EP0188718B1 - Procédé pour la décomposition chimique-thermique d'hydrocarbures hautement halogénés - Google Patents

Procédé pour la décomposition chimique-thermique d'hydrocarbures hautement halogénés Download PDF

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Publication number
EP0188718B1
EP0188718B1 EP85115514A EP85115514A EP0188718B1 EP 0188718 B1 EP0188718 B1 EP 0188718B1 EP 85115514 A EP85115514 A EP 85115514A EP 85115514 A EP85115514 A EP 85115514A EP 0188718 B1 EP0188718 B1 EP 0188718B1
Authority
EP
European Patent Office
Prior art keywords
calcium
halogenated hydrocarbons
oxide
iron oxide
chemical
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.)
Expired
Application number
EP85115514A
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German (de)
English (en)
Other versions
EP0188718A1 (fr
Inventor
Paul-Gerhard Dr. Dipl.-Chem. Maurer
Daniel Dr. Dipl.-Chem. Neupert
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.)
Nukem GmbH
Original Assignee
Nukem 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 Nukem GmbH filed Critical Nukem GmbH
Priority to AT85115514T priority Critical patent/ATE30120T1/de
Publication of EP0188718A1 publication Critical patent/EP0188718A1/fr
Application granted granted Critical
Publication of EP0188718B1 publication Critical patent/EP0188718B1/fr
Expired legal-status Critical Current

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Classifications

    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
    • A62D3/40—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by heating to effect chemical change, e.g. pyrolysis
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
    • A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
    • A62D3/36—Detoxification by using acid or alkaline reagents
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
    • A62D2101/04—Pesticides, e.g. insecticides, herbicides, fungicides or nematocides
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
    • A62D2101/06—Explosives, propellants or pyrotechnics, e.g. rocket fuel or napalm
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
    • A62D2101/20—Organic substances
    • A62D2101/22—Organic substances containing halogen
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D2203/00—Aspects of processes for making harmful chemical substances harmless, or less harmful, by effecting chemical change in the substances
    • A62D2203/04—Combined processes involving two or more non-distinct steps covered by groups A62D3/10 - A62D3/40

