WO2016041380A1 - Catalyseur supporté approprié pour purifier l'air à température normale - Google Patents

Catalyseur supporté approprié pour purifier l'air à température normale Download PDF

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Publication number
WO2016041380A1
WO2016041380A1 PCT/CN2015/080483 CN2015080483W WO2016041380A1 WO 2016041380 A1 WO2016041380 A1 WO 2016041380A1 CN 2015080483 W CN2015080483 W CN 2015080483W WO 2016041380 A1 WO2016041380 A1 WO 2016041380A1
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nano
supported catalyst
copper
manganese
normal temperature
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PCT/CN2015/080483
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English (en)
Chinese (zh)
Inventor
许钧强
康伦国
姚东生
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合众（佛山）化工有限公司
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Publication of WO2016041380A1 publication Critical patent/WO2016041380A1/fr

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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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/16—Clays or other mineral silicates
    • 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
    • B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
    • 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
    • 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
    • B01J23/72—Copper
    • 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
    • B01J23/83—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 rare earths or actinides
    • 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

Definitions

  • the invention relates to a preparation method of a supported catalyst for purifying air, in particular to a suitable supported catalyst for purifying air at a normal temperature, and belongs to the technical field of catalysts.
  • indoor decoration pollution is mainly chemical pollutants such as formaldehyde, benzene, ammonia, etc.
  • the release period of such pollutants is up to 15 years, and it is not a problem of two months to solve the problem.
  • indoor decoration pollution is mainly chemical pollutants such as formaldehyde, benzene, ammonia, etc.
  • the release period of such pollutants is up to 15 years, and it is not a problem of two months to solve the problem.
  • In the enclosed room of summer air conditioning and cold winter heating Due to the lack of outdoor fresh air, the damage is even more serious!
  • hotel, conference room, furniture mall, building materials market, etc. do you have headaches, dazzling, cough, chest tightness, nausea, vomiting, etc.
  • Indoor invisible killer caused by air pollutants The main pollution of indoor air comes from materials such as construction, decoration and furniture, including formaldehyde, benzene and ammonia. Among them, formaldehyde pollution is the most harmful to human health.
  • formaldehyde scavenger or formaldehyde lyase these are chemical methods to "remove" formaldehyde, the essence of this method is to reduce the target substance to reduce toxicity or conversion to non-toxic substances, formaldehyde can be oxygen The formation of formic acid can also be reduced to methanol. The toxicity of these two substances still exists, which is easy to cause secondary pollution, and it is impossible to "spray forever".
  • photocatalyst method but the photocatalyst should play a role, there must be ultraviolet light to stimulate, no effect at night and no visible light.
  • the particles of the photocatalyst are very small and easily suspended in the air. It is like dust and cannot be seen with the naked eye. Even if it is inhaled, it is not noticeable, and it is easy to cause secondary pollution, which is likely to cause damage to the human lungs.
  • photocatalysts that have the property of decomposing organic substances, which can damage any organism such as leather products, hair grass and high-grade clothing and skin.
  • photocatalyst manufacturers do not mention it, do not inform consumers, and even mislead consumers of photocatalysts as long as they have Light is good, and such behavior should be blamed.
  • photocatalysts have a limited effect on removing polluting gases from the air, so they are rarely used in developed countries as civilian photocatalytic materials.
  • the plasma technology method is to generate a large amount of plasma to oxidize formaldehyde in the air to achieve the purpose of purifying air. This method is easy to generate ozone to cause secondary pollution to the air, and the device is complicated and consumes a large amount of energy; the conventional thermal catalytic oxidation method It is the use of a catalyst to catalyze the oxidation of formaldehyde under the action of thermal energy. However, this method generally requires a higher temperature.
  • room temperature-supported formaldehyde-removing catalysts contain precious metals such as gold, palladium, rhodium, iridium, and platinum. Due to the scarcity of precious metal resources, the price is expensive, which limits The promotion and application of formaldehyde removal by room temperature catalytic oxidation, such as patents CN100360224C, CN102284288B, CN103894194A contain precious metals.
  • Patent CN103599793A, CN103433054A, CN101274281B although excluding precious metals, but only in the air VOC S formaldehyde removal, and in addition to air VOC S-trityl there formaldehyde, ammonia, carbon monoxide, nitric oxide, sulfur dioxide and other pollutants Therefore, it is very important to develop an economical catalyst that can effectively remove harmful substances in the air at normal temperature.
  • An object of the present invention is to provide an economical applicability and a supported composite catalyst capable of removing formaldehyde, triphenyl, CO, NO, and SO 2 in air VOC S under normal temperature conditions.
