EP0809531A1 - Procede de traitement catalytique de fumees - Google Patents

Procede de traitement catalytique de fumees

Info

Publication number
EP0809531A1
EP0809531A1 EP96902886A EP96902886A EP0809531A1 EP 0809531 A1 EP0809531 A1 EP 0809531A1 EP 96902886 A EP96902886 A EP 96902886A EP 96902886 A EP96902886 A EP 96902886A EP 0809531 A1 EP0809531 A1 EP 0809531A1
Authority
EP
European Patent Office
Prior art keywords
catalyst
flue gas
calcium aluminate
honeycomb
temperature
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Withdrawn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
EP96902886A
Other languages
German (de)
English (en)
Inventor
Siegfried Nowak
Heinrich Klare
Dagmar Sittig
Freimut J. Marold
Manfred Voigt
Karl H. Schugarcz
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.)
Uve Institut fur Technische Chemie und Umweltschutz GmbH
Original Assignee
Uve Institut fur Technische Chemie und Umweltschutz 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 Uve Institut fur Technische Chemie und Umweltschutz GmbH filed Critical Uve Institut fur Technische Chemie und Umweltschutz GmbH
Publication of EP0809531A1 publication Critical patent/EP0809531A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • B01J35/56—
    • 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
    • B01D53/864—Removing carbon monoxide or hydrocarbons
    • 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
    • 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
    • B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
    • 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
    • B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
    • 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

