CN1714930A - Formaldehyde gas cyaniding catalyst under the room temperature condition - Google Patents

Formaldehyde gas cyaniding catalyst under the room temperature condition Download PDF

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Publication number
CN1714930A
CN1714930A CN 200410047973 CN200410047973A CN1714930A CN 1714930 A CN1714930 A CN 1714930A CN 200410047973 CN200410047973 CN 200410047973 CN 200410047973 A CN200410047973 A CN 200410047973A CN 1714930 A CN1714930 A CN 1714930A
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catalyst
metal oxide
noble metal
formaldehyde
metal
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CN 200410047973
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CN100360224C (en
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贺泓
石晓燕
张长斌
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Research Center for Eco Environmental Sciences of CAS
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Research Center for Eco Environmental Sciences of CAS
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Abstract

The invention provides a kind of catalyst that is used for oxidation of formaldehyde gas under the room temperature condition.With soluble inorganic salt classes such as the nitrate of metal or carbonate, obtain metal oxide by oxidation precipitation.The a spot of noble metal of load on metal oxide obtains oxidation of formaldehyde activity under the high room temperature condition.This catalyst is a main body by metal oxide, and the carried noble metal component constitutes on metal oxide.It is characterized in that the aforementioned metal oxide component can be at least a among the following metal oxide group, aforementioned noble metal component can be at least a among the following noble metal group.Metal oxide: alundum (Al, nickel oxide, manganese dioxide, silica, di-iron trioxide noble metal group: platinum, ruthenium, gold, rhodium, palladium.Catalyst of the present invention is made up of common metal oxide and small amount of precious metals, can effectively be applied to the catalytic oxidation of formaldehyde under the room temperature condition.The catalytic activity height of catalyst of the present invention, longer duration.The conversion ratio of the interior formaldehyde of scope can be up to 100% in actual working time for catalyst of the present invention.Catalyst of the present invention does not need other additional external condition when using, energy savings has the value of popularization.

