EP0225849B1 - Procédé pour déshalogéner les composés halogénés aliphatiques et aromatiques - Google Patents

Procédé pour déshalogéner les composés halogénés aliphatiques et aromatiques Download PDF

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Publication number
EP0225849B1
EP0225849B1 EP19860810553 EP86810553A EP0225849B1 EP 0225849 B1 EP0225849 B1 EP 0225849B1 EP 19860810553 EP19860810553 EP 19860810553 EP 86810553 A EP86810553 A EP 86810553A EP 0225849 B1 EP0225849 B1 EP 0225849B1
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EP
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Prior art keywords
sodium
parts
solvent
process according
proton donor
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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 - Lifetime
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EP19860810553
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German (de)
English (en)
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EP0225849A1 (fr
Inventor
Martin Dr. Bürli
Jürgen Dr. Beyrich
Kurt Plattner
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Novartis AG
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Ciba Geigy AG
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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
    • A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
    • A62D3/34—Dehalogenation using reactive chemical agents able to degrade
    • 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
    • A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
    • A62D2101/20—Organic substances
    • A62D2101/28—Organic substances containing oxygen, sulfur, selenium or tellurium, i.e. chalcogen

Definitions

  • the invention relates to a process for the dehalogenation of halogenated, in particular polyhalogenated, aliphatic or aromatic compounds by treating the organohalogen compounds with activated sodium.
  • PCBs Polychlorinated biphenyls
  • pentachlorophenols have been widely used. Compounds of this kind are sometimes found in nature. degrades extremely slowly and also often contains traces of highly toxic polychlorinated dibenzofurans or polychlorinated dibenzo-p-dioxins. Residues of these compounds or waste materials containing polychlorinated aromatics, e.g. Transformer oils must therefore be removed with special care.
  • Dechlorination using the sodium method is generally carried out by first dispersing metallic sodium in an inert solvent and then adding naphthalene, whereupon the sodium naphthalide is formed. This reagent is then added to the chlorinated aromatic compounds, e.g. PCBs that are in contaminated transformer oil and react. Subsequently, unreacted sodium naphthalide is hydrolyzed and the residue obtained after separating off the solvent is burned. The sodium can also only be dispersed in an inert solvent in the heat and then immediately brought into contact with the organochlorine compound. In this process variant, however, reaction times are observed to be significantly longer, which is apparently due to the fact that the sodium metal is passivated on the surface.
  • Dehalogenation methods have also become known from organic chemical synthesis. It is known e.g. the sodium ethanol method for the reductive dehalogenation of. polychlorinated alicyclic compounds that work with sodium in boiling ethanol (BV Lap et al., J.Org.Chem. 44, 4979 (1979) or the direct sodium dechlorination of 7,7, -dimethoxy-1,2,3 , 4-tetrachlorobicyclo [2.2.1] hepten- (2), the reaction being carried out in tetrahydrofuran in the presence of tert-butyl alcohol.
  • the present invention thus relates to a process for the dehalogenation of halogenated, in particular polyhalogenated, aliphatic or aromatic compounds by treatment with metallic sodium in an inert solvent and in the presence of a proton donor, characterized in that the halogenated compounds are mixed with 2 to 4 equivalents of sodium per equivalent bound halogen in the inert solvent in the presence of 0.5 to 2 mol of a branched or unbranched C 1 - to Cs alcohol or water per equivalent of bound halogen as a proton donor at a temperature of 100 to 150 ° C.
  • Aliphatic and aromatic halogen compounds can be almost completely removed from chlorine, bromine or iodine by this process.
  • the dehalogenated substance mixtures can then be safely deposited or burned. It may also be possible to reuse them after appropriate cleaning operations.
  • the chlorine compounds are primarily the polyhalogenated aromatic compounds mentioned at the outset, such as the polychlorinated biphenyls and pentachlorophenols, polychlorinated dibenzofurans and dibenzo-p-dioxins, and also mono-, di- or polyhalogenated saturated and unsaturated aliphatic hydrocarbons, such as Cz-G2 haloalkanes or Halogen alkenes.
  • chlorinated cyclodienes such as aldrin or hexachlorocyclopentadienes, or also the trichloroethanes, trichlorethylene, 1,6-dichlorohexane and I-chlorododecane, may also be mentioned by way of example.
