WO1999001203A1 - Procede de fabrication de catalyseurs a grains fins a partir de zeolithe naturel - Google Patents

Procede de fabrication de catalyseurs a grains fins a partir de zeolithe naturel Download PDF

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Publication number
WO1999001203A1
WO1999001203A1 PCT/EP1998/004119 EP9804119W WO9901203A1 WO 1999001203 A1 WO1999001203 A1 WO 1999001203A1 EP 9804119 W EP9804119 W EP 9804119W WO 9901203 A1 WO9901203 A1 WO 9901203A1
Authority
WO
WIPO (PCT)
Prior art keywords
ions
aqueous suspension
cation exchange
naturally occurring
zeolite
Prior art date
Application number
PCT/EP1998/004119
Other languages
German (de)
English (en)
Inventor
Gurudas Samant
Hansjörg Herden
Gernot Mayer-Schwinning
Original Assignee
Metallgesellschaft Aktiengesellschaft
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 Metallgesellschaft Aktiengesellschaft filed Critical Metallgesellschaft Aktiengesellschaft
Priority to AU89731/98A priority Critical patent/AU8973198A/en
Publication of WO1999001203A1 publication Critical patent/WO1999001203A1/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
    • B01J29/00—Catalysts comprising molecular sieves
    • 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

Definitions

  • the invention relates to a method for producing fine-grained catalysts from naturally occurring zeolite for the catalytic reduction of nitrogen oxides contained in oxygen-containing exhaust gases from combustion devices in a suspension reactor.
  • DE-PS 3 912 596 describes a process for producing a catalyst for exhaust gas purification with a copper-containing synthetic zeolite.
  • the production takes place by an ion exchange in which a refractory support coated with the zeolite is immersed for the ion exchange in a mixed solution of a copper carboxylate and ammonia.
  • Catalyst produced in this way is intended for the use of automobile exhaust gases.
  • the high costs of synthetic zeolites are disadvantageous. Use in large-scale combustion facilities is inefficient.
  • a method for producing a catalyst for the purification of gases and exhaust gases of NO x with ammonia and / or urea as a reducing agent is known using copper-containing synthetic zeolite.
  • the hydrophobic dealuminated Y-type zeolite is treated with an aqueous solution of a copper compound, in particular copper chloride, and the moist zeolite is dried at from 110 to 200 ° C.
  • the copper content is up to 20%.
  • the disadvantage of a catalyst produced in this way is that the copper salt on the surface of the zeolite is rubbed off and discharged from the reaction space.
  • the invention has for its object to provide a process for the production of fine-grained catalysts from naturally occurring zeolite, with which a high denitrification performance can be achieved, in which the catalytic substance remains firmly connected to the zeolite and thus a constant denitrification performance is ensured.
  • the object on which the invention is based is achieved in that the hydrogen ions and / or alkali metal and / or alkaline earth metal ions present as compensation ions in naturally occurring zeolite in the lattice partially or completely by cation exchange in an aqueous suspension by ions of Fe and / or Cu and / or Mn and / or V and / or Cr and / or Ni and / or Co and / or Zn and / or Mo and / or Nb and / or W can be replaced.
  • the metal ions are incorporated into the lattice of the zeolite. It has surprisingly been found that the incorporation of these metal ions by cation exchange in natural zeolite is possible in an advantageous manner, so that the catalysts have a high denitrification performance, particularly in a suspension reactor.
  • the process is simple and, because of the inexpensive, naturally occurring zeolites, can be carried out economically and economically.
  • a preferred embodiment of the invention is that mordenite is used as the naturally occurring zeolite.
  • mordenite enables simple and quick cation exchange of the contaminants present in the lattice due to metal ions.
  • the cation exchange can be realized relatively quickly and completely.
  • the molar ratio of Si0 2 to A1 2 0 3 of the mordenite is in the range from 2 to 10. This measure has an advantageous effect on the denitrification performance of the catalyst.
  • the naturally occurring zeolite consists of 10 to 20% by weight mordenite, 60 to 70% by weight clinoptilolite, 0 to 5% by weight montmorillonite, the rest Si0 2 and iron.
  • Zeolite with these components can be used in a particularly advantageous manner as a denitrification catalyst.
  • the suspension is treated with liquid or gaseous ammonia compounds and / or ammonia before the cation exchange.
  • ammonium chloride or ammonium sulfate are used as ammonia compounds.
  • the pretreatment with ammonia and / or ammonia compounds facilitates the incorporation of the metal ions into the zeolite lattice during the cation exchange.
  • the cation exchange can advantageously take place in a short time.
  • the cation exchange is carried out at a temperature of the aqueous suspension of 10 to 50 ° C., which enables a relatively simple incorporation of the metal ions into the zeolite lattice in a relatively short time.
  • the cation exchange is carried out by stirring in the aqueous suspension for 2 to 24 hours, the metal ions of Fe and / or Cu and / or Mn and / or V and / or Cr and / or Ni and / or Co and / or Zn and / or Mo and / or Nb and / or W and the ions of the ammonia compounds in the form of their chlorides, sulfates, nitrates or other soluble salts.
  • the naturally occurring zeolite catalysts produced by this process have a relatively high denitrification performance.
  • a molar ratio of alkali ions to introduced metal ions of 0.1 to 10 is set in the suspension. By setting this molar ratio, the consumption of the chemicals necessary for the cation exchange can be reduced.
  • a molar ratio of sodium and / or potassium ions to introduced metal ions of 1 to 5 is set in the aqueous suspension. This measure also has an advantageous effect on the consumption of chemicals during cation exchange.
  • an average particle size for the catalyst has become so d ⁇ 0.2 mm, preferably from 5 microns to 50 proved.

