WO1995005236A1 - Utilisation de catalyseurs de denitruration usages pour reduire l'emission de produits chlororganiques de combustion incomplete - Google Patents

Utilisation de catalyseurs de denitruration usages pour reduire l'emission de produits chlororganiques de combustion incomplete Download PDF

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Publication number
WO1995005236A1
WO1995005236A1 PCT/EP1994/002728 EP9402728W WO9505236A1 WO 1995005236 A1 WO1995005236 A1 WO 1995005236A1 EP 9402728 W EP9402728 W EP 9402728W WO 9505236 A1 WO9505236 A1 WO 9505236A1
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WIPO (PCT)
Prior art keywords
catalysts
catalyst
deno
emission
products
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Ceased
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PCT/EP1994/002728
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German (de)
English (en)
Inventor
Peter Dransfeld
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BASF SE
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BASF SE
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Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of WO1995005236A1 publication Critical patent/WO1995005236A1/fr
Anticipated expiration legal-status Critical
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    • 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
    • B01D53/8659—Removing halogens or halogen compounds
    • B01D53/8662—Organic halogen compounds

Definitions

  • the invention relates to the use of spent DeNO x - or modified used DeNO x catalysts in a process for reducing the emission of chlorinated organic products • incomplete combustion in waste gases of incineration plants by treatment of chlorinated organic products containing exhaust gases, in particular polyhalogenated dibenzodioxins and polyhalogenated benzofurans containing Exhaust gases at a temperature of 150 to 500 ° C under oxidative conditions.
  • PIC Products of Incomplete Combustion
  • organohalogen compounds chlorobenzenes, chlorophenols, polychlorinated biphenyls, polyhalogenated (chlorine, bromine) dibenzodioxins and dibenzofurans etc.
  • These compounds are toxic, are extremely difficult to degrade and are therefore harmful to the environment, with late damage in particular being feared.
  • the polyhalogenated dibenzodioxins and dibenzofurans (hereinafter collectively and briefly referred to as "dioxins”) are of particular importance with regard to the potential health risk of emissions from incineration plants.
  • DeNO ⁇ catalysts have been known for a long time and are used for the catalytic reduction of nitrogen oxides NO x with ammonia in nitric acid plants and large combustion plants.
  • the DeNO x catalysts and their manufacture are described, for example, in VDI Report No. 730, 1989, pages 121 to 156, and in
  • DeNO x catalysts of the titanium oxide type, iron oxide or zeolite type, which may contain conventional donors, are particularly suitable. Titanium oxide catalysts are preferred, in particular those with a titanium oxide content of> 70% by weight, based on the total weight of the catalyst.
  • DeNO x catalysts ie exhausted for denitrification, are still well suited for the oxidative destruction of halogenated aromatic compounds.
  • the invention relates to the use of deNO x catalysts deactivated with respect to NO x reduction for the removal of halogenated aromatic compounds in exhaust gases under the conditions of the process of PCT application WO 91/04780, to which reference is hereby made.
  • the old catalysts can either be used directly or used after pretreatment. Depending on the task and condition of the old catalyst, the catalyst can be washed, etched or sandblasted. The old catalyst can also be comminuted with the purpose of using it, for example, as a packed bed, fluidized bed or filter auxiliary layer catalyst. The shredded old catalytic converter can also be used as a raw material for the production of new - less active - honeycomb bodies. The shredding increases the specific DeNO x activity again because less poisoned material is exposed, but the original specific activity is not achieved again.
  • honeycomb catalysts come into consideration, e.g. those of titanium dioxide type, iron oxide type or zeolite type.
  • donors e.g. Tungsten oxide, molybdenum oxide and / or vanadium oxide to name.
  • the amount of donors is generally 0.5 to 20 wt .-%, based on the total weight of the catalyst. Catalysts with a content of 70 to 95% by weight Ti0, 2 to 10% by weight WO 3 , 0.5 to 5% by weight V 2 Os are preferred, in each case based on the total weight of the catalyst, where appropriate the The rest of the usual auxiliaries such as fillers, for example glass fibers, clay or possibly SO 4 .
  • the removal of the organochlorine compounds takes place in a known manner under oxidative conditions.
  • the process is therefore carried out in such a way that sufficient oxygen is present so that the oxygen sorption outweighs the sorption of possibly added reducing substances such as NH 3 , CH 4 or HS, for example 0 6%, NH 3 ⁇ 30 ppm,. It is preferable to work at a 0 content of 0.5 to 21, in particular 6 to 12% by volume.
  • a honeycomb-shaped catalyst based on Ti0 2 with vanadium and tungsten doping composition
  • Flue gas from a special waste incineration plant flowed through it at a temperature of 320 ° C. In the first half of the Oxidized conditions prevailed due to the oxygen present in the flue gas. Then enough NH 3 was added to the flue gas that nitrogen oxides were reduced on the catalyst in the second half.
  • the catalyst was operated at a space velocity of typically 2000 / h for a period of about 2 years.
  • FIG. 1 shows the course of the ratio of current activity through initial activity with regard to the reduction in NO x (curve 1) and dioxin (curve 2) plotted over the operating time in hours as the abscissa.
  • the activity A was calculated from the concentrations present in the gas stream before (Cgin) and after the catalyst bed (C Aus ), which were determined using customary methods
  • t is the residence time of the gas in the corresponding catalyst bed.

