EP0848628B1 - Verfahren zur dekontaminierung, mit einer persäure enthaltenden zusammensetzung, von materialien die durch toxische mittel kontaminiert sind - Google Patents

Verfahren zur dekontaminierung, mit einer persäure enthaltenden zusammensetzung, von materialien die durch toxische mittel kontaminiert sind Download PDF

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Publication number
EP0848628B1
EP0848628B1 EP97905197A EP97905197A EP0848628B1 EP 0848628 B1 EP0848628 B1 EP 0848628B1 EP 97905197 A EP97905197 A EP 97905197A EP 97905197 A EP97905197 A EP 97905197A EP 0848628 B1 EP0848628 B1 EP 0848628B1
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EP
European Patent Office
Prior art keywords
group
surfactant
acid
peracid
bromide
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.)
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English (en)
French (fr)
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EP0848628A1 (de
Inventor
Claude Lion
Claude Charvy
Gérard DELMAS
Gilbert Magnaud
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Direction General de lArmement DGA
Gouvernement de la Republique Francaise
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Delegation Generale pour lArmement
Gouvernement de la Republique Francaise
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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
    • A62D3/38—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
    • A62D2101/26—Organic substances containing nitrogen or phosphorus
    • 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 present invention relates to a method of decontamination of materials soiled by agents toxic, more particularly using a composition based on peracids ensuring efficient decontamination of materials contaminated by toxic agents such as compounds organophosphorus or organosulfur, without causing degradation notable of said materials
  • organophosphate inhibitor compounds cholinesterases such as organophosphates, amidophosphates, organoamidophosphates, phosphorothionates, phosphonothionates and phosphoroamidothionates, can be used in agriculture as insecticides and pesticides.
  • organosulfur are known as blistering agents and used as poisonous agents of war.
  • organophosphorus compounds used as pesticides or insecticides in agriculture we may especially mention O, O-diethyl-O-p-nitrophenyl phosphate (Paraoxon) and O, O-diethyl-O-p-nitrophenyl phosphorothioate (Parathion), while O-ethyl-S- (diisopropylaminoethyl-2) -methylphosphorothiolate (VX) is a toxic agent of war well known.
  • VX O-ethyl-S- (diisopropylaminoethyl-2) -methylphosphorothiolate
  • VX is a toxic agent of war well known.
  • These compounds work by blocking irreversible nerve transmission, by binding covalent to acetylcholinesterase, causing death by accumulation of acetylcholine in the body.
  • compound organosulfur used as a war toxicant we can also cite dichloro-2,2'-dieth
  • compositions most effective currently used in the technique of decontamination are soda solutions in the methylglycol with diethylamine, or hypochlorite calcium, but these solutions are very corrosive.
  • nucleophilic compounds have the qualities required to remove toxic substances from the organophosphate and organosulfur series.
  • CA Bunton et al., J. Am. Chem. Soc ., 95 , 2912 (1973) have demonstrated the properties of the hydroxyl ion for this purpose; other reagents have also been proposed, including hydroxamic acids, oximes, mono- and polyphenols, aldehyde hydrates, certain amines, as well as calcium or sodium hypochlorites.
  • peroxyanions as hydrogen peroxide, tert-butyl hydroperoxide, perborates and peracids, due to their properties at the both nucleophilic and oxidative.
  • compositions still containing surfactants improving the contact between the reagent used and the agent toxic to eliminate, to speed up decontamination.
  • ammonium type surfactants quaternary accelerates the destruction of toxins by a micellar catalysis.
  • patent FR-A-2,651,133 describes compositions consisting of solutions containing peracids linear long carbon chain, pH between 6 and 8, generally associated with surfactants such as cetyl trimethyl ammonium bromide, cetyl bromide 2-dimethyl hydroxyethyl ammonium, cetyl methyl bromide bis (hydroxyethyl-2) ammonium or cetyl diaza-1,4-bromide bicyclo (2.2.2) octyl ammonium.
  • surfactants such as cetyl trimethyl ammonium bromide, cetyl bromide 2-dimethyl hydroxyethyl ammonium, cetyl methyl bromide bis (hydroxyethyl-2) ammonium or cetyl diaza-1,4-bromide bicyclo (2.2.2) octyl ammonium.
  • Such compositions allow to destroy Paraoxon, VX and Yperite.
  • the peracids used are not available in the trade and the stability of the compositions
  • FR-A-2,676,368 describes aqueous compositions based on magnesium monoperoxyphthalate and surfactant of the quaternary ammonium salt type, usable for the decontamination of materials soiled by certain agents neurotoxic, including VX, and vesicants such as yperite.
  • the composition consists of a solution aqueous pH buffered between 8 and 11, and preferably between 9 and 10.
