EP0344306A1 - Catalyseur et son procede de production - Google Patents

Catalyseur et son procede de production

Info

Publication number
EP0344306A1
EP0344306A1 EP89906302A EP89906302A EP0344306A1 EP 0344306 A1 EP0344306 A1 EP 0344306A1 EP 89906302 A EP89906302 A EP 89906302A EP 89906302 A EP89906302 A EP 89906302A EP 0344306 A1 EP0344306 A1 EP 0344306A1
Authority
EP
European Patent Office
Prior art keywords
catalyst
representative
oxide
manganese
iron
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.)
Ceased
Application number
EP89906302A
Other languages
German (de)
English (en)
Inventor
Wing Fong Chu
Franz-Josef Rohr
Norbert Pfeifer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ABB AG Germany
ABB AB
Original Assignee
Asea Brown Boveri AG Germany
Asea Brown Boveri AB
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Asea Brown Boveri AG Germany, Asea Brown Boveri AB filed Critical Asea Brown Boveri AG Germany
Publication of EP0344306A1 publication Critical patent/EP0344306A1/fr
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • B01D53/9445—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC]
    • B01D53/945—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC] characterised by a specific catalyst
    • 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
    • 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
    • B01J23/78—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 alkali- or alkaline earth metals
    • 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
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/10—Internal combustion engine [ICE] based vehicles
    • Y02T10/12—Improving ICE efficiencies
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S502/00—Catalyst, solid sorbent, or support therefor: product or process of making
    • Y10S502/524—Spinel
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S502/00—Catalyst, solid sorbent, or support therefor: product or process of making
    • Y10S502/525—Perovskite