Description

Formaldehyde gas cyaniding catalyst under the room temperature condition
Technical field
The present invention is used for oxidation of formaldehyde gas under the room temperature condition, can at ambient temperature formaldehyde gas be oxidized to carbon dioxide and water.
Technical background
Formaldehyde is more typical indoor environmental pollution thing.The multiple indoor finishing material, as furniture paint, wallpaper, plastic floor, chemical fibre carpet, door and window etc., all might be to indoor release formaldehyde, especially now artificial board generally uses phenolic resins etc. can discharge the adhesive of formaldehyde, the sustainable several years of release formaldehyde in indoor environment, grievous injury human healthy.Studies show that, contact low concentration formaldehyde (0.017mg/m for a long time 3~0.068mg/m 3), though the symptom intensity that causes a little less than, the acute effect that symptom and formaldehyde produce is consistent.
At present, the pollutants such as strong adsorptivity absorbing formaldehyde of the main applied activated carbon of various air purifiers.Use porous carbon material always, Alveolate activated carbon capable is arranged, spheric active carbon, NACF, novel absorbent charcoal and molecular sieve, zeolite, adobe ore, activated alumina and silica gel etc. are as adsorbent.This kind method is fairly simple, but adsorbent need regularly replace.Traditional catalytic decomposition that formaldehyde is decomposed into harmless tasteless substance need be finished at a certain temperature (generally more than 200 ℃) with catalysis technique, operating cost is higher.Though the plasma-catalytic technology can be under normal temperature, normal pressure resolving harmful gas, can produce accessory substances such as carbon monoxide, ozone and nitrogen oxide, and the equipment price costliness of plasma can take place.The many catalytic decomposition formaldehyde technology of current research are nano-photo catalytic, as obtaining the nano solid supper corrosive acid photochemical catalyst of national inventing patent (patent No. ZL98115808.0).This class catalyst is mainly with TiO 2Nano-powder or film be as photochemical catalyst, the method for preparing raw material complexity, and the specification requirement height, and nano-photocatalyst needs specific excitation source.
Summary of the invention
The present invention is directed to the problems referred to above, a kind of high-selectivity catalyst that is used for non-photochemical catalytic oxidation low concentration formaldehyde under the room temperature condition is provided.This catalyst use be simple and easy to metal oxide and very small amount of noble metal be raw material, the preparation method is simple.The present invention is fully taking into account on the basis of previous studies, is carrying out the result of big quantity research.The catalyst that is provided just can be catalytically conveted to carbon dioxide and water with formaldehyde at ambient temperature fully, and conversion ratio remains on 100% in the considerable time scope.Do not need light source and complicated auxiliary device and external condition.
Catalyst of the present invention is carrier with the metal oxide, other noble metal of load 0.5~1%.The aforementioned metal oxide can be at least a in alundum (Al, nickel oxide, manganese dioxide, silica, the di-iron trioxide, and aforementioned noble metal component can platinum, at least a in the gold, rhodium, palladium.
Aforesaid catalyst, if solution acidity control is improper in the preparation process of metal oxide, activity of such catalysts is that the conversion ratio of formaldehyde can reduce.And noble metal component is during less than 0.5% (metallic element weight scaled value), and the durability of catalyst can reduce, and noble metal component then can reduce selection of catalysts greater than 1%.The aforementioned metal oxide component can directly be the oxide of this metal, also can be obtained by certain method by the inorganic salts of other modes with some form such as nitrate carbonate of this metal.The noble metal component of aforementioned 0.5-1% (metallic element weight scaled value) can be the form of the oxide of this metal or this metal and any inorganic salts and do not change its effect, it act as the co-catalyst or second carrier, looks application and condition and adjusts.The feature of this catalyst is that the metal oxide carrier surface has a certain amount of oxygen species O 2 -, O -, O 2-, and be mainly O -Noble metal component can improve the durability and the activity of catalyst.
According to the present invention, metal oxide carrier can be by the nitrate of this metal, and inorganic salt forms such as carbonate prepare by the co-precipitation oxidizing process.With the nitrate dissolving of certain metal, with sodium hydroxide solution pH value is adjusted to 12~13 such as earlier under stirring state, slowly adds the liquor natrii hypochloritis again, placement is spent the night.Solution is filtered with suction method, and the sediment that obtains is used deionized water drip washing repeatedly, up to detecting less than the chlorion in the filtrate with liquor argenti nitratis ophthalmicus.To be deposited in 70 ℃ of dryings then.Obtained after the metal oxide, in the above-mentioned noble metal one or both have been loaded on the metal oxide according to 0.5-1% (metallic element weight scaled value).Remove moisture with Rotary Evaporators after the load, again at 70 ℃ of finish-dryings.The catalyst screening that makes is the particle of certain order number.
Aforesaid catalyst according to different needs, can be made various structures, as load on the wall surface of honeycomb ceramic body or metal mesh structure, or open-celled foams also can be as the structural carrier of catalyst.Also catalyst can be made spherical or tabular use.
Preparation process of the present invention is simple, and is easy to operate.Compare with prior art, the present invention has following advantage:
(1) cheap being easy to get of Preparation of Catalyst raw material of the present invention, service condition is simple, can effectively be applied to oxidation of formaldehyde under the room temperature condition.
(2) catalyst of the present invention can catalysis formaldehyde be harmless carbon dioxide and water just at ambient temperature.
(3) catalyst of the present invention interval in actual working time in the conversion ratio of formaldehyde can reach 100%.
(4) catalyst amount of the present invention is few, and does not need to expend electric power heating power, energy savings.
In order to be illustrated more clearly in the present invention, enumerate following examples, but it there is not any restriction to scope of the present invention.
Embodiment 1
Get 100 gram manganese nitrates and be dissolved in a certain amount of water, under stirring state, with sodium hydroxide solution solution being transferred to PH is 12~13, adds the liquor natrii hypochloritis gradually according to manganese nitrate and clorox molar ratio 2~3, and placement is spent the night.Filtering-depositing is used deionized water drip washing.Drip washing is to detecting less than chlorion is arranged in the filtrate with liquor argenti nitratis ophthalmicus.To be deposited in 70 ℃ of dry for standby.Precipitation after the oven dry be impregnated in 1% the Pt solution.Behind the rotary evaporation 70 ℃ of oven dry.It is that 40~60 order size particles are standby that catalyst after the oven dry is sieved.
Embodiment 2
Get 100 gram nickel nitrates and be dissolved in a certain amount of water, under stirring state, with sodium hydroxide solution solution being transferred to PH is 12~13, adds the liquor natrii hypochloritis gradually according to nickel nitrate and clorox molar ratio 2~3, and placement is spent the night.Filtering-depositing is used deionized water drip washing.Drip washing is to detecting less than chlorion is arranged in the filtrate with liquor argenti nitratis ophthalmicus.To be deposited in 70 ℃ of dry for standby.Precipitation after the oven dry be impregnated in 1% the Au solution.Behind the rotary evaporation 70 ℃ of oven dry.It is that 40~60 order size particles are standby that catalyst after the oven dry is sieved.
Embodiment 3
Get 100 gram nickel nitrates and be dissolved in a certain amount of water, under stirring state, with sodium hydroxide solution solution being transferred to PH is 12~13, adds the liquor natrii hypochloritis gradually according to nickel nitrate and clorox molar ratio 2~3, and placement is spent the night.Filtering-depositing is used deionized water drip washing.Drip washing is to detecting less than chlorion is arranged in the filtrate with liquor argenti nitratis ophthalmicus.To be deposited in 70 ℃ of dry for standby.Precipitation after the oven dry be impregnated in the 0.5%Au-0.5%Pd solution.Behind the rotary evaporation 70 ℃ of oven dry.It is that 40~60 order size particles are standby that catalyst after the oven dry is sieved.
Embodiment 4
0.066 gram embodiment 1 catalyst is positioned in the tubular fixed-bed reactor reacts, experiment condition is as follows:
Volume is formed: oxygen: 20%, and nitrogen: 80%, formaldehyde gas produces with the formaldehyde gas generator, is blown into reaction system by nitrogen, and the control concentration of formaldehyde is 0.05%, and reaction velocity (GHSV) is 50,000/ hours.At ambient temperature, the conversion ratio of formaldehyde is 100%, and 48 hours duration, conversion ratio descends and to be about 70% afterwards, keeps 60 hours afterwards conversion ratio do not fall as follows.
Embodiment 5
0.066 gram embodiment 2 catalyst are positioned in the tubular fixed-bed reactor react, experiment condition is as follows:
Volume is formed: oxygen: 20%, and nitrogen: 80%, formaldehyde gas produces with the formaldehyde gas generator, is blown into reaction system by nitrogen, and the control concentration of formaldehyde is 0.05%, and reaction velocity (GHSV) is 50,000/ hours.At ambient temperature, the conversion ratio of formaldehyde is 100%, and 48 hours duration, descending afterwards is about 80%, keeps 48 hours afterwards conversion ratio do not fall as follows.
Embodiment 6
0.066 gram embodiment 3 catalyst are positioned in the tubular fixed-bed reactor react, experiment condition is as follows:
Volume is formed: oxygen: 20%, and nitrogen: 80%, formaldehyde gas produces with the formaldehyde gas generator, is blown into reaction system by nitrogen, and the control concentration of formaldehyde is 0.05%, and reaction velocity (GHSV) is 50,000/ hours.At ambient temperature, the conversion ratio of formaldehyde is 100%, and 48 hours duration, descending afterwards is about 70%, keeps 78 hours afterwards conversion ratio do not fall as follows.