  • R 1 and R 2 preferably represent an alkyl group of 1 to 4 carbon atoms, and for example a methyl, ethyl or n-propyl group.
  • the peracids used in the invention are products available commercially or the preparation of which can be carried out easily by usual techniques, by the action of hydrogen peroxide in an acid medium (for example in cold concentrated sulfuric acid medium) on the corresponding acids.
  • a method of preparing such peracids is described by C. Lion et al. Bull. Soc. Chim . Belg. 99 (2) 127 (1990).
  • the cationic surfactant of the quaternary ammonium type is preferably represented by the general formula (III): in which R 1 , R 2 and R 3 , identical or different, represent an alkyl or hydroxyalkyl group of 1 to 4 carbon atoms, R 4 represents a linear or branched alkyl group of 11 to 18 carbon atoms, and X represents a halogen or a hydroxyl radical.
  • R 1 , R 2 and R 3 represent a methyl group, an ethyl group or a hydroxyethyl group
  • R 4 represents a cetyl group
  • X is chlorine, bromine or a radical -OH.
  • the surfactant of general formula (III) is chosen from bromide or cetyl trimethyl chloride ammonium, cetyl dimethyl hydroxyethyl-2 bromide ammonium, cetyl methyl bis (2-hydroxyethyl) bromide ammonium or cetyl diaza-1,4 bicyclo (2.2.2) octyl bromide ammonium.
  • surfactants are known and, for the most part, commercially available. They can be prepared by the methods described by CA Bunton et al. (cited above) and by L. Horner et al., Phosphorus and Sulfur, 11 , 339 (1981). For example, cetyl dimethyl hydroxyethyl-2-ammonium bromide can be obtained by refluxing a solution of hexadecyl bromide and dimethylethanolamine in a mixture of acetonitrile and methanol and by recrystallizing the crystals obtained from methanol.
  • the composition according to the invention preferably comes in the form of a solution buffered aqueous, pH between 8 and 11, preferably between 9 and 10, for example an aqueous solution of a mixture baking soda and sodium bicarbonate.
  • This aqueous solution is applied to the material to be decontaminate, by spraying, spraying or simple washing, or it is possible to dip the materials in a tank containing a composition according to the invention.
  • the peracid and the quaternary ammonium type surfactant when X is a hydroxyl, can be combined within the same molecule, to form a tetraalkylammonium percarboxylate.
  • Such compound can be obtained by action of the peracid of formula (I) or (II) on a tetraalkylammonium hydroxide, in amounts stoichiometric.
  • This variant is particularly advantageous because the percarboxylate can be generated in situ, and looks like this in aqueous solution, without the need to use a carbonate buffer which is replaced here by hydroxide tetraalkylammonium.
  • Tetraalkylammonium hydroxide can be prepared using the method described by L. Sepulveda et al., J. Phys. Chem ., 89 , 5322 (1985), starting from carbon sulphide and sodium ethylate, and action of a tetraalkylammonium bromide in sulfuric medium, then treatment with a base such as barium hydroxide.
  • compositions according to the invention for the decontamination of materials contaminated with compounds organophosphorus or toxic organosulfur has been verified by causing them to act on known compounds such as O, O-diethyl-O-p-nitrophenyl phosphate (Paraoxon), in the series of organophosphorus compounds, and 2-phenyl-2'-chlorodiethyl sulfide, analog of Yperite, in the organosulfur series.
  • compositions of the invention cause the destruction of compounds such as Paraoxon and the analogue of Yperite practically Instant.
  • This result is obtained with the composition containing the peracid of formula (I) or (II) in combination with the quaternary ammonium type surfactant, as well that with the composition containing a percarboxylate of tetraalkylammonium.
  • composition of the invention has excellent stability over time, unlike to conventional compositions based on peracids, and is not aggressive towards the various materials commonly treated.
  • compositions according to the invention comprising either a combination of peracid and surfactant (Example 1), or a tetraalkylammonium percarboxylate (Example 2).
  • the kinetics of destruction are carried out for the Paraoxon according to a usual technique, in UV spectroscopy at 402 nm, corresponding to the maximum absorption of the p-nitrophenate ion released, at 25 ° C.
  • the destruction speeds of the Yperite analog above are determined by chromatographic analysis at regular intervals, after addition of a mineral reducer (ferrous sulfate) or organic (triphenylphosphine). We operate at a pH of 9.
  • Table 1 below indicates the half-reaction time (in s.), At 25 ° C., per action of each of the four peracids indicated below, in 2.10 -3 M solution at pH 9, on the Paraoxon ( 5.10 -5 M).
  • compositions of the invention provide results equivalent to those obtained with magnesium monoperphthalate (MPPM) which is the best decontaminant currently known for Paraoxon.
  • MPPM magnesium monoperphthalate
  • the compositions of the invention are also effective against organosulfur compounds.

