EP2596836B1 - Verfahren zur Zersetzung einer halogenierten organischen Verbindung - Google Patents

Verfahren zur Zersetzung einer halogenierten organischen Verbindung Download PDF

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Publication number
EP2596836B1
EP2596836B1 EP20110190293 EP11190293A EP2596836B1 EP 2596836 B1 EP2596836 B1 EP 2596836B1 EP 20110190293 EP20110190293 EP 20110190293 EP 11190293 A EP11190293 A EP 11190293A EP 2596836 B1 EP2596836 B1 EP 2596836B1
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Prior art keywords
compound
halogenated
organic compound
halogenated organic
superoxide
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EP20110190293
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English (en)
French (fr)
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EP2596836A1 (de
Inventor
Inas Muen AlNashef
Saeed Mohammed Al-Zahrani
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King Saud University
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King Saud University
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    • 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
    • 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
    • A62D3/38—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents by oxidation; by combustion
    • 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
    • A62D2101/02—Chemical warfare substances, e.g. cholinesterase inhibitors
    • 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
    • A62D2101/20—Organic substances
    • A62D2101/22—Organic substances containing halogen

Definitions

  • the present invention relates to a method for decomposing a halogenated organic compound.
  • a deep eutectic solvent is a type of ionic solvent with special properties composed of a mixture of compounds which form an eutectic with a melting point much lower than either of the individual components.
  • DESs are useful as solvents, as electrolytes and as catalysts. Although DESs have many common characteristics with ionic liquids, they are considered as different type of solvents. Ionic liquids are composed entirely from ions while DESs have both ions and neutral molecules. In addition, ionic liquids are synthesized by chemical reactions while DESs are prepared by mixing and heating only. The first generation of eutectic solvents was based on mixtures of quaternary ammonium salts with hydrogen bond donors such as amines and carboxylic acids.
  • DESs Compared to ionic liquids they share many characteristics but are ionic compounds and not ionic mixtures, deep eutectic solvents are cheaper to make, much less toxic and sometimes biodegradable.
  • the major advantages of the approach used for the synthesis of DESs is that common, non-toxic components can be used and that they are easy to make by just mixing two compounds with gentle heating and subsequent cooling to room temperature.
  • WO 02/26701 relates to a method for the synthesis of DES by the mixing of one amine salt, such as choline chloride, with an organic compound capable of forming hydrogen bond with the ion of the amine salt, such as urea.
  • WO 00/56700 relates to a method for the synthesis of deep eutectic solvents formed by mixing a quaternary ammonium compound or a mixture of two or more thereof with a halide of zinc, tin or iron or a mixture of two or more thereof.
  • US 7,763,768 discloses the use of a deep eutectic solvent comprising a quaternary ammonium salt and different hydrogen bond donors as a solvent for the preparation of hydrogen peroxide.
  • Thermal oxidation is a standard method of destroying hazardous chemicals. Destructive oxidation is done in high-efficiency thermal incinerators or in cement kilns but the potential for emission of dioxins makes regulations on these operations very strict.
  • Sugimoto et al., Sci. Technol. 1988, 22, 1182 relates to polyhalogenated aromatic hydrocarbons, by example PCBs and hexachlorobenzene and its rapid degradation by the superoxide ions in dimethylformamide to carbonate and halide ions.