Claims (5)

1. the catalyst of oxidation of formaldehyde gas at ambient temperature is characterized in that this catalyst constitutes for a spot of noble metal component of load on metal oxide.
2. the described catalyst of claim 1 as described above is characterized in that, the aforementioned metal oxide component can be at least a in the following metal oxide, and aforementioned noble metal component can be at least a among the following noble metal group.
Metal oxide: alundum (Al, nickel oxide, manganese dioxide, silica, di-iron trioxide
Noble metal group: platinum, gold, rhodium, palladium
3. the described catalyst of claim 1 as described above is characterized in that, the aforementioned metal oxide component is by the peroxidating and obtaining under strong alkaline condition of the nitrate of this metal or carbonate.Noble metal component is carried on the metal oxide by infusion process.
4. the described catalyst of claim 1 as described above is characterized in that the load capacity of the noble metal component on the aforementioned metal oxide carrier is 0.5-1% (a metallic element weight scaled value).
5. the described catalyst of claim 1 as described above is characterized in that metal oxide carrier can be a nickel oxide, alundum (Al, manganese dioxide, silica, di-iron trioxide one or more hopcalites wherein.The noble metal component of load can be a kind of in platinum, gold, rhodium, the palladium or more than one.
CNB2004100479737A 2004-06-14 2004-06-14 Formaldehyde gas oxidation catalyst under room temperature Expired - Fee Related CN100360224C (en)