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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)
  • Detergent Compositions (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Claims (6)

  1. Verfahren zur Dekontaminierung von durch toxische Organophosphoroder Organoschwefel-Verbindungen kontaminierten Materialien, bei dem eine Zusammensetzung verwendet wird, die eine Persäure und ein oberflächenaktives Mittel enthält, dadurch gekennzeichnet, daß die Zusammensetzung umfaßt
    eine Persäure oder eines ihrer Salze, ausgewählt aus
    einer Imidopersäure der allgemeinen Formel (I)
    Figure 00160001
    worin n eine ganze Zahl zwischen 3 und 8 ist und der Rest R1, der in jeder Gruppe -CHR1- gleich oder verschieden sein kann, eine Alkylgruppe oder eine Phenylgruppe ist,
    Phthalimidoperpropionsäure oder Phthalimidopercapronsäure,
    einer Dipersäure der allgemeinen Formel (II) HO3C - (CHR2)p - CO3H worin p eine ganze Zahl zwischen 2 und 10 ist und R2 die gleiche Bedeutung wie R1 hat, und
    Perdidekansäure, Perdinonansäure und Perdidodekansäure,
    sowie ein kationisches oberflächenaktives Mittel vom Typ einer quater nären Ammoniumverbindung.
  2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß das oberflächenaktive Mittel vom Typ einer quaternären Ammoniumverbindung der allgemeinen Formel (III) entspricht,
    Figure 00170001
    worin R1, R2 und R3, die gleich oder verschieden sein können, eine Alkyl- oder Hydroxyalkylgruppe mit 1 bis 4 Kohlenstoffatomen, R4 eine geradkettige oder verzweigte Alkylgruppe mit 11 bis 18 Kohlenstoffatomen und X ein Halogen oder einen Hydroxylrest bedeuten.
  3. Verfahren nach Anspruch 2, dadurch gekennzeichnet, daß R1, R2 und R3 eine Methyl-, Ethyl- oder Hydroxyethylgruppe, R4 eine Cetylgruppe und X Chlor, Brom oder eine OH-Gruppe bedeuten.
  4. Verfahren nach Anspruch 3, dadurch gekennzeichnet, daß das oberflächenaktive Mittel der allgemeinen Formel (III) aus folgenden Verbindungen ausgewählt wird: Cetyltrimethylammoniumbromid oder Cetyltrimethylammoniumchlorid, Cetyldimethyl-2-hydroxyethyl-ammoniumbromid, Cetylmethyl-bis-(2-hydroxyethyl)-ammoniumbromid oder Cetyldiaza-1,4-bicyclo(2.2.2)-octylammoniumbromid.
  5. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß die Zusammensetzung aus einer wäßrigen Lösung gebildet wird, die auf einen pH-Wert zwischen 8 und 11 gepuffert ist.
  6. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß die Persäure und das oberflächenaktive Mittel innerhalb desselben Moleküls unter Bildung eines Tetraalkylammoniumpercarboxylats vereint vorliegen.
EP97905197A 1996-03-14 1997-02-13 Verfahren zur dekontaminierung, mit einer persäure enthaltenden zusammensetzung, von materialien die durch toxische mittel kontaminiert sind Expired - Lifetime EP0848628B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR9603204A FR2746020B1 (fr) 1996-03-14 1996-03-14 Composition a base de peracides pour la decontamination de materiaux souilles par des agents toxiques
FR9603204 1996-03-14
PCT/FR1997/000274 WO1997033655A1 (fr) 1996-03-14 1997-02-13 Composition a base de peracides pour la decontamination de materiaux souilles par des agents toxiques