Definitions

  • the invention relates to a catalyst according to the preamble of claim 1.
  • Such catalysts are preferably used to remove pollutants in exhaust gases.
  • the nitrogen oxides (NO x ) are reduced by the ammonia (NH3) added to the flue gas over a catalyst made of titanium oxide / vanadium oxide (TiO 2 / V 2 O 3 ) at 300 to 400 ° C with the formation of harmless nitrogen and water.
  • a disadvantage of the catalysts used in the SCR process is that they are not suitable for fuel or exhaust gas-own reducing agents such as carbon monoxide, hydrogen or hydrocarbons, and they only have a very short lifespan in practical use. These disadvantages, as well as the need for ammonia as a reduction The use of agents considerably limits the technical application of the SCR process. Additional difficulties arise from the storage of the ammonia, as well as the exact dosage of the same. Furthermore, the formation of solid ammonium sulfide residues makes the use of this process difficult.
  • the invention is therefore based on the object of providing a catalyst which enables the reduction of nitrogen oxides with the aid of carbon monoxide, hydrogen and hydrocarbons and ammonia, and also to show a process with which such a catalyst can be produced.
  • the catalyst according to the invention is distinguished by a long service life, which is due to its thermal, chemical and mechanical stability. With it, it is possible to reduce nitrogen oxides with the help of carbon monoxide, hydrogen and hydrocarbons, which are contained in every exhaust gas from internal combustion engines and combustion plants. The reduction through the additional use of ammonia is also possible with this catalyst.
  • the pore size of the catalyst material is chosen so that the active surface is not reduced by large pores. The pores are also not too small, so that the diffusion of the chemical reactants and the diffusion out of the reaction products are not hindered. Further features essential to the invention are characterized in the subclaims.
  • the mixed oxides with perovskite structure or perovskite spinel structure used to produce the catalyst are characterized by high thermal stability and chemical resistance to hot gases, which are corrosive components, in a wide temperature range, namely between room temperature and a temperature of 1200 ° C Fabrics such as Carry oxygen, sulfur, sulfur oxides, sulfates, vanates and various alkali salts with them.
  • the catalytic activity of these mixed oxides in particular in the reduction of nitrogen oxides by carbon monoxide, hydrogen, hydrocarbons or ammonia, is based on the action of the d-electron orbitals of the transition metal ions which are contained in each of these mixed oxides and are preferably located on the surface of the finished catalyst .
  • the cubic perovskite grid of the above Mixed oxides contain the ions of the transition metals as well as the oxygen ions on the 100 grid surface.
  • the ions of the transition metals of these mixed oxides are unsaturated on the surface of these crystallites because of the lack of oxygen ions. These unsaturated ions cause charge transfer processes with adsorbed molecules from the gas phase. This brings about the reduction of nitrogen oxides in the presence of suitable reducing agents such as carbon monoxide, hydrogen and hydrocarbons and ammonia.
  • Mixed oxides with a spinel structure also contain ions of the transition metals on the crystal surface.
  • the catalytic activity of the pure spinels is in ver lower than the mixed oxides with a pure perovskite structure.
  • a suitable combination of mixed oxides with a perovskite structure and those with a spinel structure can very significantly improve the catalytic activity of these mixed oxides for the reduction of the nitrogen oxides.
  • the only figure belonging to the description shows a catalyst 1.
  • the actual catalyst material 2 is applied to a carrier 3. It is formed by a single or multi-phase mixed oxide system.
  • This mixed oxide system can have, for example, a pure perovskite structure or a mixed perovskite spinel structure.
  • the preferred mixed oxide systems have the following composition:
  • SUBSCRIPTION 3 / BN 2 O 4 is also suitable as a catalyst material.
  • the mixed oxide also has a phase mixture with a perovskite and spinel structure.
  • A represents lanthanum
  • M represents magnesium, calcium, strontium or barium
  • B represents manganese, iron, cobalt, nickel and chromium
  • N represents iron, manganese, copper or vanadium
  • x may have a value between 0 and 0.6 in the compositions shown above, while y may have a value between 0 and 0.6.
  • Specific examples of the general compositions of the possible mixed oxides described above are shown below.
  • the first composition shows a mixed oxide with a pure perovskite structure:
  • compositions shown below are examples of mixed oxides with a perovskite and spinel structure:
  • Carbonates or oxides of the metals which form the mixed oxides are used to produce these compositions described above.
  • lanthanum oxide (La 2 O 3 ), strontium oxide (SrO), manganese oxide (MnO 2 ), iron oxide (Fe 2 O 3 ) and copper oxide (CuO or CU 2 O) are mixed with one another in such quantities that the composition desired in each case is achieved.
  • the mixture, formed from the oxides mentioned, is dry milled in a ball mill or an oscillating mill for at least one hour.
  • the powder mixture is then sintered for four hours at 1300 ° C., the desired mixed oxide compound having a pure perovskite structure or a perovskite spinel structure being formed by solid reactions.
  • the sinter cake is ground in a vibratory mill to a very fine-grained powder.
  • the desired powder should have a grain size between 0.1 and 5 ⁇ m.
  • the sinter cake is processed into the powder with the desired grain size to form a porous granulate with a diameter between 2 and 5 mm or to form porous honeycomb bodies.
  • an organic binder and possibly a blowing agent or a pore former are added to the fine-grained powder. All three conditions, for example, meet ammonium bicarbonate and polyethylene glycols.
  • a catalyst in the form of the porous granules with the desired diameter or in the form of the desired honeycomb body can be formed by pressing or extrusion.
  • a suspension is first formed from 50% by weight of the fine-grained powder, the preparation of which is described above.
  • a powder is preferably used which has a grain size between 0.1 and 5 ⁇ m. 7.5% by weight of ammonium carbonate or polyethylene glycols and 42.5% by weight of ethanol, which serves as a suspending agent, are added to this powder.
  • the weight data relate to the total weight of the suspension to be produced.
  • the amount of blowing agent and pore formers is chosen so large that pores with a diameter are present in the catalyst material. 0.1 to 0.5 ⁇ m are formed and at least 30% of the pores formed have this size.
  • the catalyst material 2 is applied to a ceramic carrier 3.
  • the carrier 3 can be made of fine-pored alpha alumina, cordierite or mullite. Other ceramic materials that meet the required conditions can also be used to form the support.
  • the carrier material must also have pores with a diameter of 6 to 7 ⁇ m. At least 50% of the pores should have this diameter.
  • the ceramic material must meet the condition that it is well compatible with the catalyst material 2.
  • the catalyst material 2 can be applied to the surface of the support by dipping or spraying from the suspension prepared above. By drying and heating in air, the suspension medium and the blowing agents are thermally decomposed. What remains is the fine-grained catalyst material 2. This is sintered onto the surface of the support 3 at 1200 ° C.
  • a ceramic support is not absolutely necessary. It only facilitates the attachment of the catalyst 1 to components (not shown here). At the same time, the carrier can protect the catalyst material against corrosive effects or prevent incompatibilities with materials of other components, since this avoids direct contact.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Biomedical Technology (AREA)
  • Environmental & Geological Engineering (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Catalysts (AREA)
  • Exhaust Gas Treatment By Means Of Catalyst (AREA)