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CN101905159A (en) * 2010-08-13 2010-12-08 北京工业大学 Preparation method and application of Au and Ag loaded mesoporous beta-MnO2 catalyst
CN101274281B (en) * 2007-03-16 2011-06-15 苏州工业园区安泽汶环保技术有限公司 Room temperature catalyst for removing formaldehyde in air and method of preparing the same
CN102284285A (en) * 2010-06-18 2011-12-21 上海牛翼新能源科技有限公司 High-efficiency cold catalyst for simultaneously eliminating formaldehyde and carbon oxide in air purifier
CN102527228A (en) * 2011-12-31 2012-07-04 南京亿谱环境服务有限公司 Novel visible color change formaldehyde scavenger
CN102114428B (en) * 2009-12-31 2012-09-26 中国船舶重工集团公司第七一八研究所 Monolithic catalyst used for oxidizing CO and methanal under ordinary temperature and preparation method thereof
CN102019189B (en) * 2009-09-21 2013-01-09 北京纳维达斯科技有限公司 Catalyst and material for formaldehyde decomposition
CN102895971A (en) * 2011-07-25 2013-01-30 中国科学院理化技术研究所 Loaded Au1-xPtxMnO of alloy nanoparticles2Catalyst, preparation method and application thereof
CN103433054A (en) * 2013-08-13 2013-12-11 桐乡市健民过滤材料有限公司 Compound catalyst for removing formaldehyde and preparation method of compound catalyst
CN104693159A (en) * 2015-02-17 2015-06-10 华东师范大学 Method for preparing gamma-valerolactone by liquid-phase hydrogenation and catalyst used by same
CN104941406A (en) * 2015-05-25 2015-09-30 上海赛菲环境科技有限公司 Efficient targeted filling material of formaldehyde removal filter screen
CN105688907A (en) * 2016-02-06 2016-06-22 慈溪市梦园果蔬专业合作社 Formaldehyde mesoporous catalyst and preparation method thereof
CN106362765A (en) * 2015-07-24 2017-02-01 苏州工业园区新国大研究院 Formaldehyde room temperature oxidation catalyst preparation method and catalyst prepared through method
CN106513013A (en) * 2016-11-14 2017-03-22 江汉大学 Preparation method of Pt/graphene oxide/ferric oxide catalyst used for enhancing room temperature catalytic oxidation activity of formaldehyde
CN106582637A (en) * 2016-12-08 2017-04-26 中国科学院上海高等研究院 Formaldehyde oxidation catalyst and preparation method thereof
CN107362823A (en) * 2017-09-22 2017-11-21 临沂恺峰生物科技有限公司 A kind of catalysis material of room temperature degraded indoor formaldehyde and preparation method thereof
CN107684916A (en) * 2017-09-26 2018-02-13 嘉兴学院 A kind of integer catalyzer for being used for low temperature removal formaldehyde using carbide wood as carrier and preparation method thereof
CN108069636A (en) * 2017-12-19 2018-05-25 上海亮龙晋保新材料科技有限公司 A kind of non-photocatalyst-type is except formaldehyde diatom ooze and preparation method thereof
CN109011920A (en) * 2018-08-27 2018-12-18 杭州博大净化设备有限公司 A kind of antibacterial air-filtering membrane
CN109045959A (en) * 2018-09-18 2018-12-21 南京大学射阳高新技术研究院 A kind of reagent and method removing formaldehyde
CN109794160A (en) * 2017-11-16 2019-05-24 浙江盾安人工环境股份有限公司 A kind of catalyst and preparation method thereof for decomposing formaldehyde
CN110841627A (en) * 2019-11-09 2020-02-28 上海纳米技术及应用国家工程研究中心有限公司 Rare earth modified adsorption enrichment-catalytic oxidation bifunctional catalyst and preparation method and application thereof
CN111167281A (en) * 2020-01-09 2020-05-19 珠海格力电器股份有限公司 Manganese cerium oxide/active carbon composite material for formaldehyde decomposition and preparation method thereof
CN113426287A (en) * 2021-06-08 2021-09-24 广州大学 Formaldehyde removal material and preparation method and application thereof