  • the efficient desctruction of such materials is accomplished via the in situ electrolytic reduction of dioxygen to generate the superoxide ion which reacts with the polyaromatics by nucleophilic substitution.
  • US 7,812,211 relates to a process for the destruction of small to large quantities of halo-genated hydrocarbons using superoxide ions in ammonium salt based deep eutectic solvents.
  • a method shall be provided in which the halogenated organic compound is decomposed by the reaction with superoxide ions in a non-ammonium salt based deep eutectic solvent.
  • non-ammonium salt based deep eutectic solvents an efficient decomposition of compounds which exhibit poor solubility in ammonium salt based deep eutectic solvents shall be enabled.
  • the first object is achieved by a method for decomposing a halogenated organic compound comprising the steps:
  • R 1 , R 2 , R 3 and R 4 are independently selected from substituted or unsubstituted, linear or branched C 1 -C 18 alkyl, C 1 -C 10 alkoxy, C 6 -C 10 cycloalkyl, C 6 -C 12 aryl or C 7 -C 12 alkaryl.
  • X is chlorine or bromine, more preferably chlorine.
  • the halogenated organic compound contains at least one chlorine atom.
  • the halogenated organic compound is a chemical warfare agent, more preferably sulfur mustard gas, nitrogen mustard gas Lewisite or derivatives thereof.
  • the halogenated organic compound is a halogenated hydrocarbon, more preferably halogenated aromatic hydrocarbon, halogenated polyaromatic hydrocarbon, halogenated aliphatic hydrocarbon and/or halogenated cycloaliphatic hydrocarbon.
  • the molar ratio of compound (I) to compound (II) is 1:2.
  • the electrochemical generating takes place in a membrane electrochemical reactor.
  • the deep eutectic solvent has a freezing point of up to 100°C.
  • superoxide ions can be provided in the DES according to step a) of the inventive method by preferably dissolving alkali superoxides or alkaline earth metal superoxides in the DES without the addition of any other chemicals, such as crown ethers. It was also found that the solubility of alkali superoxides or alkaline earth metal superoxides in phosphonium based DESs is significant higher than in ammonium based DESs.
  • the method of the present invention provides the opportunity to decompose small to large quantities of hazardous chemicals at ambient conditions without producing any toxic byproducts.
  • the method of the present invention can be carried out in a fast, cost-effective, easy manner to substantially completely decompose the hazardous chemicals.
  • the used halogenated compounds were obtained from different sources, e.g. Sigma-Aldrich, Acros. The stated purity of most of the used substrates was ⁇ 99. The deep eutectic solvents were obtained from Scionix, UK. All chemicals were used without further purification.
  • Sulfur mustard (SM) and nitrogen mustard (HN1) were synthesized in our labs using methods reported in the literature. GC/MS and HPLC analysis showed that the purity of said compounds was ⁇ 99%.
  • the conductivity of the used DES is in a range of 1-20 mS/cm.
  • a membrane electrochemical reactor was used for decomposition experiments using an electrochemically generated superoxide ion.
  • the cathode and anode compartments were made of Plexiglas with appropriate openings to accommodate the electrodes and to load and unload solutions.
  • Proton exchange membranes of different thicknesses were used as a separator between the cathode and anode compartment.
  • the membranes were soaked in a boiling 5M NaOH solution for 2-3 h to get rid of H + and then in boiling distilled water for about 1 h.
  • the membrane was soaked with DES for 24 h before being used.
  • the anode and cathode compartments were made of Plexiglas.