Definitions

  • the invention relates to a process for the chemical-thermal decomposition of higher halogenated hydrocarbons by reaction with calcium oxide and / or calcium hydroxide in a superstoichiometric ratio at temperatures of 600 to 800 ° C in a reactor.
  • halogenated hydrocarbons are used very frequently in industry and research.
  • fluorocarbons serve as dough gas and refrigerants and are the starting materials for the production of chemically very resistant plastics.
  • Chlorinated hydrocarbons are used in large quantities as degreasing agents in metal processing plants. Other areas of application are chemical cleaning of all kinds.
  • chlorinated hydrocarbons are the starting materials for the production of polymers, pesticides and herbicides.
  • the polychlorinated hydrocarbons were used as heat transfer oils or hydraulic fluids due to their high chemical and thermal resistance.
  • the polychlorinated biphenyls (PCB) are typical representatives of this class of substances.
  • PCBs which in the past were mainly used as transformer oils and as dielectrics in capacitors. Simply by replacing these liquids with substitutes, the Federal Republic of Germany expects to dispose of around 6000 t of polychlorinated biphenyls annually over the next ten years.
  • DE-OS 3028193 describes a process for the pyrolytic decomposition of halogens and / or phosphorus-containing organic substances, these being reacted with calcium oxide / calcium hydroxide in a superstoichiometric ratio at temperatures of 300 to 800 ° C. in a reactor.
  • the disadvantage of this process is that not all halogenated hydrocarbons can be decomposed without problems.
  • the temperatures required for the quantitative decomposition of the chemically and thermally very stable higher halogenated hydrocarbons, to which the polychlorinated biphenyls in particular must be counted, are above 600 ° C. Above this temperature, mixtures of CaO and Ca (OH) 2 form with the corresponding calcium chlorides, Melt. This fact presents considerable difficulties since the necessary continuous throughput of solids through the reactor is thereby hindered and may even become impossible.
  • the formation of melts also leads to a considerable reduction in the decomposition rate of the halogenated hydrocarbons. This is due to the large reduction in the surface area of the solid reactants, which have a significant influence on the reaction in gas-solid reactions. Even a strong excess of the basic compounds mentioned cannot prevent melt formation with subsequent incrustation in the cooling phase at temperatures above 600 ° C.
  • This object was achieved according to the invention in that the calcium oxide and / or calcium hydroxide, based on the halogen to be set, is present in at least a two-fold stoichiometric excess and contains 2 to 30% by weight of iron oxide.
  • a two to five-fold stoichiometric excess of calcium oxide and / or calcium hydroxide is preferably used, it being possible for some of the calcium compounds to be replaced by the corresponding magnesium compounds.
  • Iron oxide additives in the size of 3 to 25% by weight have proven successful, it being possible for the iron oxide to be present as such or in the form of substances containing iron oxide.
  • the red mud obtained in the production of aluminum can be used fly ash from combustion plants is advantageously used.
  • the added iron oxide also has a catalytic effect on the chemical-thermal decomposition of halogenated hydrocarbons.
  • the amount of calcium oxide and / or calcium hydroxide used, based on the halogen to be set is used in twice the stoichiometric amount. Equally good results cannot be achieved without the addition of iron oxide.
  • the iron oxide can be replaced by cheaper iron oxide-containing substitutes.
  • fly ash has proven to be particularly advantageous. Fly ash is produced in large quantities during the combustion of hard coal and lignite in power plants and must also be disposed of so that no further costs arise when using the fly ash. Typical levels of iron oxide in fly ash are 5 to 18% by weight. In addition, fly ash also sometimes contains considerable amounts of calcium oxide, so that calcium oxide can also be saved.
  • the resulting gaseous reaction products are halogen-free.
  • the exhaust gas contains corresponding amounts of hydrogen, methane and possibly other partly saturated and partly unsaturated low hydrocarbons as well as small amounts of carbon monoxide.
  • the exhaust gas still has a considerable calorific value and can be used accordingly or simply post-burned to carbon dioxide and water in a post-combustion chamber.
  • the chemical-thermal decomposition according to the invention of higher halogenated hydrocarbons by reaction with calcium oxide and / or calcium hydroxide and iron oxide or substances containing iron oxide is a very environmentally friendly and inexpensive method of disposing of these substances. No formation of metabolites, such as polychlorinated dibenzodioxins or furans, takes place in the process mentioned, so that there are no safety-related concerns from this point of view either.
  • the waste gases escaping from the reactor during the test are free of halogenated hydrocarbons and are re-burned in a post-combustion chamber with a slight excess of air.

Landscapes

  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Business, Economics & Management (AREA)
  • Emergency Management (AREA)
  • Fire-Extinguishing Compositions (AREA)
  • Processing Of Solid Wastes (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Claims (4)

1. Procédé de décomposition thermochimique d'hydrocarbures fortement halogénés, par réaction avec de l'oxyde de calcium et/ou de l'hydroxyde de calcium, dans un rapport hyper- stoechiométrique à des températures de 600 à 800° C, dans un réacteur, procédé caractérisé en ce que l'oxyde et/ou l'hydroxyde de calcium est présent avec un excès, calculé sur l'halogène qui doit être combiné, qui représente au moins deux fois la proportion stcechiométrique etcontient 2 à 30% en poids d'oxyde de fer.
2. Procédé suivant la revendication 1, caractérisé en ce que l'on utilise une proportion d'oxyde et/ou d'hydroxyde de calcium qui représente deux à cinq fois la proportion stœchiométrique.
3. Procédé suivant l'une des revendications 1 et 2, caractérisé en ce que l'oxyde et/ou l'hydroxyde de calcium contient de 3 à 25% d'oxyde de fer.
4. Procédé suivant l'une des revendications 1 à 3, caractérisé en ce que l'oxyde de fer se présente sous forme de cendres volantes de chaufferies.
EP85115514A 1984-12-24 1985-12-06 Procédé pour la décomposition chimique-thermique d'hydrocarbures hautement halogénés Expired EP0188718B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT85115514T ATE30120T1 (de) 1984-12-24 1985-12-06 Verfahren zur chemisch-thermischen zersetzung von hoeher halogenierten kohlenwasserstoffen.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3447337 1984-12-24
DE3447337A DE3447337C2 (de) 1984-12-24 1984-12-24 Verfahren zur chemisch-thermischen Zersetzung von höher halogenierten Kohlenwasserstoffen