Abstract

Un catalyseur (1) sert à éliminer des polluants contenus dans les gaz d'échappement d'usines d'incinération et de moteurs à combustion, par réduction des polluants avec du monoxyde de carbone, de l'hydrogène, des hydrocarbures ou de l'ammoniac. On utilise à cet effet un catalyseur (1) produit au moyen d'un système d'oxydes mixtes à phase unique ou multiple et une pure structure de perowskite ou une structure mixte de perowskite et de spinelle. Afin de produire le catalyseur, on mélange, sèche et moud, de façon à obtenir une poudre fine avec des grains de 0,1 à 5 mum, des carbonates ou des oxydes de lanthane, de strontium, de manganèse, de fer et de cuivre, puis on traite cette poudre afin d'obtenir une couche catalytiquement active.
EP89906302A 1987-12-10 1988-12-08 Catalyseur et son procede de production Ceased EP0344306A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19873741888 DE3741888A1 (de) 1987-12-10 1987-12-10 Katalysator und verfahren zu seiner herstellung
DE3741888 1987-12-10

Publications (1)

Publication Number Publication Date
EP0344306A1 true EP0344306A1 (fr) 1989-12-06

Family

ID=6342302

Family Applications (1)

Application Number Title Priority Date Filing Date
EP89906302A Ceased EP0344306A1 (fr) 1987-12-10 1988-12-08 Catalyseur et son procede de production

Country Status (5)

Country Link
US (1) US5093301A (fr)
EP (1) EP0344306A1 (fr)
JP (1) JPH02502444A (fr)
DE (1) DE3741888A1 (fr)
WO (1) WO1989005186A1 (fr)