  • the composite catalyst carrier of the present invention is prepared by purifying nano attapulgite or nano-sorbitite powder and supporting manganese, copper and cerium oxide.
  • Nano attapulgite and nano-sorbitite powder are porous mineral crystal materials, and their microstructure has a unique crystal regular structure. There are a large number of nano-scale pores in the crystal, the pore size is 2.7-9.8 angstroms, and the surface of the micropores is polar. Due to its nanometer pore size, it can selectively adsorb toxic substances such as benzene, xylene, formaldehyde, carbon monoxide, sulfur dioxide and ammonia in the nanometer molecular diameter (formaldehyde, ammonia, benzene, toluene and xylene have molecular diameters of 0.4 to 0.62). Between nanometers, and these compounds are polar molecules, which are nano-scale polar compounds), so nano-attapulgite and nano-sepiolite powder pores have superior adsorption and sustainable functions.
  • Manganese-copper composite oxide can effectively treat harmful gases in the air such as formaldehyde, triphenyl, carbon monoxide, nitrogen monoxide and sulfur dioxide.
  • Rare earth cerium oxide has redox characteristics, oxygen storage and synergistic catalysis, and can effectively increase manganese at normal temperature.
  • the catalytic activity of the copper composite oxide can also improve the stability and anti-poisoning ability of the catalyst;
  • the supported catalyst prepared by loading the manganese attapulgite composite oxide with nano attapulgite or nano sepiolite powder, and having a super-normal temperature at room temperature Strong adsorption capacity, can enrich a small amount of harmful gases in the air, and can effectively remove harmful gases in the air through synergistic catalytic oxidation of manganese-copper bismuth; and high treatment efficiency, low cost, wide economic applicability, no production Secondary pollution.
  • the present invention relates to a suitable load-type catalyst for purifying air at normal temperature, characterized in that copper, cerium and manganese are active components, and the carrier is a nano attapulgite rod. Soil or nano-porphyry powder, wherein the content of copper, barium and manganese is 15% to 40% of the total mass, and the molar ratio is 1:1:1 to 1:2:4.
  • the invention provides a preparation method of a suitable load-type catalyst for purifying air at normal temperature, and the preparation process is as follows: adding nano attapulgite or nano sepiolite powder to ethanol, deionized water, and adding nanometer cerium oxide by stirring under agitation. Ultrasonic dispersion for 1h, the nanosuspension was prepared, and then an aqueous solution of copper nitrate and manganese nitrate was added according to the formula molar ratio, and stirred at 30 to 50 ° C for 2 to 4 hours, the solution was removed, and dried at 110 to 120 ° C for 5 to 10 hours. After calcination at 500 to 800 ° C for 3 to 6 hours in a muffle furnace, the fineness is milled to 20 ⁇ or less.
  • the applicable load-type catalyst for purifying air at normal temperature prepared by the invention has superior adsorption capacity, and can continuously and effectively remove triphenyl, formaldehyde, ketone, ammonia and carbon monoxide which are volatilized from the decoration materials used in the interior decoration process. Nitrogen oxide, sulfur dioxide and other harmful gases, high processing efficiency, low cost, wide economic applicability, no secondary pollution, suitable for home, office, hotel, conference room, furniture shopping mall, building materials market and other space pollutants Removal.
  • nano-boehmite powder into 200ml ethanol-water solution, add 6g nano-cerium oxide under stirring, and disperse ultrasonically for 1h to prepare nano-sepiolite powder/cerium oxide suspension, add 50% copper nitrate aqueous solution 6g and 50% manganese nitrate.
  • 25 g of an aqueous solution was stirred at 40 to 50 ° C for 3 hours to remove the solution.
  • After drying and activating at 120 ° C for 6 h it was calcined in a muffle furnace at 700 for 4 h and then ground to a fineness of 20 ⁇ to prepare a supported catalyst with a loading of 20% and a molar ratio of copper, ruthenium and manganese of 1:2: 3.
  • Catalyst performance test The supported catalyst prepared in the example of the present invention was placed in a fixed bed reactor under the following conditions: gas composition: oxygen 20%, nitrogen 80%, formaldehyde gas, benzene gas respectively from formaldehyde gas generator, benzene
  • gas composition oxygen 20%, nitrogen 80%, formaldehyde gas, benzene gas respectively from formaldehyde gas generator, benzene
  • the gas generator is generated and blown into the reaction system by nitrogen gas to control the concentration of formaldehyde gas to be 0.05% and the concentration of benzene gas to be 0.1%.
  • Example 2 Example 3 Formaldehyde removal rate 95.6% 92.5% 94.6% Formaldehyde removal effect persistence 76.4% 73.8% 75.2% Benzene removal rate 97.5% 96.2% 95.6% Benzene removal effect persistence 77.5% 73.6% 74.8%
  • Catalyst performance test The supported catalyst prepared in the example of the present invention was placed in a fixed bed reactor under the following conditions: a gas sampler was used to take the automobile exhaust gas, a dryer was used to remove the moisture in the exhaust gas, and the CO in the exhaust gas was tested. The content of NO and SO 2 was further injected into the reaction system by nitrogen gas, and after reacting at 25 ° C for 48 hours, the contents of CO, NO and SO 2 were tested according to standard methods. The catalytic performance CO emission rate, NO removal rate, and SO 2 removal rate test results of the three examples are shown in Table 2.
  • Example 1 Example 2
  • Example 3 CO removal rate 82.5% 80.6% 81.2% NO removal rate 78.4% 72.6% 75.3% SO 2 removal rate 87.2% 86.5% 85.4%