  • the outside frames of the reactor were made of either Plexiglas for clear visualization of the reactor contents or from metallic alloy with proper grooves to accommodate electrical heating elements. Silicon rubber gaskets were used for leak prevention. A reticulated vitreous carbon or Pt mesh was used as a working electrode.
  • the cathode chamber containing DES ( ⁇ 20 mL) was purged with argon for 20 min. The catholyte was first pre-electrolyzed until the background current fell to ⁇ 1 mA. Then a weighed amount of the substrate to be destroyed was added to the DES and the solution was stirred with a magnet stirrer for several hours. A sample from the solution was then analyzed using HPLC to be sure that the substrate is totally dissolved in the DES.
  • Oxygen was bubbled through the solution during the electrolysis period. Agitation of the catholyte was achieved by using a magnetic stirrer and through bubbling of oxygen. After electrolysis, diethyl ether was used to extract the products and the remaining reactant from the DES. A sample of the extract was then analyzed using HPLC and GC/MS.
  • a gas-sampling bag had been used for the collection of evolved gaseous products from the reactor.
  • the gaseous products and the sample drawn from the reaction mixture were analyzed for the identification of volatile and non-volatile products monitored by GC/MS.
  • the results were compared with authentic samples.
  • the gaseous contents in the sampling bags were analyzed as such by GC/MS using gas tight syringe, the analysis results showed the formation of SO 2 , NO 2 , and chlorine which were matched with spectral library. These gases may be readily contained and prevented from escaping to the atmosphere.
  • the superoxide ions can be generated by dissolving Group 1 (alkali metals) or Group 2 (alkaline earth metals) superoxides, e.g. potassium superoxide in DES without the need to use any additional chemicals which are usually used to enhance the solubility of these metal superoxides in aprotic solvents, e.g. crown ethers.
  • aprotic solvents e.g. crown ethers.
  • increasing the temperature to about 50°C increased the solubility of said superoxides drastically.
  • the presence and stability of the superoxide ion in the tested DES were checked using UV-vis spectrophotometer.
  • a weighed amount of the selected hazardous chemical was added to about 10 g of DES.
  • the solution was mixed vigorously. After enough time, a sample from the solution was withdrawn and analyzed using HPLC and the resulting peak was compared to the peak of the corresponding pure chemical. Then small weighed amounts of the metal superoxide, e.g. potassium superoxide, were added to the solution under vigorous mixing. Samples were then taken and analyzed using HPLC until no peak for the hazardous chemical is detected. The solution was then extracted using a proper solvent, e.g. diethyl ether, and the sample was analyzed using GC/MS. No peaks were detected for the hazardous chemical or any known degradation products.
  • Fig. 1 shows a GC chromatogram of the sulfur mustard before being processed according to the inventive method.
  • Fig. 2 shows a mass spectrum of the peak of Fig. 1
  • Fig. 3 shows a GC chromatogram of the sulfur mustard after being processed according to the inventive method. As can be taken, no sulfur mustard can be detected.
  • Example 2 The same procedure used in Example 1 was repeated except that the superoxide ion was generated electrochemically by the electrochemical reduction of oxygen dissolved in the DES using a membrane electrochemical reactor.
  • the working, reference, and counter electrodes were reticulated carbon, Ag/AgCl, and Pt mesh, respectively.
  • Example 2 The same procedure used in Example 1 was repeated except that the used DES is synthesized by mixing methyltriphenylphosphonium bromide with nickel nitrate hexahydrate in the molar ratio of 1:2.
  • HN1 nitrogen mustard gas
  • examples 2-4 are as for example 1. No hazardous chemical could be detected after processing according to the present invention.

