WO2009094891A1 - Catalyseur au cu-ce-al permettant d'enlever des particules de suie et du nox simultanément, et procédé de préparation associé - Google Patents

Catalyseur au cu-ce-al permettant d'enlever des particules de suie et du nox simultanément, et procédé de préparation associé Download PDF

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Publication number
WO2009094891A1
WO2009094891A1 PCT/CN2008/073916 CN2008073916W WO2009094891A1 WO 2009094891 A1 WO2009094891 A1 WO 2009094891A1 CN 2008073916 W CN2008073916 W CN 2008073916W WO 2009094891 A1 WO2009094891 A1 WO 2009094891A1
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Prior art keywords
catalyst
copper
soot particles
gel
solution
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PCT/CN2008/073916
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English (en)
Chinese (zh)
Inventor
Xiaodong Wu
Duan WENG
Fan LIN
Jia Li
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Tsinghua University
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Publication of WO2009094891A1 publication Critical patent/WO2009094891A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • 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
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • 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
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/207—Transition metals
    • B01D2255/20761—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/209—Other metals
    • B01D2255/2092—Aluminium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/40—Nitrogen compounds
    • B01D2257/404—Nitrogen oxides other than dinitrogen oxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B01D2257/702—Hydrocarbons
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/01—Engine exhaust gases
    • B01D2258/012—Diesel engines and lean burn gasoline engines
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts

Definitions

  • Copper beryllium aluminum catalyst for removing soot particles and nitrogen oxides at the same time and preparation method thereof
  • the invention belongs to the technical field of preparation of diesel exhaust gas catalysts, in particular to a copper-rhenium-aluminum catalyst for removing carbon smoke particles and nitrogen oxides simultaneously by selective oxidation removal of diesel vehicle exhaust gas by using ruthenium oxide as carrier. Preparation.
  • diesel engines Compared with gasoline engines, diesel engines have high thermal efficiency, economy and low CO 2 emissions, so they have a bright future. With the increasingly strict environmental regulations, diesel exhaust pollutants, especially soot and nitrogen oxides (NOx), have been seriously polluted by the environment. Since the diesel engine is oxy-combusted, the most effective three-way catalyst (TWC) for gasoline engine exhaust purification is not suitable for diesel engines. The development of diesel vehicle exhaust catalytic purification materials and technologies such as gasoline TWC is in front of researchers. A challenging and urgent task.
  • Catalysts can be used to ensure the coating properties and thermal stability of the catalyst on DPF. Dispersed in high specific surface materials such as Y-A1 2 0 3 [Zhongpeng Wang et al, Catal. Commun. 8 (2007) 1659-1664; N. Nejar et al, Appl. Catal. B 70 (2007) 261-268] or zeolite Molecular sieves [ ⁇ Nejar et al., Catal. Today 119 (2007) 262-266].
  • An object of the present invention is to provide a copper beryllium aluminum catalyst which is inexpensive and has a good application effect while removing soot particles and nitrogen oxides, and a preparation method thereof.
  • the technical solution adopted by the present invention is: a copper beryllium aluminum catalyst which simultaneously removes soot particles and nitrogen oxides, and the copper beryllium aluminum catalyst has the general formula CuO-Ce0 2 -Al 2 0 3 , Wherein the Cu: Ce molar ratio is 1: 19 ⁇ 1: 4, (Cu0+Ce0 2 ): A1 2 0 3 mass ratio is 9:1 ⁇ 1: 2.
  • Another technical solution provided by the present invention is: a preparation method of a copper bismuth aluminum catalyst for simultaneously removing soot particles and nitrogen oxides, wherein the copper bismuth aluminum catalyst is prepared by a sol-gel method or a coprecipitation method, and is prepared. Proceed as follows:
  • Coprecipitation method adding the precipitant ammonia water and the oxidant 0 2 to the mixed solution obtained in the step 1, adding hydrogen peroxide when the Ce 3+ salt is used in the mixed solution, and adding hydrogen peroxide when using the Ce 4+ salt, wherein the ammonia water is added in an amount of Maintaining the pH value of the final solution > 10, the amount of addition of 0 2 is equivalent to 1.2 times the molar content of the ruthenium ion, and the precipitate is stirred to obtain a suspension;
  • the suspension obtained in the step 3 is continuously heated and stirred at 100 to 12 (TC is evaporated to form a gel; or the suspension obtained in the step 3 is obtained by the coprecipitation method. Stirring was stopped, allowed to stand for 24 h, the supernatant liquid was poured off, and suction filtration was performed to obtain a lumpy precipitate, which was washed with water 2 to 3 times, and then the obtained gel or precipitate was baked at 120 ° C;
  • the soluble salt of A1 is also added at the same time, and the ratio of the final product (CuO+Ce0 2 ) :Al 2 0 3 is 9:1 to 1:2. It is mixed with a soluble salt of Cu and Ce, and the catalyst powder is obtained in the same manner as in the other steps except that the step (3) is omitted.
  • the copper salt is Cu(N0 3 ) 2 *6H 2 0, and CuS0 4 *5H 2 0 or CuCl 2 *2H 2 0 may also be used in the coprecipitation method.
  • the sulfonium salt is Ce(N0 3 ) 3 *6H 2 0 or Ce ( ⁇ ) 2 ( ⁇ 0 3 ) 6 ⁇ 2 ⁇ 2 0, and Ce (S0 4 ) 2 *4H 2 0 may be used in the coprecipitation method.
  • the alumina is a high specific surface Y-A1 2 0 3 (120 ⁇ 200m7g), the aluminum salt is Al ( ⁇ 0 3 ) 3 ⁇ 9 ⁇ 2 0, and the Al 2 (S0 4 ) 3 can also be used in the coprecipitation method. ⁇ 183 ⁇ 40 or A1C1 3 .
  • the invention has the beneficial effects that: the cheap non-precious metal salt is used as the raw material, and the catalyst production cost is low; the simple catalyst preparation process such as the sol-gel method and the coprecipitation method is adopted, the reaction process is easy to control, and the industrial production is easy to be realized;
  • the obtained CuO-Ce0 2 -Al 2 0 3 catalyst can greatly reduce the temperature of burning the soot collected on the particulate trap to C0 2 and at the same time have the ability to reduce nitrogen oxides, thereby simultaneously eliminating soot particles and The effect of nitrogen oxides.
  • the catalyst still has a large specific surface area after being treated at 800 ° C for 10 hours in an air atmosphere.
  • the alumina acts to prevent the growth of cerium oxide and copper oxide grains, and can catalytically burn soot particles at 455 ° C. And the reduction rate of NO is 34%, indicating that the catalyst has high high temperature resistance.
  • a 5 g copper beryllium aluminum catalyst (CuCeA19) was prepared by a sol-gel method. About 30 ml of deionized water was added to a 200 ml beaker, and 10.78 g of cerium nitrate, 0.68 g of copper nitrate, and 3.68 g of aluminum nitrate were added and dissolved by stirring. 28 g of citric acid and 0.8 g of polyethylene glycol were added to the solution and mixed well. The solution was continuously heated and stirred at 110 ° C until evaporated to form a gel; then dried in an oven at 120 ° C. The obtained gel solid was chopped, ground, and calcined at 500 ° C for 3 hours to obtain a CuCeA19 catalyst powder sample. The molar ratio of Cu to Ce in the catalyst was 1:9, and the mass ratio of (Cu0+Ce0 2 ) to A1 2 0 3 was 9:1.
  • CuCeA12 copper beryllium aluminum catalyst
  • the obtained gel solid was chopped, ground, and calcined at 500 ° C for 3 hours to obtain a CuCeA12 catalyst powder sample.
  • the molar ratio of Cu to Ce in the catalyst was 1:9, and the mass ratio of (Cu0+Ce0 2 ) to A1 2 0 3 was 2:1.
  • CuCeAll copper beryllium aluminum catalyst
  • the obtained precipitate was crushed, ground, and calcined at 500 ° C for 3 hours to obtain a CuO-Ce0 2 -Al 2 O 3 catalyst powder.
  • the molar ratio of Cu to Ce in the catalyst was 1:4, and the mass ratio of (Cu0+Ce0 2 ) to A1 2 0 3 was 1:2.
  • CuCeA12 copper beryllium aluminum catalyst
  • the obtained gel solid was chopped, ground, and calcined at 500 ° C for 3 hours to obtain a powder sample of CuO-Ce0 2 -Al 2 O 3 catalyst.
  • the molar ratio of Cu to Ce in the catalyst was 1:19, and the mass ratio of (Cu0+Ce0 2 ) to A1 2 0 3 was 4:1.
  • a 5 g copper ruthenium catalyst (CuCe) was prepared by a sol-gel method. About 30 ml of deionized water was added to a 200 ml beaker, and 11.98 g of cerium nitrate and 0.776 g of copper nitrate were added and stirred to dissolve. 21 g of citric acid and 0.6 g of polyethylene glycol were added to the solution, and the mixture was uniformly mixed. The solution was continuously heated and stirred at 110 ° C until it was evaporated to form a gel; then dried at 120 ° C in an oven. The obtained gel solid was chopped, ground, and calcined at 500 ° C for 3 hours to obtain a CuCe catalyst powder sample. The molar ratio of Cu to Ce in the catalyst was 1:9.
  • TP0 temperature-programmed activity test curve for CuCe and CuCeA12 catalyst aged samples, wherein the test atmosphere: 10% 0 2 + lOOOOppm N0 + N 2 equilibrium; gas flow rate: 500 mL / min; heating rate: 20 ° C / Min.
  • CuCeA19, CuCeA12, CuCeAl1 in Example 1, 2, and 3 and CuCeAl1 in Comparative Example 1 were respectively placed in a crucible, and treated in an electric resistance furnace at 800 ° C for 10 hours, and after cooling, a catalyst sample after heat treatment was obtained. Marked with the suffix "_a”. Taking CuCeA19_a, CuCeA12_a, CuCeAl l_a and CuCe_a catalysts as an example, the catalytic activity of soot catalytic combustion under the catalyst-smoke loose contact mode was tested in the atmosphere of simulated diesel exhaust.
  • test procedure Take 100 mg of catalyst, mix with 10 mg of soot (Printex-U, Degussa), gently scrape it in a mortar with a spatula for 5 min, and install the mixture in a quartz tube reactor for temperature-programmed reaction (TPR). experiment.
  • the test atmosphere is 10%0 2 /N 2 or 1000ppmNO/10%0 2 /N 2 , and the space velocity is 40000h—