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • Exhaust Gas Treatment By Means Of Catalyst (AREA)
  • Catalysts (AREA)
  • Disinfection, Sterilisation Or Deodorisation Of Air (AREA)

Abstract

La présente invention concerne un catalyseur supporté approprié pour purifier l'air à température normale, comprenant du cuivre, du cérium et du manganèse en tant qu'ingrédients actifs avec une nanopoudre d'attapulgite ou de sépiolite en tant que support, la teneur en cuivre, cérium et manganèse représentant 15 % à 40 % de la masse totale et le rapport molaire de ceux-ci étant 1:1:1-1:2:4 ; les matières premières sont dispersées par ultrasons pendant 1 h, agitées pendant 2 h à 4 h dans les conditions de 30 °C à 50 °C, séchées à une température de 110 °C à 120 °C pendant 5 h à 10 h pour activation, calcinées dans un four à moufle à une température de 500 °C à 800 °C pendant 3 h à 6 h et broyées ensuite à une finesse de pas plus de 20 μ ; le catalyseur supporté préparé dans la présente invention présente une forte capacité d'adsorption, peut éliminer le benzène, le toluène, le xylène, le formaldéhyde, le CO, le NO, le SO2 et d'autres gaz nocifs dans l'air en continu et de manière efficace, présente une efficacité de traitement élevée, de faibles coûts, une large applicabilité économique et ne produit pas de pollution secondaire, et est approprié pour éliminer les polluants dans des maisons, des bureaux, des hôtels, des salles de conférence, des magasins de meubles, des marchés de matériaux de construction et d'autres espaces.
PCT/CN2015/080483 2014-09-19 2015-06-01 Catalyseur supporté approprié pour purifier l'air à température normale WO2016041380A1 (fr)