Families Citing this family (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03161052A (ja) * 1989-11-17 1991-07-11 Matsushita Electric Ind Co Ltd 排気ガス浄化触媒体およびその製造方法
FR2665089B1 (fr) * 1990-07-25 1993-11-19 Stts Catalyseurs de post-combustion.
US5622680A (en) * 1990-07-25 1997-04-22 Specialites Et Techniques En Traitement De Surfaces-Stts Post-combustion catalysts
CN1022542C (zh) * 1990-07-26 1993-10-27 北京大学 钙钛矿型稀土复合氧化物燃烧催化剂
JP2838336B2 (ja) * 1991-09-12 1998-12-16 工業技術院長 窒素酸化物接触還元用触媒
US5380692A (en) * 1991-09-12 1995-01-10 Sakai Chemical Industry Co., Ltd. Catalyst for catalytic reduction of nitrogen oxide
FR2696109B1 (fr) * 1992-09-28 1994-11-04 Inst Francais Du Petrole Catalyseur d'oxydation et procédé d'oxydation partielle du méthane.
DE4242099A1 (de) * 1992-12-14 1994-06-16 Abb Patent Gmbh Vorrichtung, insbesondere Gasturbineneinrichtung, mit einer Beschichtung von Einrichtungsteilen
US5364517A (en) * 1993-02-19 1994-11-15 Chevron Research And Technology Company Perovskite-spinel FCC NOx reduction additive
US5403461A (en) * 1993-03-10 1995-04-04 Massachusetts Institute Of Technology Solid electrolyte-electrode system for an electrochemical cell
WO1997035928A1 (fr) * 1996-03-26 1997-10-02 Ferro Enamels (Japan) Limited Technique de fabrication d'un pigment inorganique
US6017504A (en) * 1998-07-16 2000-01-25 Universite Laval Process for synthesizing perovskites using high energy milling
US6328914B1 (en) * 1999-01-29 2001-12-11 Delphi Technologies, Inc. Thick-film paste with insoluble additive
IT1319198B1 (it) * 2000-10-11 2003-09-26 Sued Chemie Mt Srl Catalizzatori per ossidazione.
US7247598B2 (en) * 2002-07-23 2007-07-24 Beijing University Of Chemical Technology Nano-scale magnetic solid base catalyst and its preparation method
US20040024071A1 (en) * 2002-08-01 2004-02-05 Meier Paul F. Perovskite compositions and method of making and process of using such compositions
AU2003291044A1 (en) * 2002-11-15 2004-06-15 Battelle Memorial Institute Copper-substituted perovskite compositions for solid oxide fuel cell cathodes and oxygen reduction electrochemical devices
US20040214070A1 (en) * 2003-04-28 2004-10-28 Simner Steven P. Low sintering lanthanum ferrite materials for use as solid oxide fuel cell cathodes and oxygen reduction electrodes and other electrochemical devices
US8962518B2 (en) * 2009-03-17 2015-02-24 Nippon Shokubai Co., Ltd. Catalyst for production of hydrogen and process for producing hydrogen using the catalyst, and catalyst for combustion of ammonia, process for producing the catalyst and process for combusting ammonia using the catalyst
JP5822682B2 (ja) * 2011-11-25 2015-11-24 ダイハツ工業株式会社 排ガス浄化用触媒
EP2878368B1 (fr) * 2013-11-29 2019-05-22 Umicore Ag & Co. Kg Matériau de stockage de l'oxygène
EP2878359B1 (fr) * 2013-11-29 2016-04-13 Umicore Ag & Co. Kg Utilisation d'oxydes mixtes comme composants de stockage d'oxygène
FR3086282B1 (fr) * 2018-09-20 2020-09-25 Saint Gobain Ct Recherches Produit fondu polycristallin a base de brownmillerite
CN112740445B (zh) * 2018-09-27 2024-05-24 堺化学工业株式会社 固体氧化物型燃料电池空气极用粉体及其制造方法
IT202000011578A1 (it) * 2020-05-19 2021-11-19 Univ Degli Studi Di Bergamo Processo efficiente che utilizza la sinergia del sistema fenton e la fotocatalisi per la degradazione di inquinanti in acque reflue
CN111992211B (zh) * 2020-09-27 2023-04-28 宁夏共宣环保科技有限责任公司 一种核壳结构的脱硝催化剂及其制备方法和应用

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US3900428A (en) * 1971-10-19 1975-08-19 Heraeus Gmbh W C Catalyst for the reduction of nitric oxides
JPS521396B2 (fr) * 1972-08-25 1977-01-13
US3905918A (en) * 1972-09-16 1975-09-16 Heraeus Gmbh W C Catalyst for purifying exhaust gases
US3904553A (en) * 1973-08-20 1975-09-09 Corning Glass Works Thermally stable composite base metal oxide catalysts
US4055513A (en) * 1976-04-13 1977-10-25 Exxon Research & Engineering Co. Perovskite catalysts and process for their preparation
JPS58156350A (ja) * 1982-03-12 1983-09-17 Matsushita Electric Ind Co Ltd 排ガス浄化装置
CN1004992B (zh) * 1986-07-30 1989-08-16 北京工业大学 制备稀土金属复合氧化物/合金蜂窝体催化剂的方法

Non-Patent Citations (1)

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Title
See references of WO8905186A1 *

Also Published As

Publication number Publication date
US5093301A (en) 1992-03-03
DE3741888A1 (de) 1989-06-22
JPH02502444A (ja) 1990-08-09
WO1989005186A1 (fr) 1989-06-15

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