultrafine Grinding treatment process
In, each oxide obtains sufficient dispersion in the milled processed of high speed high energy, merges into each other, to greatly reinforce multiple
Close the catalytic decomposition ability of catalyst.
The above is only a preferred embodiment of the present invention, for those of ordinary skill in the art, according to the present invention
Thought, there will be changes in the specific implementation manner and application range, and the content of the present specification should not be construed as to the present invention
Limitation.
Claims (23)
1. a kind of preparation method of the composite catalyst of ozone decomposition, the described method comprises the following steps: by permanganate, MnⅡ
Salt and CuⅡRespectively dissolution obtains three kinds of salting liquids to salt respectively；These three salting liquids are mixed and stirred for rapidly to carry out redox
Then reaction obtains the filter residue of composite oxides by filtering, cleaning；Filter residue addition water is mixed, filter residue is formed
With the suspension of water, Ultrafine Grinding processing is carried out to the suspension, is fully ground after the suspension using freeze-drying work
Skill is to get the composite catalyst for arriving the ozone decomposition.
2. the preparation method of the composite catalyst of ozone decomposition according to claim 1, the permanganate is selected high
Potassium manganate.
3. the preparation method of the composite catalyst of ozone decomposition according to claim 1 or 2, the MnⅡSalt selects sulphur
Sour manganese, manganese nitrate, manganese carbonate, any one or more in manganese chloride.
4. the preparation method of the composite catalyst of ozone decomposition according to claim 3, the CuⅡSalt can select sulphur
It is one or more in sour copper, copper nitrate and copper chloride.
5. the preparation method of the composite catalyst of ozone decomposition according to claim 3, the permanganate solution is matched
Concentration processed is 10-30wt%.
6. the preparation method of the composite catalyst of ozone decomposition according to claim 3, the MnⅡSalting liquid is prepared dense
Degree is 5-30wt%.
7. the preparation method of the composite catalyst of ozone decomposition according to claim 3, the CuⅡSalting liquid is prepared dense
Degree is 3-30wt%.
8. the preparation method of the composite catalyst of ozone decomposition according to claim 3, the MnⅡSalt, permanganate
And CuⅡThe molar ratio of salt is 1:(2.1-4): (0.05-1).
9. the preparation method of the composite catalyst of ozone decomposition according to claim 3, the redox reaction
Temperature range is -10-99 DEG C.
10. the preparation method of the composite catalyst of ozone decomposition according to claim 3, the redox reaction
Time range is 0.5-30h.
11. the preparation method of the composite catalyst of ozone decomposition according to claim 3, ground in the Ultrafine Grinding processing
Abrading-ball partial size is 0.2-0.5mm, revolving speed 1000-2100r/min.
12. the preparation method of the composite catalyst of ozone decomposition according to claim 3, solid content in the suspension
For 5-50wt%.
13. the preparation method of the composite catalyst of ozone decomposition according to claim 3, the time that is fully ground are
30-600min。
14. the preparation method of the composite catalyst of ozone decomposition according to claim 3, the suspension freeze-drying
Temperature is no more than room temperature.
15. the preparation method of the composite catalyst of ozone decomposition according to claim 3, the suspension freeze-drying
Time is 5-48h.
16. the preparation method of the composite catalyst of ozone decomposition according to claim 3, the permanganate solution is matched
Concentration processed is 10-25wt%.
17. the preparation method of the composite catalyst of ozone decomposition according to claim 3, the MnⅡSalting liquid is prepared
Concentration is 10-20wt%.
18. the preparation method of the composite catalyst of ozone decomposition according to claim 3, the CuⅡSalting liquid is prepared
Concentration is 8-20wt%.
19. the preparation method of the composite catalyst of ozone decomposition according to claim 3, the MnⅡSalt, permanganate
And CuⅡThe molar ratio of salt is 1:(2.2-3.5): (0.2-1).
20. the preparation method of the composite catalyst of ozone decomposition according to claim 3, the redox reaction
Temperature range is 10-90 DEG C.
21. the preparation method of the composite catalyst of ozone decomposition according to claim 3, the redox reaction
Time range is 0.5-20h.
