CN104888793B - Catalyst for catalyzing ozone to oxidize volatile organic compounds and preparation method of catalyst - Google Patents
Catalyst for catalyzing ozone to oxidize volatile organic compounds and preparation method of catalyst Download PDFInfo
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- CN104888793B CN104888793B CN201510377785.9A CN201510377785A CN104888793B CN 104888793 B CN104888793 B CN 104888793B CN 201510377785 A CN201510377785 A CN 201510377785A CN 104888793 B CN104888793 B CN 104888793B
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Abstract
The invention provides a catalyst for catalyzing ozone to oxidize volatile organic compounds. The catalyst comprises a nickel foam carrier and a MnOx-SnOx-CeOx-SbOx compound oxide. A preparation method is characterized in that the nickel foam is impregnated or coated with a metallic salt solution and is roasted at high temperature to obtain the catalyst for catalyzing the ozone to oxidize the volatile organic compounds. The catalyst has the advantages of high catalytic activity, low price and better mechanical and chemical stability, and can be used for catalyzing the ozone to oxidize and purify the volatile organic compounds in waste gases and indoor air.
Description
Technical field
The present invention relates to field of environmental technology, more particularly to a kind of catalysis for O3 catalytic oxidation volatile organic matter
Agent and preparation method.
Background technology
Volatile organic matter (VOCs) is component relatively active in air, and it is not only directly detrimental to health, can also be
The secondary pollution such as photochemical fog and Organic aerosol is formed in air, to Global climate change, environmental quality, human health
Deng producing material impact.Therefore, the purifying treatment method of VOCs is explored, reducing the discharge of VOCs contributes to improving atmospheric environment
Quality, preserve the ecological environment and ensure health, be also the urgent needss of Sustainable Socioeconomic Development.
Ozone has strong oxidizing property, is 1.5 times of chlorine oxidation ability, is a kind of wide-spectrum bactericide, is usually used in medical treatment and defends
Raw and dining food industry sterilizing.Ozone can pass through at normal temperatures additive reaction, electrophilic reaction and necleophilic reaction directly handle
Volatile organic matter oxidation Decomposition.But just because of the selectivity of ozone oxidation, it is dirty to difficult degradations such as saturated alkane, aromatic hydrocarbon
The clearance of dye thing is relatively low.For the oxidability for further improving ozone, H can be adopted2O2/O3、UV/O3, metallic catalyst/O3Deng
High-level oxidation technology, produces hydroxyl radical free radical, indirect utilization ozone oxidation hardly degraded organic substance.
O3 catalytic oxidation at present has been used for refractory wastewater, and such as CN103111290A discloses a kind of catalysis ozone
Oxidation depth processes the preparation method of coal chemical industrial waste water catalyst, using activated carbon supported metal oxide, catalysis ozone depth
Difficult degradation poisonous and harmful substances in oxidation removal water, improve wastewater biodegradability, it is ensured that effluent quality reaches country's discharge one-level mark
It is accurate.CN102941084 discloses a kind of activated alumina Supported Manganese, cerium dual-component metal-oxide ozone catalytic oxidation catalyst
Preparation method, the catalyst of preparation is remarkably improved clearance of the ozone to hardly degraded organic substance in water body.
In atmospheric environment, ozone is a kind of harmful substance, and China's ambient air quality (GB3095-2012) specifies
Day, maximum 8 hour average concentration was less than 0.16mgm-3.In exhaust-gas treatment field, it is a kind of effective process that catalysis ozone decomposes
Means containing ozone waste gas, such as CN1259398A, CN10260861A respectively disclose a kind of ozone decomposition catalyst and preparation method,
The ozone that can effectively go in removing exhaust gas.In fact, using ozone oxidation and catalysis oxidation can remove waste gas in VOCs, and by
In the effect of catalyst, ozone is converted into the intermediate products such as hydroxyl, active oxygen, even if not consuming completely in the reaction, finally
It is transformed into oxygen and water, does not produce secondary pollution.
The content of the invention
The invention provides a kind of catalyst and preparation method for O3 catalytic oxidation volatile organic matter, purpose exists
In deep oxidation of the ozone to VOCs is improved, VOCs is degraded to CO2And H2The innocuous substances such as O.Catalysis ozone oxygen prepared by the present invention
The catalyst for changing volatile organic matter can be used for the O3 catalytic oxidation of industrial waste gas and room air VOCs.
The present invention is implemented by following technical scheme：
A kind of preparation method of the catalyst for O3 catalytic oxidation volatile organic matter, including step：
(1) by the nickel foam in 0.1～2mm apertures, 80 DEG C of constant temperature water bath soaks 2h in 20% NaOH aqueous solutions, spends
Ionized water is rinsed well, drying, then 95 DEG C of immersion 2h of constant temperature water bath in 15% oxalic acid aqueous solution, and deionized water is rinsed
Totally, dry, as catalyst carrier.
