EP1113873A1 - Catalyseur ceramique de decomposition selective de n 2?o et procede permettant de le produire - Google Patents

Catalyseur ceramique de decomposition selective de n 2?o et procede permettant de le produire

Info

Publication number
EP1113873A1
EP1113873A1 EP99946074A EP99946074A EP1113873A1 EP 1113873 A1 EP1113873 A1 EP 1113873A1 EP 99946074 A EP99946074 A EP 99946074A EP 99946074 A EP99946074 A EP 99946074A EP 1113873 A1 EP1113873 A1 EP 1113873A1
Authority
EP
European Patent Office
Prior art keywords
mass
catalyst according
catalyst
active phase
alkaline earth
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.)
Withdrawn
Application number
EP99946074A
Other languages
German (de)
English (en)
Inventor
Wolfgang Burckhardt
Frank Seifert
Manfred Voigt
Georg Winterstein
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.)
Porzellanwerk Kloster Veilsdorf GmbH
Original Assignee
Porzellanwerk Kloster Veilsdorf GmbH
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 Porzellanwerk Kloster Veilsdorf GmbH filed Critical Porzellanwerk Kloster Veilsdorf GmbH
Publication of EP1113873A1 publication Critical patent/EP1113873A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/20—Nitrogen oxides; Oxyacids of nitrogen; Salts thereof
    • C01B21/24—Nitric oxide (NO)
    • C01B21/26—Preparation by catalytic or non-catalytic oxidation of ammonia
    • C01B21/265—Preparation by catalytic or non-catalytic oxidation of ammonia characterised by the catalyst
    • 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
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8621—Removing nitrogen compounds
    • B01D53/8625—Nitrogen oxides
    • B01D53/8628—Processes 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/10—Magnesium; Oxides or hydroxides thereof
    • 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
    • B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
    • 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
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/10—Capture or disposal of greenhouse gases of nitrous oxide (N2O)