22. the preparation method of the composite catalyst of ozone decomposition according to claim 3, the time that is fully ground are
60-480min。
23. made from a kind of preparation method of the composite catalyst of ozone decomposition described in any one of -22 according to claim 1
The composite catalyst of ozone decomposition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610543720.1A CN106179396B (en) | 2016-07-08 | 2016-07-08 | A kind of composite catalyst for decomposing ozone and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610543720.1A CN106179396B (en) | 2016-07-08 | 2016-07-08 | A kind of composite catalyst for decomposing ozone and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106179396A CN106179396A (en) | 2016-12-07 |
| CN106179396B true CN106179396B (en) | 2019-02-15 |
Family
ID=57478105
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610543720.1A Active CN106179396B (en) | 2016-07-08 | 2016-07-08 | A kind of composite catalyst for decomposing ozone and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106179396B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107456978A (en) * | 2017-09-01 | 2017-12-12 | 深圳市高斯宝电气技术有限公司 | A kind of ozone decomposition catalyst and preparation method thereof |
| CN109772159B (en) * | 2019-03-14 | 2021-06-25 | 中山大学 | Amorphous manganese oxide catalyst, preparation method and application thereof |
| CN111744498B (en) * | 2020-05-25 | 2021-05-25 | 广州广钢气体能源股份有限公司 | Manganese-copper composite oxide catalyst and preparation method and application thereof |
| CN112108152B (en) * | 2020-09-23 | 2023-01-24 | 上海化工研究院有限公司 | Catalyst for fish meal odor treatment and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1785507A (en) * | 2005-11-22 | 2006-06-14 | 天津化工研究设计院 | Ozone decomposition catalyst and its preparation method |
| WO2007049778A1 (en) * | 2005-10-24 | 2007-05-03 | Toyota Jidosha Kabushiki Kaisha | Catalyst support and catalyst for exhaust-gas purification |
| CN102600861A (en) * | 2012-03-26 | 2012-07-25 | 中国科学院生态环境研究中心 | Manganese-based composite oxide catalyst for catalytically decomposing ozone, and preparation method of manganese-based composite oxide catalyst |
| CN103816918A (en) * | 2014-03-21 | 2014-05-28 | 中国科学院上海硅酸盐研究所 | Weak-crystallization nanometer manganese oxide base adsorbing/catalyzing agent and preparation method thereof |
-
2016
- 2016-07-08 CN CN201610543720.1A patent/CN106179396B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007049778A1 (en) * | 2005-10-24 | 2007-05-03 | Toyota Jidosha Kabushiki Kaisha | Catalyst support and catalyst for exhaust-gas purification |
| CN1785507A (en) * | 2005-11-22 | 2006-06-14 | 天津化工研究设计院 | Ozone decomposition catalyst and its preparation method |
| CN102600861A (en) * | 2012-03-26 | 2012-07-25 | 中国科学院生态环境研究中心 | Manganese-based composite oxide catalyst for catalytically decomposing ozone, and preparation method of manganese-based composite oxide catalyst |
| CN103816918A (en) * | 2014-03-21 | 2014-05-28 | 中国科学院上海硅酸盐研究所 | Weak-crystallization nanometer manganese oxide base adsorbing/catalyzing agent and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106179396A (en) | 2016-12-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106179396B (en) | A kind of composite catalyst for decomposing ozone and preparation method thereof | |
| CN108435160B (en) | Cerium-manganese catalyst for decomposing ozone at wide temperature and high airspeed, preparation method and application | |
| CN107519861A (en) | A kind of cerium manganese composite oxides catalyst, preparation method and the usage | |
| CN105797741B (en) | A kind of Copper-cladding Aluminum Bar type manganese dioxide-catalyst and preparation method thereof | |
| CN104001502B (en) | Cerium Mn catalyst, the preparation method and its usage of ozone decomposition under a kind of room temperature high humility | |
| CN112958089B (en) | Preparation method of copper oxide catalyst for catalyzing persulfate to degrade pollutants in water | |
| CN110124660A (en) | A kind of Z- mechanism Bi rich in Lacking oxygen2O3@CeO2Photochemical catalyst and the preparation method and application thereof | |
| CN108114711A (en) | A kind of catalyst of transition metal oxide and preparation method of catalytic eliminating ozone | |
| CN104827860B (en) | Air purifier and vehicle | |
| CN103894194B (en) | A kind of room temperature removes the loaded catalyst of formaldehyde | |
| Ren et al. | Effective mineralization of p-nitrophenol by catalytic ozonation using Ce-substituted La1‒xCexFeO3 catalyst | |
| CN107555481A (en) | A kind of Mn oxide material and preparation method thereof | |
| CN114180614A (en) | Application of Compounds of General Formula AM2O5-x in Catalysis of Hydrogen Peroxide at Room Temperature | |
| CN108126709A (en) | A kind of support type formaldehyde catalyst and preparation method thereof | |
| CN104190435A (en) | Manganese-cobalt nanocrystalline catalyst for catalytic oxidation of methylbenzene as well as preparation method and application thereof | |
| CN102068994B (en) | Catalyst and preparation method thereof | |
| CN105233833B (en) | Magnetic rare earth barium ferrite nanometer cleaning catalyst and preparation method and application | |
| CN105413697B (en) | The preparation method of magnetic rare earth barium ferrite nanometer cleaning catalyst | |
| CN102728299B (en) | A kind of titania-doped compound magnetic nano adsorber and its preparation method, application | |
| CN107321355A (en) | A kind of preparation method and application of tetracycline pollution waters restoration material | |
| CN102443455A (en) | Composite oxides oxygen carrier of chemical-looping combustion and preparation method and application thereof | |
| CN102580723B (en) | Cerium-manganese-titanium catalyst and its preparation method and application | |
| KR102046269B1 (en) | Purification processing method of toxic substance containing liquid and toxic substance containing liquid for performing this | |
| CN110813257B (en) | Preparation and application method of magnetic adsorption catalytic material for simultaneous removal of nitrate and perchlorate in water | |
| JP2018203546A (en) | Porous functional material, and production method and production apparatus thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20241012 Address after: 314599 Room 468, Building 1, No. 86, Guanghua Road, Tongxiang City, Jiaxing City, Zhejiang Province Patentee after: Jiaxing Youhao Jingkong Material Technology Co.,Ltd. Country or region after: China Address before: 315000 Yinzhou Economic Development Zone, Ningbo City, Zhejiang Province Patentee before: NINGBO TAIAN NEW MATERIAL TECHNOLOGY Co.,Ltd. Country or region before: China |
|
| TR01 | Transfer of patent right |