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

Abstract

Le procédé consiste à fabriquer des catalyseurs à grains fins à base de zéolithe naturel, destinés à effectuer la réduction catalytique d'oxydes d'azote pour réacteurs à combustible en suspension. Selon ce procédé, les ions hydrogène et/ou les métaux alcalins et/ou les métaux alcalino-terreux que l'on trouve dans les zéolithes existant à l'état naturel sont remplacés partiellement ou entièrement, par échange d'ions dans une suspension aqueuse, par des ions de Fe et/ou de Cu et/ou de Mn et/ou de V et/ou de Cr et/ou de Ni et/ou de Co et/ou de Zn et/ou de Mo et/ou de Nb et/ou de W.
PCT/EP1998/004119 1997-07-04 1998-07-03 Procede de fabrication de catalyseurs a grains fins a partir de zeolithe naturel WO1999001203A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU89731/98A AU8973198A (en) 1997-07-04 1998-07-03 Method for producing fine-grained catalysts from natural zeolite

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE1997128701 DE19728701A1 (de) 1997-07-04 1997-07-04 Verfahren zur Herstellung feinkörniger Katalysatoren aus natürlich vorkommendem Zeolith
DE19728701.8 1997-07-04

Publications (1)

Publication Number Publication Date
WO1999001203A1 true WO1999001203A1 (fr) 1999-01-14

Family

ID=7834711

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1998/004119 WO1999001203A1 (fr) 1997-07-04 1998-07-03 Procede de fabrication de catalyseurs a grains fins a partir de zeolithe naturel

Country Status (3)

Country Link
AU (1) AU8973198A (fr)
DE (1) DE19728701A1 (fr)
WO (1) WO1999001203A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6835687B2 (en) 2000-04-20 2004-12-28 Bayer Aktiengesellschaft Method for producing double metal cyanide (DMC) catalysts
CN114072222A (zh) * 2018-08-31 2022-02-18 庄信万丰股份有限公司 用于选择性催化还原的双金属Cu/Mn催化剂

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113368865B (zh) * 2021-06-08 2022-12-02 中国科学院山西煤炭化学研究所 脱硝催化剂及其制备方法和废气脱硝方法

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2411853A1 (de) * 1973-03-13 1974-09-19 Us Atomic Energy Commission Wa Verfahren zur katalytischen reduktion von stickstoffoxyden
US4046888A (en) * 1975-06-12 1977-09-06 Toa Nenryo Kogyo Kabushiki Kaisha Methods for catalytic reduction of nitrogen oxides
US4571329A (en) * 1984-08-13 1986-02-18 Babcock-Hitachi Kabushiki Kaisha Ammonia reduction-denitration process and apparatus therefor
US4735927A (en) * 1985-10-22 1988-04-05 Norton Company Catalyst for the reduction of oxides of nitrogen
US5270024A (en) * 1989-08-31 1993-12-14 Tosoh Corporation Process for reducing nitrogen oxides from exhaust gas
US5433933A (en) * 1989-12-21 1995-07-18 Toyota Jidosha Kabushiki Kaisha Method of purifying oxygen-excess exhaust gas
US5543125A (en) * 1994-02-15 1996-08-06 Tokyo Gas Co., Ltd. Method of purifying non-containing exhaust gases using iron containing mordenite

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3379640A (en) * 1966-01-24 1968-04-23 Mobil Oil Corp Selective catalytic conversion with a crystalline aluminosilicate
DE3841990A1 (de) * 1988-12-14 1990-06-21 Degussa Verfahren zur reduktion von stickoxiden aus abgasen

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2411853A1 (de) * 1973-03-13 1974-09-19 Us Atomic Energy Commission Wa Verfahren zur katalytischen reduktion von stickstoffoxyden
US4046888A (en) * 1975-06-12 1977-09-06 Toa Nenryo Kogyo Kabushiki Kaisha Methods for catalytic reduction of nitrogen oxides
US4571329A (en) * 1984-08-13 1986-02-18 Babcock-Hitachi Kabushiki Kaisha Ammonia reduction-denitration process and apparatus therefor
US4735927A (en) * 1985-10-22 1988-04-05 Norton Company Catalyst for the reduction of oxides of nitrogen
US5270024A (en) * 1989-08-31 1993-12-14 Tosoh Corporation Process for reducing nitrogen oxides from exhaust gas
US5433933A (en) * 1989-12-21 1995-07-18 Toyota Jidosha Kabushiki Kaisha Method of purifying oxygen-excess exhaust gas
US5543125A (en) * 1994-02-15 1996-08-06 Tokyo Gas Co., Ltd. Method of purifying non-containing exhaust gases using iron containing mordenite

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6835687B2 (en) 2000-04-20 2004-12-28 Bayer Aktiengesellschaft Method for producing double metal cyanide (DMC) catalysts
CN114072222A (zh) * 2018-08-31 2022-02-18 庄信万丰股份有限公司 用于选择性催化还原的双金属Cu/Mn催化剂

Also Published As

Publication number Publication date
DE19728701A1 (de) 1999-01-07
AU8973198A (en) 1999-01-25

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