Definitions

  • the invention relates to a ceramic catalyst for the selective decomposition of N2O (nitrous oxide) in a mixture of nitrous gases to N 2 and O 2 and a process for its production.
  • N2O nitrous oxide
  • N 2 O (laughing gas) is released in a wide variety of processes, such as in fluidized bed combustion plants and in processes for the chemical synthesis of nylon, adipic and nitric acid. Due to its inertia, it reaches the stratosphere undecomposed, where it contributes to the long-term damage to the earth's protective ozone layer. Therefore, at the World Environment Conference in Kyoto in 1997, requirements for the global emission reduction of this gas were laid down for the first time. This requires the use of suitable catalysts to treat the exhaust gas flows.
  • ceramic materials for example modified zeolites and mixed oxides with a perovskite structure, can be used as potential catalyst materials. Because of their price advantage over precious metals and their better temperature resistance, perovskite compounds are considered cheap.
  • Catal. Lett. (1995), 34 (3, 4) pp. 373-382 is described by N.
  • the previously known catalysts for the decomposition of N 2 O undergo an irreversible deactivation at temperatures above 700 ° C., which is caused by sintering processes (noble metal catalysts), by insufficient thermal stability of the framework structure (zeolites) or by irreversible reactions between the transition metal oxides of the active components with carrier materials, how such is caused with a high content of Al 2 O 3 .
  • a special feature of the use in the production of nitric acid lies in the required selectivity in relation to other oxides of nitrogen, one of which is the target product of the synthesis. Such selectivity is not required or even undesirable in other exhaust treatment processes.
  • the invention is therefore based on the object of providing a catalyst for the selective decomposition of N 2 O in a mixture of nitrous gases, which should be usable in the temperature range from 700 ° C. to at least 1000 ° C. without impairing its catalyst activity.
  • alkaline earth compounds for example clays or aluminosilicates
  • alkaline earth compounds in particular magnesium oxide
  • the catalyst prevents the catalyst from being deactivated by a chemical reaction between the active phase and the carrier material at temperatures above 700 ° C., as is the case in the prior art, for example Spinel formation takes place between the oxides of aluminum and cobalt.
  • various alkaline earth oxides themselves have a certain catalytic activity during nitrous oxide decomposition.
  • the alkaline earth oxide is produced, for example, by calcining a salt, preferably the carbonate, the calcining temperature depending on the resistance of the carbonate of the element in question, on the desired grain size of the alkaline earth oxide and on the subsequent operating temperature of the catalyst.
  • the oxides and mixed oxides of the catalytically active component are preferably produced wet-chemically by mixed precipitation, drying and thermal decomposition of the drying products.
  • Alternative processes are the production by means of a solid-state reaction at high temperatures, pyrolytic processes and all other known processes for powder production.
  • the active components can be added in the form of precursor compounds (salts), oxides or mixed oxides before or after the calcination of the carrier material.
  • precursor compounds salts
  • oxides oxides
  • mixed oxides oxides
  • the mixtures mentioned are plasticized and homogenized with the addition of suitable plasticizing aids and water, as is known in ceramic production.
  • Strength-increasing binders such as, for example, silica sols, inorganic polymers, for example in the form of magnesium, aluminum or boron phosphates or binders, can be added, the proportion of which should be kept as low as possible, provided it is not an alkaline earth compound.
  • These strength-increasing binders can be mixed in homogeneously before or after the calcination of the alkaline earth metal salt. Completion takes place according to the known ceramic processes, such as granulation or extrusion. Subsequent debinding and sintering can produce catalyst elements in the form of granules, bulk material or honeycomb bodies.
  • Fig. 2 the selectivity of the catalyst of Fig. 1 over NO x also as a function of temperature.
  • Fig. 4 the selectivity of the catalyst of Fig. 3 over NO x also as a function of temperature.
  • Fig. 6 the selectivity of the catalyst of Fig. 5 over NO x also as a function of temperature.
  • a catalyst according to the invention in granular form was made from 2000 vol. ⁇ Ppm N 2 O; using a test gas emulated from the process gas of nitric acid production; 9.0 vol% NO, 6.0 vol% O 2 ; 0.14 vol% H 2 O; Rest N 2 tested.
  • the active phase consists of a heavy metal catalyst with the main components Mn, Fe, Cr and Co.
  • the active phase is a lanthanum-strontium-manganese-cobalt-perovskite.
  • the alkaline earth compounds for the carrier material are mixed with 15% by mass of an SiO 2 sol with an SiO 2 content of 13%. After the firing customary in ceramic technology, the SiO 2 content of the ceramic carrier material with good strength values is 1.95% by mass.
  • the alkaline earth compounds for the carrier material are mixed with 14% by mass of a magnesium phosphate, which contains, inter alia, 6% MgO and 37% P 2 O 5 .
  • a magnesium phosphate which contains, inter alia, 6% MgO and 37% P 2 O 5 .
  • the MgO content of a ceramic carrier material essentially consists of CaO 0.84% by mass or, if the carrier material consists essentially of MgO, its proportion is increased by the same percentage.
  • the alkaline earth compounds for the carrier material become one with 12 mass%
  • Magnesium phosphates which contains 8% Al 2 O 3 and 35% P 2 O 5 , among others. After firing, the Al 2 O 3 content of the ceramic carrier material is 0.96
  • the alkaline earth compounds for the carrier material are mixed with 8% by mass of a boron phosphate, which contains, inter alia, 36% B 2 O 3 and 57% P 2 O 5 . After firing, the B 2 O 3 content of the ceramic carrier material is 2.9% by mass.
  • the alkaline earth compounds for the carrier material are 5.5% by mass
  • Alumina precursor consisting of 85% Al 2 O 3 and 15% H 2 O, added. After firing, the Al 2 O 3 content of the ceramic carrier material is 4.7 mass%.
  • the alkaline earth compounds for the carrier material are mixed with 5% by mass of a polymeric magnesium silicate, which contains, inter alia, 23.7% by mass of MgO and 57% by mass of SiO 2 .
  • a polymeric magnesium silicate which contains, inter alia, 23.7% by mass of MgO and 57% by mass of SiO 2 .
  • the MgO content of a ceramic carrier material consisting essentially of CaO is 1.2% by mass of MgO and 2.85% by mass of SiO 2, or if the carrier material consists essentially of MgO, the proportion thereof is around the mentioned Percentage increased.

Landscapes

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

Abstract

L'invention vise à mettre au point un catalyseur de décomposition sélective de N2O dans un mélange de gaz nitrosés, devant pouvoir être utilisé dans une plage de températures allant de 700 à au moins 1000 DEG C, sans que son activité ne s'en trouve altérée. A cet effet, le catalyseur consiste en un matériau support céramique poreux et en une phase à activité catalytique, le matériau support se composant à au moins 95 % en masse d'un ou de plusieurs composé(s) alcalino-terreux. Ce catalyseur s'utilise de préférence dans la préparation d'acide azotique.
EP99946074A 1998-09-09 1999-08-31 Catalyseur ceramique de decomposition selective de n 2?o et procede permettant de le produire Withdrawn EP1113873A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE1998141740 DE19841740A1 (de) 1998-09-09 1998-09-09 Keramischer Katalysator zur selektiven Zersetzung von N2O und Verfahren zu dessen Herstellung
DE19841740 1998-09-09
PCT/EP1999/006392 WO2000013789A1 (fr) 1998-09-09 1999-08-31 Catalyseur ceramique de decomposition selective de n2o et procede permettant de le produire

