EP1237628B1 - Verfahren und vorrichtung zum zerstören von organischen phosphor- und/oder schwefelverbindungsschadstoffen - Google Patents

Verfahren und vorrichtung zum zerstören von organischen phosphor- und/oder schwefelverbindungsschadstoffen Download PDF

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EP1237628B1
EP1237628B1 EP00971499A EP00971499A EP1237628B1 EP 1237628 B1 EP1237628 B1 EP 1237628B1 EP 00971499 A EP00971499 A EP 00971499A EP 00971499 A EP00971499 A EP 00971499A EP 1237628 B1 EP1237628 B1 EP 1237628B1
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Prior art keywords
acid
composition
fact
accordance
percarboxylic
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French (fr)
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EP1237628A1 (de
Inventor
Jean-Pierre Schirmann
Christian Pralus
Claude Lion
Louis Da Conceicao
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Arkema France SA
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Arkema France SA
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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
    • A62D3/38—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
    • 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 the decontamination of fragile materials soiled by toxic agents such as organophosphorus compounds and organosulfur compounds without causing significant degradation of said materials. It relates in particular to a new decontaminating agent as well as a composition and a method for destroying these organophosphorus and / or organosulfur pollutants.
  • the invention is more particularly applicable to the treatment of fragile materials contaminated with organophosphorus compounds, such as organophosphates, amidophosphates, organoamidophosphates, phosphorothionates, phosphonothionates and phosphonoamidothionates used in the field of agriculture as insecticides and pesticides.
  • organophosphorus compounds such as organophosphates, amidophosphates, organoamidophosphates, phosphorothionates, phosphonothionates and phosphonoamidothionates used in the field of agriculture as insecticides and pesticides.
  • organosulfur compounds of the RS-R 'type, R and R' especially representing hydrocarbon radicals and halogenated hydrocarbon radicals.
  • organophosphorus compounds such as O, O-diethyl-Op-nitrophenyl phosphate (Paraoxon ®), O, O-diethyl-Op-nitrophenyl phosphonothioate (Parathion ®) and O, O-diethyl- O- (2-isopropyl-9-methyl-6-pyrimidyl) -phosphorothioate x (Diazinon ®) play an important role in agriculture as insecticides or as pesticides.
  • organophosphorus compounds such as O, O-diethyl-Op-nitrophenyl phosphate (Paraoxon ®), O, O-diethyl-Op-nitrophenyl phosphonothioate (Parathion ®) and O, O-diethyl- O- (2-isopropyl-9-methyl-6-pyrimidyl) -phosphorothioate x (Diazinon ®) play an important role in agriculture as insecticides
  • toxic organosulfur compounds such as 2'-dichloro-2'-diethyl sulphide or 2-phenyl-2-chlorodiethyl sulphide are also very aggressive chemical agents and their stability allows them to persist on a ground contaminated for several years, without experiencing a significant decrease in toxicity.
  • compositions currently available in the decontamination technique are sodium hydroxide solutions in aqueous medium or in methylglycol in the presence of amine, or calcium hypochlorite; however, such solutions are corrosive with respect to fragile materials and in particular alloys of light metals.
  • nucleophilic compounds are effective products for removing toxic agents of the organophosphorus and organosulfur series.
  • the hydroxyl anion in a strongly basic medium is able to neutralize these toxic agents.
  • the efficiency obtained is accompanied by a strong aggressiveness vis-à-vis the materials to be decontaminated.
  • Another way is to use in peroxygenic compounds, such as hydrogen peroxide, tert-butyl hydroperoxide, perborates and peracids, in a relatively basic or even neutral medium, because of their properties which are both nucleophilic and oxidising.
  • peroxygenic compounds such as hydrogen peroxide, tert-butyl hydroperoxide, perborates and peracids
  • the different peroxygen compounds are used in solutions containing quaternary ammonium surfactants, improving the contact between the peroxygen reagent and the toxic agent during the decontamination.
  • the peroxides currently proposed in the decontamination of materials contaminated by the different families of toxic agents, in particular Paracxon® and sulfur compounds, are in the form of aqueous solutions of linear long-chain peracids with carbon, pH between 6 and 8, or aqueous solutions based on industrial peracids such as magnesium monoperoxyphthalate or phthalimidoperhexanoic acid, these peracids being, in both cases, associated with surface-active agents, in particular of the ammonium salt type quaternary.
  • the first peracids are not commercially available and have poor stability and solubility
  • the second peracids, although commercially available, are in ambient temperature, have poor stability at high temperature and are not easy to handle for their implementation.
  • FR-A-2,761,080 describes a composition containing an aqueous solution of a percarboxylic acid, for example perpropionic acid, in combination with a quaternary ammonium cationic agent, for example cetyltrimethylammonium bromide. This composition is used for the decontamination of materials soiled with organophosphorus compounds.
  • WO-A-94/00548 describes a composition containing an aqueous solution of a percarboxylic acid, for example peracetic acid, and a quaternary ammonium cationic surfactant.