  • the invention relates to a process for the catalytic oxidation of organic pollutants in flue gases of various origins and compositions in the presence of water vapor.
  • Thermal, physico-chemical and biological processes are used to remove organic pollutants and products of different compositions and origins.
  • the total catalytic oxidation is already being carried out on a large scale with precious metal catalysts for motor vehicle exhaust gases;
  • the precious metal catalysts used for this require a temperature level below 600 * C as well as sulfur and metal-free combustion gases.
  • catalysts are used essentially for the denitrification namely to accelerate the reaction of Ammo ⁇ niak with nitrogen oxides to nitrogen and water, which are usually used C after the dust removal, and partly also to the flue gas scrubber in the temperature range of 400 *.
  • honeycomb bodies e.g. made of titanium dioxide with a coating of vanadium or tungsten oxides.
  • oxides of cobalt and nickel is also known.
  • the invention is based on the object of developing a simple and technically applicable process for converting hydrocarbons contained in the uncleaned flue gas with the aid of a catalyst and with an energetically favorable reaction procedure.
  • the process according to the invention for the catalytic treatment of flue gases is characterized in that a honeycomb shaped body with a sieve structure, the honeycombs of which consist of a modified or unmodified calcium aluminate as a catalyst, is arranged immediately after the combustion chamber in an uncleaned flue gas stream, the flue gas being at a temperature of in the range of 400 to 1300 * C and the residence time in the honeycomb molding is 0.2 to 3 seconds.
  • This arrangement of the catalyst avoids the formation of dioxins and realizes a more technically and energetically more favorable reaction procedure.
  • the direct use of the catalyst directly in the flue gas stream after combustion processes and in the presence of water vapor requires a robust, thermostable, compared to hetero element compounds and Aggressive substances arising from the combustion process are resistant to catalysts which maintain their catalytic action even in the presence of dust particles contained in flue gases.
  • cement-containing catalysts For the conversion of CO and other hydrocarbons, cement-containing catalysts have also been recommended at high temperatures for cleaning various exhaust gases, but these are only used in "pure" oxidation processes which are not accompanied by any dust formation.
  • the previously known application of these catalysts is carried out solely in the form of strands or spheres which do not permit the conversion of dust-containing flue gases due to the risk of growth and clogging which lead to the shutdown of the processes.
  • honeycomb molded body with a defined sieve structure while tolerating a certain dust content in the flue gas, ensures the catalytic effectiveness of the molded body and the direct conversion of residual hydrocarbons into unpurified flue gases.
  • the essence of the invention therefore consists in the use of a highly temperature-resistant, steam-resistant and catalytically active honeycomb molded body which is resistant to hetero-element compounds, which is arranged directly in the flue gas stream using the temperature conditions prevailing there and a total conversion of those still contained in the flue gas burned hydrocarbons are realized in such a way that the material basis is removed from the De Novo synthesis.
  • the catalyst or honeycomb shaped body consists of a calcium aluminate modified with different promoters, which preferably contains the phases C 12 A 7 and C 3 A active for the intended reaction, and via the catalytic, thermal described and physico-chemical properties disposes.
  • honeycomb body made of calcium aluminates not previously known with this catalytic effect and its use for the direct conversion of a flue gas loaded with dust particles leads to technologically and economically more advantageous solutions than with known conventional combustion plants (saving of process steps or simpler design of the same).
  • the catalyst consists of a weight ratio of CaO: ⁇ -Al 2 03 of preferably 30:70.
  • the calcium aluminate support with elements from sub-groups V to VIII of the periodic system of the elements, in particular V, Ni, Mn and Mo , in a concentration between 0.2 - 10%, preferably up to 5%, in particular with 1% by weight, the bifunctional effect of the catalyst - the total oxidation or the thermal-catalytic cleavage of the hydrocarbons and the acceleration of the water gas crack tion - varied and greatly increased.
  • the water gas reaction which preferably takes place under certain conditions also leads to complete cleavage of aliphatic and aromatic hydrocarbon structures.
  • the gasification of coke and gum deposits on the catalytic converter is promoted, thereby achieving high long-term activity of the catalytic converter.
  • the method according to the invention can be used for the purification of waste gases from waste oil, the special waste incineration of hospital waste, solvents, chlorine and metal-containing waste from the metalworking industry and others where there is a risk of dioxin regression if combustion is incomplete;
  • honeycomb molded body is produced using customary techniques for the production of honeycomb shaped bodies, it being possible, for example, to use calcium carbonate and aluminum oxide as starting products for the calcium aluminate, which are formed, dried, and fired after slurrying with the addition of conventional auxiliaries to the shaped bodies if in compliance with intermediate temperature levels.
  • the passage openings in the honeycomb shaped body are l x l to 10 x 10 mm. Passage openings smaller than 1 mm are not expedient because of the possibility of clogging by dust components in the flue gas, but in the case of a particularly low-dust flue gas it is also possible to work with smaller openings. Openings larger than 10 mm are not practical due to the insufficient catalytic reaction given the short residence times.
  • the openings can be rectangular, square or hexagonal.
  • Fluid are understood to mean all exhaust gases from combustion processes.
  • the honeycomb molded body can be arranged as a battery of several molded bodies both horizontally and vertically and in inclined directions according to the combustion chamber in accordance with the respective spatial conditions. It is expedient if a plurality of shaped bodies are arranged in a form-fitting manner horizontally and / or vertically and / or inclined to Arrange the flue gas direction one above the other, side by side and / or one behind the other in a size or number sufficient for catalytic cleaning.
  • the actual configuration can easily be determined for the person skilled in this field depending on the amount and type of the harmful components to be removed from the fuel / flue gas and the selection of the corresponding catalyst (doping).
  • Fig. 1 shows the honeycomb shaped body in section
  • results presented in the following examples come from laboratory apparatus, which essentially consists of a preheating zone and the subsequent combustion zone / catalyst zone.
  • the gaseous reaction product obtained after cooling and condensation was examined by gas chromatography and by coupling GC and mass spectrometry.
  • catalysts of the following composition were used
  • Table 2 shows the results and shows that with increasing temperature over time (Example 2: 750-800 * C, 4 hours; Example 3: 850 * C, 10 hours; Example 4: 850 'C 20 hours) the oxidation products also largely disappear, the concentration of these substances being in the range of ng / 1.
  • Acetonitrile, benzene, naphthalene and n-hexane is almost completely umge ⁇ on a doped catalyst already at 750 * C. Chlorobenzene achieves a conversion of approx. 80% at this temperature. At 850 * C, this value also increases to 100%. The oxygen conversion and the formation of carbon dioxide correspond to the complete oxidative conversion at a reaction temperature of 800-850 * C.
  • Catalyst calcium aluminate, C 3 A, C 12 A 7 with 1% Ni, 70 g
  • Air volume 42.54 1 / h; Dwell time: approx. 1 s; Temperature: 800 ° C Table 4
  • Benzene was chosen as the substrate because it is the most difficult to oxidize of all hydrocarbons.