Publications (2)

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EP0848628A1 EP0848628A1 (de) 1998-06-24
EP0848628B1 true EP0848628B1 (de) 2003-04-23

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US (1) US6143088A (de)
EP (1) EP0848628B1 (de)
CA (1) CA2218079A1 (de)
DE (1) DE69721197T2 (de)
ES (1) ES2192666T3 (de)
FR (1) FR2746020B1 (de)
IL (1) IL121824A (de)
WO (1) WO1997033655A1 (de)

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US7582594B2 (en) * 2003-10-17 2009-09-01 Applied Research Associates, Inc. Dioxirane formulations for decontamination
US8110538B2 (en) * 2005-01-11 2012-02-07 Biomed Protect, Llc Peracid/peroxide composition and use thereof as an anti-microbial and a photosensitizer
EP1928946A2 (de) * 2005-01-11 2008-06-11 Clean Earth Technologies, LLC Formulierungen zur dekontamination toxischer chemikalien
US8084662B2 (en) * 2005-05-09 2011-12-27 ChK Group Inc. Method for degrading chemical warfare agents using Mn(VII) oxide with-and-without solid support
US20100179368A1 (en) * 2008-11-07 2010-07-15 Aries Associates, Inc. Novel Chemistries, Solutions, and Dispersal Systems for Decontamination of Chemical and Biological Systems

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1054473A (de) * 1964-05-08
US3749673A (en) * 1971-02-22 1973-07-31 Procter & Gamble Bleach-fabric softener compositions
US3749674A (en) * 1971-02-22 1973-07-31 Procter & Gamble Bleach compositions
US3996152A (en) * 1975-03-27 1976-12-07 The Procter & Gamble Company Bleaching composition
DE3575574D1 (de) * 1984-05-01 1990-03-01 Unilever Nv Fluessige bleichmittelzusammensetzungen.
US4902441A (en) * 1988-03-31 1990-02-20 The United States Of America As Represented By The Secretary Of The Navy Self moistening composition for deactivating toxic substances and method of use
DE3823172C2 (de) * 1988-07-08 1998-01-22 Hoechst Ag omega-Phthalimidoperoxihexansäure, Verfahren zu dessen Herstellung und dessen Verwendung
US4992194A (en) * 1989-06-12 1991-02-12 Lever Brothers Company, Division Of Conopco Inc. Stably suspended organic peroxy bleach in a structured aqueous liquid
FR2651133B1 (fr) * 1989-08-22 1992-10-23 France Etat Armement Procede de decontamination par des solutions de peracides de materiaux contamines par des agents toxiques.
FR2676368B1 (fr) * 1991-05-15 1994-10-28 France Etat Armement Composition de decontamination a base de monoperoxyphtalate de magnesium et procede de decontamination de materiaux contamines par des agents toxiques utilisant cette composition.

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Publication number Publication date
US6143088A (en) 2000-11-07
IL121824A (en) 2002-04-21
WO1997033655A1 (fr) 1997-09-18
CA2218079A1 (fr) 1997-09-18
IL121824A0 (en) 1998-02-22
FR2746020A1 (fr) 1997-09-19
FR2746020B1 (fr) 1998-04-24
DE69721197D1 (de) 2003-05-28
DE69721197T2 (de) 2004-04-01
ES2192666T3 (es) 2003-10-16
EP0848628A1 (de) 1998-06-24

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