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Application Number Priority Date Filing Date Title
CN2014104826152 2014-09-19
CN201410482615.2A CN105478134B (zh) 2014-09-19 2014-09-19 一种在常温下净化空气的适用性负载型催化剂

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CN110052275A (zh) * 2019-02-11 2019-07-26 北京工业大学 钠化海泡石负载Cu-Er或Cu-Nb复合型催化剂的制备方法和应用
CN110294949A (zh) * 2019-07-16 2019-10-01 东莞市艾呼吸电子科技有限责任公司 一种光触媒空气净化粉及涂料
CN113088146A (zh) * 2021-04-01 2021-07-09 联科华技术有限公司 一种具有除甲醛功能的单原子涂料及其制备方法
CN113663668A (zh) * 2021-09-01 2021-11-19 南大恩洁优环境技术(江苏)股份公司 一种VOCs净化用炭纤维负载室温催化剂及其制备方法
CN114433032A (zh) * 2022-02-07 2022-05-06 杭州博华科技创新有限公司 一种仿生纳米除味剂、制备方法及应用
CN114749185A (zh) * 2022-04-29 2022-07-15 西安石油大学 用于室温富集-氧化甲醛的限域纳米催化剂及其制备方法
WO2022253117A1 (fr) * 2021-06-02 2022-12-08 南京风清扬健康科技有限公司 Matériau fonctionnel pour la dégradation visuelle de formaldéhyde et des cov à température ambiante et pression atmosphérique et son procédé de préparation
CN115845862A (zh) * 2022-11-30 2023-03-28 北京华能长江环保科技研究院有限公司 改性海泡石负载还原氧化石墨烯和Cu-Eu的复合催化剂及其制备方法
CN116196962A (zh) * 2023-02-20 2023-06-02 广州绿固环保科技有限公司 一种高效环保型甲醛吸附剂及其制备方法
CN116237045A (zh) * 2023-02-10 2023-06-09 山东凯大新型材料科技有限公司 一种硅藻土基光热催化复合材料的制备方法及应用
CN116651201A (zh) * 2023-07-21 2023-08-29 广州科腾环保科技有限公司 一种用于除甲醛抗菌的空气净化复合材料及其制备方法

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CN106334565B (zh) * 2016-10-12 2020-06-09 友好净控科技（浙江）有限公司 一种空气净化复合催化剂及其制备方法
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CN106693933A (zh) * 2016-12-02 2017-05-24 郑州源冉生物技术有限公司 一种NOx吸附剂及其制备方法和应用
CN106975493A (zh) * 2017-04-20 2017-07-25 宁波钛安新材料科技有限公司 一种蜂窝状催化剂材料及其成型方法
CN107442130B (zh) * 2017-08-24 2019-10-22 中国科学院广州地球化学研究所 一种坡缕石负载型铜锰氧化物及其制备方法和应用
CN108607356B (zh) * 2018-03-30 2021-04-23 杭州恒清科技有限公司 一种多功能环保空气净化复合新材料及其制备方法
CN110038566A (zh) * 2019-04-29 2019-07-23 南京融众环境工程研究院有限公司 一种负载型纳米Ag/MnCeOx/凹凸棒土催化剂及其制备方法
CN112535952A (zh) * 2020-12-23 2021-03-23 常州北化澳联环保科技有限公司 用于净化VOCs的瓷砖的制备方法
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Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110052275A (zh) * 2019-02-11 2019-07-26 北京工业大学 钠化海泡石负载Cu-Er或Cu-Nb复合型催化剂的制备方法和应用
CN110294949A (zh) * 2019-07-16 2019-10-01 东莞市艾呼吸电子科技有限责任公司 一种光触媒空气净化粉及涂料
CN113088146A (zh) * 2021-04-01 2021-07-09 联科华技术有限公司 一种具有除甲醛功能的单原子涂料及其制备方法
WO2022253117A1 (fr) * 2021-06-02 2022-12-08 南京风清扬健康科技有限公司 Matériau fonctionnel pour la dégradation visuelle de formaldéhyde et des cov à température ambiante et pression atmosphérique et son procédé de préparation
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