Abstract

La présente invention concerne un procédé d'oxydation catalytique de produits nocifs organiques qui se trouvent dans les fumées d'origines et de compositions diverses. L'inconvénient de la pyrolyse et de la combustion à haute température qui visent à éliminer les déchets solides, liquides et gazeux, réside dans le fait que les hydrocarbures ne sont pas entièrement dégradés et sont partiellement oxydés. Jusqu'à présent, on n'est parvenu à obtenir une oxydation totale que sur des catalyseurs à base de métaux précieux, pour les gaz d'échappement de véhicules. Le but de l'invention est donc la mise au point d'un procédé simple et applicable techniquement, qui permette de transformer les hydrocarbures contenus dans les fumées non épurées, à l'aide d'un catalyseur et avec une réaction qui soit intéressante du point de vue énergétique. Le nouveau procédé se caractérise en ce qu'un bloc en nid d'abeilles à structure en tamis, dont les alvéoles constituées par un aluminate de calcium, modifié ou non, servent de catalyseur, est placé dans un flux de fumées non épurées, immédiatement en aval de la chambre de combustion. Les fumées sont à une température de 400 à 1 300 °C et elles séjournent de 0,2 à 3 secondes dans le bloc en nid d'abeilles.
EP96902886A 1995-02-16 1996-02-15 Procede de traitement catalytique de fumees Withdrawn EP0809531A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19506864A DE19506864A1 (de) 1995-02-16 1995-02-16 Verfahren zur katalytischen Behandlung von Rauchgasen
DE19506864 1995-02-16
PCT/DE1996/000287 WO1996025223A1 (fr) 1995-02-16 1996-02-15 Procede de traitement catalytique de fumees

Publications (1)

Publication Number Publication Date
EP0809531A1 true EP0809531A1 (fr) 1997-12-03

Family

ID=7755194

Family Applications (1)

Application Number Title Priority Date Filing Date
EP96902886A Withdrawn EP0809531A1 (fr) 1995-02-16 1996-02-15 Procede de traitement catalytique de fumees

Country Status (3)

Country Link
EP (1) EP0809531A1 (fr)
DE (1) DE19506864A1 (fr)
WO (1) WO1996025223A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10164480A1 (de) * 2001-12-29 2003-07-17 Schumacher Umwelt Trenntech Filterelement
CN115634569A (zh) * 2022-10-21 2023-01-24 湖北禾谷环保有限公司 一种脱氯剂及其制备方法和应用

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL6919238A (fr) * 1969-03-24 1970-09-28
JPS5285089A (en) * 1976-01-07 1977-07-15 Mitsubishi Heavy Ind Ltd Flue gas denitration catalyst
JPS57113842A (en) * 1981-01-08 1982-07-15 Matsushita Electric Ind Co Ltd Production of catalyst body for purification of gas
US4483259A (en) * 1981-07-07 1984-11-20 Benmol Corporation Method and composition for removal of gaseous contaminants produced in combustion of fossil fuels or present in reducing gases
US4960737A (en) * 1988-09-06 1990-10-02 Corning Incorporated Calcium dialuminate/hexaluminate ceramic structures
DE3926574A1 (de) * 1989-08-11 1991-02-14 Metallgesellschaft Ag Verfahren zur abscheidung von alkali- und schwermetallverbindungen aus heissen gasen

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9625223A1 *

Also Published As

Publication number Publication date
DE19506864A1 (de) 1996-08-22
WO1996025223A1 (fr) 1996-08-22

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