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

Abstract

L'invention concerne l'utilisation de catalyseurs de dénitruration désactivés au niveau de leur pouvoir réducteur de NOx, afin de diminuer l'émission de produits chlororganiques de combustion incomplète contenus dans des gaz d'échappement, dans des conditions d'oxydation comprises entre 150 et 500 °C.
PCT/EP1994/002728 1993-08-18 1994-08-16 Utilisation de catalyseurs de denitruration usages pour reduire l'emission de produits chlororganiques de combustion incomplete Ceased WO1995005236A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19934327691 DE4327691A1 (de) 1993-08-18 1993-08-18 Verwendung von gebrauchten Katalysatoren der NO¶x¶-Entfernung zur Verringerung der Emission von chlororganischen Produkten unvollständiger Verbrennung
DEP4327691.1 1993-08-18

Publications (1)

Publication Number Publication Date
WO1995005236A1 true WO1995005236A1 (fr) 1995-02-23

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1994/002728 Ceased WO1995005236A1 (fr) 1993-08-18 1994-08-16 Utilisation de catalyseurs de denitruration usages pour reduire l'emission de produits chlororganiques de combustion incomplete

Country Status (2)

Country Link
DE (1) DE4327691A1 (fr)
WO (1) WO1995005236A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999013970A1 (fr) * 1997-09-16 1999-03-25 Siemens Aktiengesellschaft Procede de recyclage de catalyseurs usages

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SU912673A1 (ru) * 1980-03-17 1982-03-15 Волгоградский Политехнический Институт Способ очистки сточных вод от органических соединений
EP0240064A1 (fr) * 1986-03-27 1987-10-07 Shell Internationale Researchmaatschappij B.V. Procédé pour éliminer des TiCl4-vapeurs dans des courants gazeux
WO1991004780A1 (fr) * 1989-10-06 1991-04-18 Babcock Deutsche Babcock Anlagen Ag Procede de reduction des emissions de produits organiques d'une combustion incomplete
DE4013720A1 (de) * 1990-04-28 1991-10-31 Huels Chemische Werke Ag Verfahren zur verwertung von gebrauchten denox-katalysatoren
JPH04110038A (ja) * 1990-08-31 1992-04-10 Mitsubishi Heavy Ind Ltd 窒素酸化物除去用触媒
EP0556717A1 (fr) * 1992-02-14 1993-08-25 Hüls Aktiengesellschaft Elimination de fluor ou de composés anorganiques de fluor de gaz utilisant des catalyseurs TiO2 usés

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SU912673A1 (ru) * 1980-03-17 1982-03-15 Волгоградский Политехнический Институт Способ очистки сточных вод от органических соединений
EP0240064A1 (fr) * 1986-03-27 1987-10-07 Shell Internationale Researchmaatschappij B.V. Procédé pour éliminer des TiCl4-vapeurs dans des courants gazeux
WO1991004780A1 (fr) * 1989-10-06 1991-04-18 Babcock Deutsche Babcock Anlagen Ag Procede de reduction des emissions de produits organiques d'une combustion incomplete
DE4013720A1 (de) * 1990-04-28 1991-10-31 Huels Chemische Werke Ag Verfahren zur verwertung von gebrauchten denox-katalysatoren
JPH04110038A (ja) * 1990-08-31 1992-04-10 Mitsubishi Heavy Ind Ltd 窒素酸化物除去用触媒
EP0556717A1 (fr) * 1992-02-14 1993-08-25 Hüls Aktiengesellschaft Elimination de fluor ou de composés anorganiques de fluor de gaz utilisant des catalyseurs TiO2 usés

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 8303, Derwent World Patents Index; Class A25, AN 83-06852K *
DATABASE WPI Section Ch Week 9221, Derwent World Patents Index; Class E36, AN 92-172419 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999013970A1 (fr) * 1997-09-16 1999-03-25 Siemens Aktiengesellschaft Procede de recyclage de catalyseurs usages
EP0908220A1 (fr) * 1997-09-16 1999-04-14 Siemens Aktiengesellschaft Procédé d'utilisation de catalysateur usé

Also Published As

Publication number Publication date
DE4327691A1 (de) 1995-03-02

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