  • bromine compounds are tribromoethylene, 1,6-dibromohexane and bromobenzenes or called brominated biphenyls.
  • Compounds which contain both chlorine and bromine, for example dibromochloropropane, are also suitable.
  • the dehalogenation is carried out in an inert solvent, for example in ethers such as dimethyl ether, diethyl ether, diisopropyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether or also tetrahydrofuran or dioxane;
  • ethers such as dimethyl ether, diethyl ether, diisopropyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether or also tetrahydrofuran or dioxane
  • hydrocarbons or hydrocarbon mixtures such as octane, decane, dodecane or branched hydrocarbons, such as isooctane, furthermore isoparaffin mixtures with a boiling range from 155 ° to 175 ° C., 170 ° to 190 ° C. or 160 ° to 200 ° C.
  • aromatic solvents such as xylene mixtures or corresponding waste solvents
  • mixture of solvent and halogen-free residues present after the dehalogenation, after extraction with water and subsequent drying by azeotropic distillation, can also be used directly as a reaction medium for a subsequent batch.
  • halogen compounds intended for dehalogenation e.g. in oils
  • they can already serve as inert solvents and the addition of such solvents is generally no longer necessary.
  • the solvent is usually in a large size. Excess used.
  • the concentration of the halogenated aliphatic or aromatic compounds in the solvent is advantageously between 1 and 10%. If substance mixtures with only a low content of organohalogen compounds are reacted, the concentration can also be below 1% by weight. It is not necessary for the compounds to dissolve completely in the solvent, even in suspension there is still a sufficiently rapid and complete reaction with the activated sodium.
  • the proton donor used is, in particular, branched or unbranched G to C 5 alcohols, such as methanol, ethanol, propanol, isopropanol, tert-butanol or pentyl alcohol and water.
  • Good activation of the sodium succeeds above all with the alcohols mentioned, in particular methanol or ethanol, and water.
  • the sodium based on the halogen to be removed, is used in excess, using 2 to 4 equivalents, in particular 2 to 3 equivalents, of sodium per equivalent of bound chlorine, bromine or iodine.
  • the proton donor is used in an amount of about 0.5 to 2 mol, in particular in an amount of 1 to 2 mol or 1 to 1.5 mol, per equivalent of bound halogen.
  • the temperature range is from about 100 to 150 ° C.
  • the sodium is in molten form and is finely dispersed in the reaction medium. If appropriate, the reaction can also be carried out under pressure.
  • the sodium is first dispersed in the hot solvent and the polyhalogenated compound is added.
  • the proton donor is then added continuously or discontinuously over a longer period, depending on the size of the batch.
  • the sodium is dispersed in the hot solvent and then a mixture of organohalogen compound and proton donor is slowly added.
  • the polyhalogenated compound is placed in a hot solvent, then liquid sodium and the proton donor are added simultaneously, but separately.
  • variant (C) is preferred, since hardly any polymers are formed here and the reaction can be interrupted at any time, so that there is no accumulation of unreacted sodium in the reactor.
  • the method according to the invention is particularly suitable for working up e.g. Waste oils (motor oils, transformer oils, etc.) that are contaminated with or contain halogenated compounds. In this workup, there is generally no need to add an inert solvent, as indicated.
  • Waste oils motor oils, transformer oils, etc.
  • the cooled batch is mixed with water and the sodium chloride is extracted.
  • the degree of dechlorination is over 99.7%.
  • the solvent phase contains only 36 ppm of organically bound chlorine.
  • Example 1 The procedure described in Example 1 is followed, except that 2.4 parts of butanol are used as proton donor instead of methanol, and 4.7 parts of butanol are added at the end of the reaction to destroy the excess sodium.
  • the degree of dechlorination is over 99.3%.
  • the solvent phase contains only 80 ppm of organically bound chlorine.
  • the sodium chloride formed is extracted from the cooled batch with water.
  • the degree of dechlorination is 99.93%.
  • the solvent phase contains only 5.2 ppm of organically bound chlorine.
  • the dechlorination is carried out as described in Example 4, but the process is carried out at a temperature of 50 ° C. with finely suspended sodium.
  • the degree of dechlorination is 98.3%.
  • the solvent phase contains only 100 ppm of organically bound chlorine.
  • the dechlorination is carried out as described in Example 7, but the process is carried out at a temperature of 150 ° C.
  • the degree of dechlorination is in the same range as that of Example 7.