Publications (1)

Publication Number Publication Date
EP1113873A1 true EP1113873A1 (fr) 2001-07-11

Family

ID=7880714

Family Applications (1)

Application Number Title Priority Date Filing Date
EP99946074A Withdrawn EP1113873A1 (fr) 1998-09-09 1999-08-31 Catalyseur ceramique de decomposition selective de n 2?o et procede permettant de le produire

Country Status (6)

Country Link
EP (1) EP1113873A1 (fr)
AU (1) AU5857199A (fr)
BR (1) BR9912871A (fr)
DE (1) DE19841740A1 (fr)
RU (1) RU2221642C2 (fr)
WO (1) WO2000013789A1 (fr)

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10006103A1 (de) 2000-02-11 2001-08-16 Krupp Uhde Gmbh Katalysator zum Abbau von N¶2¶O, dessen Verwendung bei der Salpetersäureproduktion sowie Verfahren zu seiner Herstellung
DE10011738A1 (de) * 2000-03-13 2002-03-28 Porzellanwerk Kloster Veilsdor Keramischer Katalysatorformkörper und Verfahren zur Herstellung solcher Katalysatorformkörper
GB0315643D0 (en) * 2003-04-29 2003-08-13 Johnson Matthey Plc Improved catalyst charge design
US8178068B2 (en) 2003-04-29 2012-05-15 Johnson Matthey Plc Catalyst charge design
DE102007038711A1 (de) 2007-08-14 2009-02-19 Uhde Gmbh Katalysator, Verfahren zu dessen Herstellung und dessen Verwendung
FR2922543B1 (fr) * 2007-10-18 2011-10-14 Commissariat Energie Atomique Procede de preparation d'un geopolymere a porosite controlee, le geopolymere ainsi obtenu et ses differentes applications
DE502008001533D1 (de) 2008-07-16 2010-11-25 Umicore Ag & Co Kg Katalysator zur Umsetzung von Distickstoffmonoxid und seine Verwendung bei der industriellen Salpetersäureherstellung
GB0819094D0 (en) 2008-10-20 2008-11-26 Johnson Matthey Plc Catalyst containment unit
PL388518A1 (pl) 2009-07-10 2011-01-17 Instytut Nawozów Sztucznych Katalizator do wysokotemperaturowego rozkładu podtlenku azotu
DE102010005105A1 (de) 2010-01-19 2011-07-21 Umicore AG & Co. KG, 63457 Katalysator
PL237044B1 (pl) 2015-03-13 2021-03-08 Inst Nowych Syntez Chemicznych Nośnikowy katalizator do redukcji emisji tlenku azotu(I) z instalacji kwasu azotowego oraz sposób jego wytwarzania
CN106390710A (zh) * 2016-06-14 2017-02-15 东莞市联洲知识产权运营管理有限公司 一种高效中低温焦炉烟道废气脱硫脱硝工艺
CN115501741B (zh) * 2022-08-30 2023-11-03 四川轻化工大学 一种基于改性载体的高活性氧化铁脱硫剂及其制备方法和应用

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1451091A (en) * 1973-10-04 1976-09-29 Teijin Ltd Preparation of 2,4,6-trimethylphenol
JPS5390184A (en) * 1977-01-21 1978-08-08 Mitsubishi Heavy Ind Ltd Production of exhaust gas treatment catalyst
JPS5853571B2 (ja) * 1977-03-26 1983-11-30 宇部興産株式会社 排煙脱硝用触媒担体の製造方法
DE4000692A1 (de) * 1990-01-12 1991-07-18 Henkel Kgaa Verwendung von kolloidalem kieselsaeuresol als hilfsstoff fuer katalysatoren
JPH0639282A (ja) * 1992-07-27 1994-02-15 Hitachi Ltd 窒素酸化物の分解触媒、それを用いた分解方法及び排ガス浄化装置
JPH07171346A (ja) * 1993-12-22 1995-07-11 Yuichi Murakami 亜酸化窒素の除去方法
US5705136A (en) * 1995-11-13 1998-01-06 University Of Florida Research Foundation, Inc. Catalyzed decomposition of nitrogen oxides on metal oxide supports

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0013789A1 *

Also Published As

Publication number Publication date
BR9912871A (pt) 2001-10-16
WO2000013789A8 (fr) 2000-07-27
AU5857199A (en) 2000-03-27
RU2221642C2 (ru) 2004-01-20
WO2000013789A1 (fr) 2000-03-16
DE19841740A1 (de) 2000-03-16

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