(2) pH value of ethanol solution is adjusted with analysis pure hydrochloric acid between 1～4, the soluble-salt of Mn, Sn, Ce, Sb will be contained
Ethanol solution is dissolved in, impregnation liquid is obtained.Preferably manganese nitrate, cerous nitrate, stannic chloride, antimony chloride, Mn in the impregnation liquid of preparation,
The mol ratio of Sn, Ce, Sb is 10:10:1:1.
(3) nickel foam prepared by step (1) is soaked in the impregnation liquid 15min of step (2) preparation, or is prepared by rapid (2)
Impregnation liquid be painted in the nickel foam of step (1) preparation, in≤80 DEG C of drying, in 200～800 DEG C of 3～5h of roasting, repeatedly 1
～10 times, a kind of catalyst for O3 catalytic oxidation volatile organic matter is obtained.
Wherein, carrier nickel purity more than 99%, is three-dimensional porous permeable structures, and porosity reaches more than 95%.
Wherein, the soluble-salt of Mn, Sn, Ce, Sb is pure for analysis, and Mn, Sn, Ce, Sb's is mole dense in the impregnation liquid of preparation
Degree respectively 0.1,0.1,0.01,0.01molL-1To 2,2,0.2,0.2molL-1。
The present invention with nickel foam as carrier, MnOx-SnOx-CeOx-SbOx composite oxides be catalytic active substance, price
It is cheap, high for O3 catalytic oxidation VOCs activity with preferably mechanically and chemically stability, life-span length.
Specific embodiment
Embodiment 1：Take 100ml dehydrated alcohol, with 37% salt acid for adjusting pH to 1, be subsequently adding the water stannic chlorides of 35g five and
The water cerous nitrates of 4.3g six, are eventually adding 50% manganese nitrate 25ml, with dehydrated alcohol constant volume to 200ml, as containing Mn, Sn, Ce
Impregnation liquid.By after cleaning, aperture soak 15min in the impregnation liquid for 0.1mm nickel foam, be placed in baking oven 70 DEG C of drying, so
500 DEG C of roasting 3h in Muffle furnace afterwards, dipping, drying, roasting 5 times repeatedly, being obtained a kind of is used for O3 catalytic oxidation volatility
The catalyst of Organic substance.Catalyst performance evaluation：Catalyst volume is 0.8L, and gas flow is 5.0L min-1, toluene and ozone
Entrance concentration is 400mg m-3, up to more than 96%, outlet ozone free detection runs 40 hours, catalyst performance toluene purifying rate
Can be without significant change.
Embodiment 2：Take 100ml dehydrated alcohol, with 37% salt acid for adjusting pH to 1, be subsequently adding the water stannic chlorides of 35g five,
The water cerous nitrates of 4.3g six and 2.3g Butter of antimony., are eventually adding 50% manganese nitrate 25ml, with dehydrated alcohol constant volume to 200ml, i.e.,
It is the impregnation liquid containing Mn, Sn, Ce, Sb.By after cleaning, aperture soak 15min in the impregnation liquid for 0.1mm nickel foam, be placed in
70 DEG C of drying in baking oven, then 500 DEG C of roasting 3h in Muffle furnace, dipping, drying, roasting 10 times repeatedly, prepared one kind is used for
The catalyst of O3 catalytic oxidation volatile organic matter.Catalyst performance evaluation：Catalyst volume is 0.8L, and gas flow is
5.0L min-1, toluene and ozone inlet concentration be 200mg m-3, up to 100%, outlet ozone free is detected toluene purifying rate.
Claims (5)
1. a kind of catalyst for O3 catalytic oxidation volatile organic matter, it is characterised in that described catalyst is by foam
Nickel carrier and composite oxide of metal are constituted, and the composite oxide of metal in catalyst is compound for MnOx-SnOx-CeOx-SbOx
Oxide, the preparation method of the catalyst, including step：
（1）Nickel foam cleaning, drying is standby as carrier；
（2）Prepare the impregnation liquid containing Mn, Sn, Ce, Sb；
（3）By step（1）The nickel foam of preparation is soaked in step（2）The impregnation liquid 15min of preparation, or by step（2）Prepare
Impregnation liquid is painted on step（1）In the nickel foam of preparation, drying, roasting 1 ~ 10 time repeatedly, is obtained a kind of for catalysis ozone oxygen
Change the catalyst of volatile organic matter；
Wherein, step（2）Described impregnation liquid, with hydrochloric acid adjust the pH value of ethanol solution between 1 ~ 4, will contain Mn, Sn, Ce,
The soluble-salt of Sb is dissolved in ethanol solution, obtains impregnation liquid, and the mol ratio of Mn, Sn, Ce, Sb is 10 in the impregnation liquid of preparation:10:
1:1。
2. catalyst according to claim 1, it is characterised in that the composite oxide of metal percentage by weight in catalyst
For 1% ~ 30%.