Publications (2)

Publication Number Publication Date
EP0188718A1 EP0188718A1 (fr) 1986-07-30
EP0188718B1 true EP0188718B1 (fr) 1987-10-07

Family

ID=6253854

Family Applications (1)

Application Number Title Priority Date Filing Date
EP85115514A Expired EP0188718B1 (fr) 1984-12-24 1985-12-06 Procédé pour la décomposition chimique-thermique d'hydrocarbures hautement halogénés

Country Status (4)

Country Link
US (1) US4654203A (fr)
EP (1) EP0188718B1 (fr)
AT (1) ATE30120T1 (fr)
DE (2) DE3447337C2 (fr)

Families Citing this family (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3517019A1 (de) * 1985-05-11 1986-11-13 Nukem Gmbh Verfahren zur chemisch-thermischen zersetzung von halogenkohlenwasserstoffen
DE3640573A1 (de) * 1985-11-28 1987-06-04 Suppan Friedrich Verfahren und anlage zur energiegewinnung aus giftigen abfallstoffen bei deren gleichzeitiger entsorgung
DE3623492A1 (de) * 1986-07-11 1988-01-21 Hagenmaier Hans Paul Verfahren zum abbau von halogenierten aromaten
US5276250A (en) * 1986-07-11 1994-01-04 Hagenmaier Hans Paul Process for decomposing polyhalogenated compounds
DE3632363A1 (de) * 1986-09-24 1988-03-31 Boelsing Friedrich Verfahren zur dehalogenierung von halogenierten kohlenwasserstoffen
DE3716444A1 (de) * 1987-05-16 1988-12-01 Hartmann Helmut Verfahren und anlage zur reinigung von kontaminierten schuettguetern
DE3731688A1 (de) * 1987-09-21 1989-03-30 Degussa Verfahren zur katalytischen umsetzung von kohlenwasserstoff, halogenkohlenwasserstoff und kohlenmonoxid enthaltenden abgasen
US4844875A (en) * 1987-10-13 1989-07-04 Westinghouse Electric Corp. Fly ash recycling to reduce toxic gaseous emissions
US5124805A (en) * 1988-12-08 1992-06-23 Daewoo Electronics, Co., Ltd. Remote control operated moving television receiver
US5021229A (en) * 1988-12-21 1991-06-04 The United States Of America As Represented By The Environmental Protection Agency Reduction of chlorinated organics in the incineration of wastes
US5185134A (en) * 1988-12-21 1993-02-09 The United States Of America As Represented By The U.S. Environmental Protection Agency Reduction of chlorinated organics in the incineration of wastes
DE3902843A1 (de) * 1989-01-27 1990-08-02 Herbst Umwelttech Gmbh Verfahren zur reinigung von gasen
DE3918716C1 (fr) * 1989-06-08 1990-06-28 Nukem Gmbh, 6450 Hanau, De
DE4119390C2 (de) * 1991-06-12 1995-09-14 Johne Patricia Vertreten Durch Verfahren zum Aufbereiten und auslaugbeständigen Verfestigen von Filterstäuben und Reaktionsprodukten aus der Rauchgasreinigung von Abfall- und Klärschlammverbrennungsanlagen
FI88364C (fi) * 1991-08-09 1993-05-10 Ahlstroem Oy Foerfarande foer behandling av halogenfoereningar innehaollande process- eller roekgaser
DE4404329C2 (de) * 1994-02-11 1996-07-11 Cs Halbleiter Solartech Entsorgung von Flourchlorkohlenwasserstoffen und Halonen