Claims (8)

1. Procédé pour la déshalogénation de composés aliphatiques ou aromatiques halogénés, par traitement par du sodium métallique dans un solvant inerte et en présence d'un donneur de protons, caractérisé en ce que l'on fait réagir les composés halogénés avec 2 à 4 équivalents de sodium par équivalent d'halogène lié. dans le solvant inerte, en présence de 0,5 à 2 moles d'un alcool en C1-C5 ramifié ou non ramifié ou d'eau, par équivalent d'halogène lié, à une température de 100 à 150°C.
2. Procédé selon la revendication 1, caractérisé en ce que l'on utilise de 2 à 3 équivalents de sodium par équivalent d'halogène lié.
3. Procédé selon les revendications 1 et 2, caractérisé en ce que l'on utilise de 1 à 2 moles d'un donneur de protons, par équivalent d'halogène lié.
4. Procédé selon les revendications 1 à 3; caractérisé en ce que l'on dispose au préalable le solvant, le sodium et le composé halogéné, et on ajoute de façon réglée le donneur de protons.
5. Procédé selon les revendications 1 à 3, caractérisé en ce que l'on dispose au préalable le solvant et le sodium, et on ajoute de façon réglée le composé halogéné, conjointement avec le donneur de protons.
6. Procédé selon les revendications 1 à 3, caractérisé en ce que l'on dispose au préalable le composé halogéné et le solvant, et on ajoute de façon réglée, simultanément mais séparément, le sodium et le donneur de protons.
7. Utilisation du procédé selon la revendication 1, pour la déchloration de composés aromatiques polychlorés.
8. Utilisation du procédé selon la revendication 7, caractérisée en ce que les composés aromatiques polychlorés sont des benzofurannes ou des dioxines chlorés.
EP19860810553 1985-12-06 1986-12-01 Procédé pour déshalogéner les composés halogénés aliphatiques et aromatiques Expired - Lifetime EP0225849B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH522585A CH668709A5 (de) 1985-12-06 1985-12-06 Verfahren zur enthalogenierung von polyhalogenierten aliphatischen und aromatischen verbindungen.
CH5225/85 1985-12-06

Publications (2)

Publication Number Publication Date
EP0225849A1 EP0225849A1 (fr) 1987-06-16
EP0225849B1 true EP0225849B1 (fr) 1990-04-18

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EP19860810553 Expired - Lifetime EP0225849B1 (fr) 1985-12-06 1986-12-01 Procédé pour déshalogéner les composés halogénés aliphatiques et aromatiques

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Country Link
EP (1) EP0225849B1 (fr)
JP (1) JPS62152479A (fr)
CH (1) CH668709A5 (fr)
DE (1) DE3670449D1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10304641A1 (de) * 2002-02-07 2003-09-04 Toshiba Kk System zur Entgiftung toxischer chlorierter organischer Verbindungen und Verfahren zum Rezyklieren des entgifteten Abfalls