3. the preparation method of catalyst according to claim 1, it is characterised in that including step：
（1）Nickel foam cleaning, drying is standby as carrier；
（2）Prepare the impregnation liquid containing Mn, Sn, Ce, Sb；
（3）By step（1）The nickel foam of preparation is soaked in step（2）The impregnation liquid 15min of preparation, or by step（2）Prepare
Impregnation liquid is painted on step（1）In the nickel foam of preparation, drying, roasting 1 ~ 10 time repeatedly, is obtained a kind of for catalysis ozone oxygen
Change the catalyst of volatile organic matter；
Wherein, step（2）Described impregnation liquid, with hydrochloric acid adjust the pH value of ethanol solution between 1 ~ 4, will contain Mn, Sn, Ce,
The soluble-salt of Sb is dissolved in ethanol solution, obtains impregnation liquid, and the mol ratio of Mn, Sn, Ce, Sb is 10 in the impregnation liquid of preparation:10:
1:1。
4. preparation method according to claim 3, it is characterised in that step（1）Described nickel foam cleaning, by 0.1 ~
The nickel foam in the 2mm apertures C of constant temperature water bath 80 immersions 2h in 20% NaOH aqueous solutions, deionized water is rinsed well, dried,
Then the C of constant temperature water bath 95 soaks 2h in 15% oxalic acid aqueous solution, and deionized water is rinsed well, dries.
5. preparation method according to claim 3, it is characterised in that step（3）Described drying temperature is less than 80 C, roasting
Burn the C of temperature 200 ~ 800,3 ~ 5h of roasting.
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|---|---|---|---|---|
| CN106040226B (en) * | 2016-06-15 | 2017-11-14 | 北京化工大学 | A kind of cerium antimony composite oxide catalysts and its preparation method and application |
| CN106362809A (en) * | 2016-08-31 | 2017-02-01 | 谢振华 | Manufacturing process of honeycomb ceramic carrier |
| CN107961789B (en) * | 2016-10-19 | 2021-02-09 | 中国石油化工股份有限公司 | Preparation method of composite metal oxide catalyst, catalyst obtained by preparation method, application of catalyst and method for catalyzing ozone oxidation |
| CN107213907B (en) * | 2017-07-25 | 2020-06-26 | 南通斐腾新材料科技有限公司 | Preparation method of foam nickel-based in-situ mesoporous catalytic oxidation catalyst |
| CN110357242B (en) * | 2018-04-10 | 2022-11-15 | 中国石油化工股份有限公司 | Fluidized catalytic oxidation treatment device and method for treating salt-containing sewage |
| CN111229244B (en) * | 2018-11-28 | 2021-12-21 | 中蓝连海设计研究院有限公司 | Ozone catalytic oxidation catalyst and preparation method and application thereof |
| CN110218304B (en) * | 2019-07-02 | 2021-07-20 | 广昌立骅科技股份有限公司 | Preparation method and modification method of air-drying waterborne alkyd resin |
| CN110586125A (en) * | 2019-09-18 | 2019-12-20 | 天津大学 | High-activity foam copper monolithic catalyst and synthesis method and application thereof |
| CN111185175B (en) * | 2020-03-09 | 2022-01-04 | 中国科学院过程工程研究所 | Metal-based multi-stage structure membrane catalyst and preparation method and application thereof |
| CN113385182B (en) * | 2020-03-13 | 2023-05-26 | 中科汇智(东莞)设备科技有限公司 | Preparation method of foam metal-supported water-resistant carbon monoxide catalyst |
| CN112978986A (en) * | 2021-02-07 | 2021-06-18 | 金风环保有限公司 | Sewage treatment unit and sewage treatment system |
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| CN102941084A (en) * | 2012-11-22 | 2013-02-27 | 大连理工大学 | Method for preparing double-component metallic oxide catalytic ozonation catalyst |
| CN104084192A (en) * | 2014-07-29 | 2014-10-08 | 山东沁宇环保科技有限公司 | Catalyst for degrading ozone and removing VOCs synergistically as well as preparation method and application of catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2781639B2 (en) * | 1990-05-07 | 1998-07-30 | 三菱重工業株式会社 | Exhaust gas treatment method |
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Patent Citations (4)
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|---|---|---|---|---|
| CN1235871A (en) * | 1998-05-18 | 1999-11-24 | 株式会社日本触媒 | Lower alkank oxidative dehydrogenation catalysts and process for producing olefins |
| CN101757933A (en) * | 2010-02-01 | 2010-06-30 | 北京亚都空气污染治理技术有限公司 | Ozonolysis catalyst and preparation method thereof |
| CN102941084A (en) * | 2012-11-22 | 2013-02-27 | 大连理工大学 | Method for preparing double-component metallic oxide catalytic ozonation catalyst |
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