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  • 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)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Claims (9)

  1. Verfahren zum Zersetzen einer halogenhaltigen organischen Verbindung, umfassend die Schritte
    a) Bereitstellen mindestens eines stark eutektischen Lösungsmittels umfassend:
    aa) mindestens eine Verbindung (I) der allgemeinen Formel

            R1R2R3R4P+X-

    und/oder

            R1R2R3S+X-; und

    bb) mindestens eine Verbindung (II), ausgewählt aus einem
    Metallhalogenid und/oder einem Metallhalogenid-Hydrat;
    wobei R1, R2, R3 und R4 unabhängig ausgewählt sind aus H, substituiertem oder unsubstituiertem, linearem oder verzweigtem Alkyl, Alkoxy, Cycloalkyl, Aryl oder Alkaryl oder wobei zwei von R1, R2, R3 oder R4 eine wahlweise substituierte Alkylengruppe, bevorzugt eine C4-C10-Alkylengruppe sind;
    X Halogen ist,
    wobei das Metall in Verbindung (II) unabhängig ausgewählt ist aus Li, Mg, Ca, Cr, Mn, Fe. Co, Ni, Cu, Zn, Cd, Sn, Pb, Bi, La oder Ce, bevorzugt Zn, Sn oder Fe, oder Gemischen hiervon, und
    das Molverhältnis von Verbindung (I) zu Verbindung (II) m einem Bereich von 1:1 bis 1:5 ist;
    b) Lösen der halogenhaltigen organischen Verbindung in dem stark eutertischen Lösungsmittel;
    c) Halten der Lösung, welche in Schritt b) erhalten wird, in einem Temperaturbereich von 15°C bis 100°C; und
    d) Zugeben von molekularem Sauerstoff zu der Losung, welche in Schritt c) erhalten wird, und elektrochemisches Erzeugen von Superoxidionen aus dem molekularen Sauerstoff und/oder Zugeben mindestens eines Alkalisuperoxids und/oder mindestens eines Erdalkalimetallsuperoxids zu der Losung, welche in Schritt c) erhalten wird
  2. Verfahren nach Anspruch 1, wobei R , R2, R3 und R4 unabhängig ausgewählt sind aus substituiertem oder unsubstituiertem, linearem oder verzweigtem C1-C18-Alkyl, C1-C10-Alkoxy, C6-C10-Cycloalkyl, C6-C12-Aryl oder C7-C2-Alkaryl
  3. Verfahren nach Anspruch 1 oder 2, wobei X Chlor oder Brom, bevorzugt Chlor ist.
  4. Verfahren nach einem der vorangehenden Ansprüche, wobei die halogenhaltige organische Verbindung mindestens ein Chloratom umfasst.
  5. Verfahren nach einem der vorangehenden Ansprüche, wobei die halogenhaltige organische Verbindung ein chemischer Kampfstoff, bevorzugt ein Schwefel-Senfgas, Stickstoff-Senfgas, Lewisit oder Derivate hiervon ist.
  6. Verfahren nach einem der vorangehenden Ansprüche, wobei die halogenhaltige organische Verbindung ein halogenhaltiger Kohlenwasserstoff, bevorzugt halogenhaltige aromatischer Kohlenwasserstoff, halogenhaltiger polyaromatischer Kohlenwasserstoff, halogenhaltiger cycloaliphatischer Kohlenwasserstoff und/oder halogenhaltiger aliphatischer Kohlenwasserstoff ist.
  7. Verfahren nach einem der vorangehenden Ansprüche, wobei das Molverhältnis von Verbindung (I) zu Verbindung (II) 1:2 ist.
  8. Verfahren nach einem der vorangehenden Ansprüche, wobei das elektrochemische Erzeugen in einem elektrochemischen Membranreaktor stattfindet.
  9. Verfahren nach einem der vorangehenden Ansprüche, wobei das stark eutektische Lösungsmittel einen Gefrierpunkt von bis zu 100°C aufweist.
EP20110190293 2011-11-23 2011-11-23 Verfahren zur Zersetzung einer halogenierten organischen Verbindung Not-in-force EP2596836B1 (de)

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EP2596836B1 true EP2596836B1 (de) 2014-03-05

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Publication number Priority date Publication date Assignee Title
CN110105619B (zh) * 2019-04-26 2020-12-25 中国科学院山西煤炭化学研究所 一种聚氨酯的可控降解回收方法

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Publication number Priority date Publication date Assignee Title
GB9906829D0 (en) 1999-03-24 1999-05-19 Univ Leicester Ionic liquids
GB0023706D0 (en) 2000-09-27 2000-11-08 Scionix Ltd Ionic liquids
US8147792B2 (en) * 2007-07-05 2012-04-03 King Saud University Method for the preparation of reactive compositions containing superoxide ion
US7812211B2 (en) * 2007-07-05 2010-10-12 King Saud University Process for the destruction of halogenated hydrocarbons and their homologous/analogous in deep eutectic solvents at ambient conditions
US7763768B2 (en) * 2007-07-05 2010-07-27 King Saud University Method for the preparation of reactive hydrogen peroxide in deep eutectic solvents

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