DE4420400A1 (de) * 1994-06-08 1995-12-14 Lemmerbrock Karl Heinrich Verfahren zur Dekontamination polychlorierte Biphenyle enthaltende Stoffe
EP0702078B1 (fr) * 1994-09-14 2001-12-05 Toda Kogyo Corporation Procédé d'incinération de déchets combustibles et scavenger de chlore
NO308831B1 (no) 1995-03-22 2000-11-06 Nkt Res Ct As FremgangsmÕte for behandling av halogenholdig avfallsmateriale
US5817284A (en) * 1995-10-30 1998-10-06 Central Glass Company, Limited Method for decomposing halide-containing gas
US5744689A (en) * 1996-10-28 1998-04-28 Hiromi Taguchi Treating material for polychlorobiphenyl-containing oils
EP0937483B1 (fr) * 1998-02-10 2003-09-24 Miyoshi Yushi Kabushiki Kaisha Procédé de traitement de déchets solides
JP2001219031A (ja) * 2000-02-08 2001-08-14 Air Liquide Japan Ltd パーフルオロ化合物の分解方法及び分解装置
US20040247508A1 (en) * 2003-06-09 2004-12-09 Kiyoharu Sakurai Decomposing dialkyl phthalates using coal fly ash
HU229808B1 (hu) 2009-09-24 2014-08-28 Mta Kemiai Kutatokoezpont Eljárás és berendezés poliklórozott szénhidrogéneket tartalmazó veszélyes hulladékok megsemmisítésére
US8128902B2 (en) * 2011-04-12 2012-03-06 Midwest Refrigerants, Llc Method for the synthesis of anhydrous hydrogen halide and anhydrous carbon dioxide
US8043574B1 (en) 2011-04-12 2011-10-25 Midwest Refrigerants, Llc Apparatus for the synthesis of anhydrous hydrogen halide and anhydrous carbon dioxide
US8834830B2 (en) 2012-09-07 2014-09-16 Midwest Inorganics LLC Method for the preparation of anhydrous hydrogen halides, inorganic substances and/or inorganic hydrides by using as reactants inorganic halides and reducing agents
CN104307193A (zh) * 2014-11-10 2015-01-28 华玉叶 一种浸没蒸发方法

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3845191A (en) * 1972-06-02 1974-10-29 Du Pont Method of removing halocarbons from gases
US4201751A (en) * 1975-05-06 1980-05-06 Heinz Gresch Gas purification
DE2855650C2 (de) * 1978-12-22 1984-10-25 Nukem Gmbh, 6450 Hanau Verfahren zur pyrohydrolytischen Zersetzung von Phosphor enthaltenden, mit hochangereichertem Uran kontaminierten Flüssigkeiten
US4230053A (en) * 1979-02-05 1980-10-28 Deardorff Paul A Method of disposing of toxic substances
DE3028193C2 (de) * 1980-07-25 1984-11-22 Nukem Gmbh, 6450 Hanau Verfahren und Vorrichtung zur pyrolytischen Zersetzung von Halogene und/oder Phosphor enthaltenden organischen Substanzen
DE3313889A1 (de) * 1983-04-16 1984-10-18 Martina Von Ahn Verfahren und vorrichtung zur beseitigung von gift- und sondermuell

Also Published As

Publication number Publication date
EP0188718A1 (fr) 1986-07-30
DE3447337A1 (de) 1986-07-03
US4654203A (en) 1987-03-31
DE3560739D1 (en) 1987-11-12
DE3447337C2 (de) 1986-11-06
ATE30120T1 (de) 1987-10-15

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