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CA1279861C (en) * 1986-05-12 1991-02-05 Karl T. Chuang Catalyst assembly
US5585083A (en) * 1995-03-30 1996-12-17 The United States As Represented By The Administrator Of The National Aeronautics And Space Administration Catalytic process for formaldehyde oxidation
JP4007721B2 (en) * 1998-05-22 2007-11-14 大阪瓦斯株式会社 Method for oxidizing and removing acetaldehyde and formaldehyde
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CN101274281B (en) * 2007-03-16 2011-06-15 苏州工业园区安泽汶环保技术有限公司 Room temperature catalyst for removing formaldehyde in air and method of preparing the same
CN102019189B (en) * 2009-09-21 2013-01-09 北京纳维达斯科技有限公司 Catalyst and material for formaldehyde decomposition
CN102114428B (en) * 2009-12-31 2012-09-26 中国船舶重工集团公司第七一八研究所 Monolithic catalyst used for oxidizing CO and methanal under ordinary temperature and preparation method thereof
CN102284285A (en) * 2010-06-18 2011-12-21 上海牛翼新能源科技有限公司 High-efficiency cold catalyst for simultaneously eliminating formaldehyde and carbon oxide in air purifier
CN101905159B (en) * 2010-08-13 2011-12-21 北京工业大学 Preparation method and application of Au and Ag loaded mesoporous beta-MnO2 catalyst
CN101905159A (en) * 2010-08-13 2010-12-08 北京工业大学 Preparation method and application of Au and Ag loaded mesoporous beta-MnO2 catalyst
CN102895971A (en) * 2011-07-25 2013-01-30 中国科学院理化技术研究所 Loaded Au1-xPtxMnO of alloy nanoparticles2Catalyst, preparation method and application thereof
CN102527228B (en) * 2011-12-31 2015-11-18 南京亿谱环境服务有限公司 A kind of formaldehyde scavenger of visible color change
CN102527228A (en) * 2011-12-31 2012-07-04 南京亿谱环境服务有限公司 Novel visible color change formaldehyde scavenger
CN103433054A (en) * 2013-08-13 2013-12-11 桐乡市健民过滤材料有限公司 Compound catalyst for removing formaldehyde and preparation method of compound catalyst
CN103433054B (en) * 2013-08-13 2016-01-20 桐乡市健民过滤材料有限公司 A kind of except formaldehyde composite catalyst and preparation method thereof
CN104693159A (en) * 2015-02-17 2015-06-10 华东师范大学 Method for preparing gamma-valerolactone by liquid-phase hydrogenation and catalyst used by same
CN104941406A (en) * 2015-05-25 2015-09-30 上海赛菲环境科技有限公司 Efficient targeted filling material of formaldehyde removal filter screen
CN106362765A (en) * 2015-07-24 2017-02-01 苏州工业园区新国大研究院 Formaldehyde room temperature oxidation catalyst preparation method and catalyst prepared through method
CN105688907A (en) * 2016-02-06 2016-06-22 慈溪市梦园果蔬专业合作社 Formaldehyde mesoporous catalyst and preparation method thereof
CN105688907B (en) * 2016-02-06 2019-02-22 广州叶子环保科技有限公司 A kind of degradation of formaldehyde mesoporous catalyst and preparation method thereof
CN106513013A (en) * 2016-11-14 2017-03-22 江汉大学 Preparation method of Pt/graphene oxide/ferric oxide catalyst used for enhancing room temperature catalytic oxidation activity of formaldehyde
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CN107684916B (en) * 2017-09-26 2020-09-11 嘉兴学院 Monolithic catalyst using carbonized wood as carrier for removing formaldehyde at low temperature and preparation method thereof
CN107684916A (en) * 2017-09-26 2018-02-13 嘉兴学院 A kind of integer catalyzer for being used for low temperature removal formaldehyde using carbide wood as carrier and preparation method thereof
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CN108069636A (en) * 2017-12-19 2018-05-25 上海亮龙晋保新材料科技有限公司 A kind of non-photocatalyst-type is except formaldehyde diatom ooze and preparation method thereof
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CN110841627B (en) * 2019-11-09 2021-12-03 上海纳米技术及应用国家工程研究中心有限公司 Rare earth modified adsorption enrichment-catalytic oxidation bifunctional catalyst and preparation method and application thereof
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