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)
  • Exhaust Gas Treatment By Means Of Catalyst (AREA)

Abstract

La présente invention concerne un catalyseur au Cu-Ce-Al permettant d'enlever des particules de suie et du NOx simultanément, ayant pour formule structurelle CuO-CeO2-Al2O3, le rapport molaire du Cu / Ce étant de 1/19 à 1/4 et le rapport massique de (CuO-CeO2)/Al2O3 étant de 9/1 à 1/2. Le catalyseur peut être préparé par un procédé sol-gel ou un procédé de coprécipitation qui utilise des sels de métaux non nobles bon marché comme matière première. Le procédé de préparation peut être facilement contrôlé et peut permettre une industrialisation facile. Le catalyseur permet d'abaisser la température de combustion des particules de suie de 500 °C à 400 °C et de réduire NO dans une certaine mesure, permettant ainsi de supprimer ces deux polluants simultanément. Le catalyseur présente une stabilité thermique supérieure.
PCT/CN2008/073916 2008-01-29 2008-12-31 Catalyseur au cu-ce-al permettant d'enlever des particules de suie et du nox simultanément, et procédé de préparation associé WO2009094891A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN200810057042.3 2008-01-29
CN2008100570423A CN101239313B (zh) 2008-01-29 2008-01-29 同时脱除碳烟颗粒和氮氧化物的铜铈铝催化剂及制备方法

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110871065A (zh) * 2018-09-04 2020-03-10 天津大学 一种水热还原制备氧化铈催化剂的方法及其应用
CN114029068A (zh) * 2021-12-03 2022-02-11 华设设计集团环境科技有限公司 一种柴油机尾气中氮氧化物和颗粒物协同控制催化剂及其制备方法和应用

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CN102909023A (zh) * 2012-09-14 2013-02-06 广州市卫斯理日化实业有限公司 汽车尾气催化剂及其制备方法
CN105126819B (zh) * 2015-09-01 2018-10-30 中国石油大学(北京) 一种同时消除nh3、no和碳烟颗粒的复合氧化物催化剂及其制备方法和用途
CN105597781A (zh) * 2016-02-01 2016-05-25 厦门大学 一种碳颗粒物燃烧催化剂及其制备方法
CN105727964B (zh) * 2016-02-02 2018-07-03 中国石油大学(北京) 一种同时消除no和炭烟颗粒物的三维复合氧化物催化剂及其制备方法和用途
WO2019042911A1 (fr) * 2017-08-29 2019-03-07 Rhodia Operations Utilisation d'un oxyde mixte pour absorber le nox
US11897779B2 (en) 2018-08-24 2024-02-13 East China Normal University Microporous aluminotitanosilicate crystalline zeolite, method of preparation and applications thereof
CN110013846B (zh) * 2018-12-22 2022-04-05 北京工业大学 铝锰共柱撑蒙脱石负载Ce-Cu或Eu-Ce复合催化剂的制备方法和应用
CN110479326A (zh) * 2019-09-10 2019-11-22 清华大学 一种磷掺杂铜铈复合金属氧化物双功能催化剂及其制备方法和应用
CN111558372B (zh) * 2020-04-27 2021-07-23 生态环境部华南环境科学研究所 一种中低温负载型纳米氧化铜颗粒催化剂及其制备方法和应用

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CN1907561A (zh) * 2006-07-28 2007-02-07 华南理工大学 超声－等离子体联合制备CuO/CeO2/γ－Al2O催化剂的方法

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US4996180A (en) * 1987-12-11 1991-02-26 Johnson Matthey Public Limited Company Catalyst of copper oxide and ceria
CN1236669A (zh) * 1998-05-22 1999-12-01 中国科学院山西煤炭化学研究所 一种用于甲酸甲酯低温合成甲醇的氢解催化剂及其制备方法
CN1907561A (zh) * 2006-07-28 2007-02-07 华南理工大学 超声－等离子体联合制备CuO/CeO2/γ－Al2O催化剂的方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110871065A (zh) * 2018-09-04 2020-03-10 天津大学 一种水热还原制备氧化铈催化剂的方法及其应用
CN114029068A (zh) * 2021-12-03 2022-02-11 华设设计集团环境科技有限公司 一种柴油机尾气中氮氧化物和颗粒物协同控制催化剂及其制备方法和应用

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CN101239313A (zh) 2008-08-13

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