Families Citing this family (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5220109A (en) * 1987-09-03 1993-06-15 Atochem Destruction of halogenated organic species
FR2620055B1 (fr) * 1987-09-03 1991-05-10 Atochem Procede chimique de destruction de produits organiques halogenes
US5185488A (en) * 1989-09-28 1993-02-09 Her Majesty The Queen In Right Of Canada, As Represented By The Minister Of Natural Resources Process for the reductive dehalogenation of polyhaloaromatics with sodium or calcium in a lower alcohol
FR2656603B1 (fr) * 1989-12-28 1993-05-21 Atochem Procedes de synthese de benzyltoluene et dibenzyltoluene a faible teneur en chlore.
DE4109639C2 (de) * 1991-03-23 1994-06-01 Metallgesellschaft Ag Verfahren zur Zersetzung von polyhalogenierten Organoverbindungen
DE4236382A1 (de) * 1992-10-28 1994-05-05 Degussa Verfahren zur Umsetzung von FCKW's mit Dispersionen von Alkalimetallen
DE4324931A1 (de) * 1993-07-24 1995-01-26 Ufz Leipzighalle Gmbh Verfahren zur reduktiven Dehalogenierung von organohalogenhaltigen festen und flüssigen Stoffen
AU5691594A (en) * 1994-01-04 1995-08-01 Neos Technology Inc. Sodium dispersion and organohalide reaction processes
JP2638483B2 (ja) * 1994-06-30 1997-08-06 株式会社関西テック 多塩素化芳香族化合物の処理方法
EP1630824A1 (fr) 1994-09-30 2006-03-01 Arkema Composition dielectrique à base de polyarylalcanes ayant des proprietes dielectriques ameliorées
DE19742297C2 (de) * 1997-09-25 2000-06-29 Volker Birke Verfahren zur reduktiven Dehalogenierung von halogenorganischen Stoffen
DE19903986A1 (de) * 1999-02-02 2000-08-10 Friedrich Boelsing Verfahren zur reduktiven Dehalogenierung von Halogenkohlenwasserstoffen
DE19903987A1 (de) * 1999-02-02 2000-08-10 Friedrich Boelsing Verfahren zur reduktiven Dehalogenierung flüssiger oder fester Halogenkohlenwasserstoffe
JP3771120B2 (ja) * 2000-07-28 2006-04-26 株式会社神鋼環境ソリューション 有機ハロゲン化合物汚染油の処理方法及びその処理装置
US6479413B1 (en) 2000-08-30 2002-11-12 Benjamin V. Booher Composite friction elements and pultrusion method of making
JP2002187858A (ja) * 2000-12-18 2002-07-05 Nippon Soda Co Ltd 難分解性ハロゲン化合物の分解方法
WO2003037442A1 (fr) * 2001-10-29 2003-05-08 Powertech Labs Inc. Procede de destruction de composes organiques halogenes dans des solides
US20030120127A1 (en) 2001-11-07 2003-06-26 Wylie Ian Gordon Norman Process for destruction of halogenated organic compounds in solids
JP2008022889A (ja) * 2006-07-18 2008-02-07 Aruze Corp 遊技機および制御基板の製造方法
CN104907314B (zh) * 2015-05-27 2017-06-13 华中科技大学 一种卤代有机固体污染物的处理方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4327027A (en) * 1979-06-15 1982-04-27 Vertac Chemical Corporation Chemical detoxification of toxic chlorinated aromatic compounds
US4337368A (en) * 1980-04-21 1982-06-29 The Franklin Institute Reagent and method for decomposing halogenated organic compounds
CA1181771A (fr) * 1982-07-27 1985-01-29 Ontario Hydro Methode de deshalogenation d'halogenures organiques
DE3410239A1 (de) * 1984-03-21 1985-10-03 Hivolin Gmbh Verfahren zur beseitigung von toxischen poly- oder perhalogenierten organischen verbindungen

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10304641A1 (de) * 2002-02-07 2003-09-04 Toshiba Kk System zur Entgiftung toxischer chlorierter organischer Verbindungen und Verfahren zum Rezyklieren des entgifteten Abfalls

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Publication number Publication date
CH668709A5 (de) 1989-01-31
JPS62152479A (ja) 1987-07-07
DE3670449D1 (de) 1990-05-23
EP0225849A1 (fr) 1987-06-16

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