  • the present invention therefore firstly relates to the use of an acid selected from C 2 -C 4 percarboxylic acids in the decontamination of materials contaminated with organophosphorus and / or organosulfur compounds.
  • the percarboxylic acid used is in the form of an anhydrous or substantially anhydrous organic solution of said percarboxylic acid, in particular such as it was obtained by reaction of an aqueous solution of hydrogen peroxide with the acid. corresponding carboxylic acid miscible with water, in the presence of a catalyst and an organic solvent, possibly including that which allowed the continuous elimination by azeotropic distillation of the water of the reaction medium.
  • a preparation method and improved embodiments thereof are described in the patents French n ° 2,464,947 and 2,519,634 and in the European patent application EP-A-954 397 .
  • Such anhydrous or substantially anhydrous solutions are liquids soluble in water, which allows an easier implementation of the decontaminating solutions.
  • the preferred percarboxylic acid is perpropionic acid because of its high stability.
  • the anhydrous or substantially anhydrous organic solution of perpropionic acid which can be used comprises perpropionic acid, as product, propionic acid as unreacted reagent, ethyl propionate as solvent, hydrogen peroxide as unreacted reagent, sulfuric acid or boric acid as a catalyst, and dipicolinic acid as a stabilizer of the manufactured peracid solution.
  • the subject of the present invention is also a composition that can be used for the decontamination of materials soiled with organophosphorus and / or organosulfur compounds, this composition being characterized by the fact that it consists of an aqueous solution based on at least one percarboxylic acid. in C 2 to C 4 .
  • the percarboxylic acid or acids, in particular, perpropionic acid have advantageously been introduced into said composition in the form of an anhydrous or substantially anhydrous organic solution of said percarboxylic acid, as indicated above.
  • the percarboxylic acid (s) are present in the aqueous solution at a concentration of, for example, 3.78 x 10 -4 to 0.15 mol / l.
  • the aqueous solution is buffered at a pH of between 7 and 10, in particular at a fold of between 9 and 10.
  • the buffers that can be used are commercial solutions of pH 7 to 10.
  • pH 9 is obtained from an aqueous solution containing a mixture of boric acid (0.05 mol / l), potassium chloride (0.05 mol / l) and sodium hydroxide ( 0.022 mol / l).
  • the aqueous decontaminating composition also comprises at least one cationic surfactant.
  • surfactants are known and, for the most part, commercially available. They can be prepared by the methods described by CA Bunton et al., J. Am. Chem. Soc., 95, 2912 (1973) ) and by L. Horner et al., Phosphorus and Sulfur, 11, 339 (1981) ).
  • the surfactant (s) are present in the decontaminating aqueous composition, in particular at a concentration of 10 -3 to 0.1 mole per liter of composition.
  • the present invention also relates to a method for decontaminating materials contaminated with organophosphorus and / or organosulfur compounds, characterized in that the composition as defined above is applied to the soiled material by spraying, spraying or simple washing, or that soiling said soiled material in a tray containing the composition as defined above.
  • the molar ratio of C 2 to C 4 percarboxylic acid relative to the pollutant is generally 5 to 10 for organophosphorus pollutants (phosphate hydrolysis) or 3 to 5 for organosulfur pollutants (oxidation to sulfone).
  • Contaminated fragile materials include electronic circuits (resin, electronic components, solder), light alloys, polymers (poly (methyl methacrylate)), etc. These materials have been polluted by deposition of the toxic substance on the surface: it is thus a decontamination in heterogeneous phase.
  • composition containing the C 2 to C 4 percarboxylic acid, in particular perpropionic acid, in combination with the quaternary ammonium surfactant allows a virtually instantaneous degradation of the organophosphorus and organosulfur toxic compounds.
  • the composition has excellent stability over time at high temperatures, in contrast to conventional peracidic compositions, and that the C 2 -C 4 percarboxylic acid is in the form of a liquid soluble in water, which has an advantage when of the use of the composition and which makes it possible to obtain the degradation of the abovementioned toxic agents, in particular the total degradation of 2-phenyl-2'-chlorodiethyl sulphide in its non-toxic sulphonated form, which is not the case of other organic peracids which are only available in solid form and which have a low solubility in aqueous phase.
  • perpropionic acid having the following composition was used: Perpropionic acid 17.1% Propionic acid 22.2% Ethyl propionate 59.5% Oxygenated water 1% Sulfuric acid 0.05% Dipicolinic acid 0.08 which had been prepared according to the method described in the patent application French FR-A-2 519 634 but with ethyl propionate as the solvent.
  • the monitoring of the degradation of Paraoxon was carried out at 25 ° C. according to a technique using UV-visible spectrometry at the wavelength of 402 nm, corresponding to the maximum absorption of the released p-nitrophenate ion.
  • the progress of the chemical destruction reaction of 2-phenyl-2'-chlorodiethyl sulphide is determined by gas chromatographic analysis, consisting of taking samples over time, analyzed by chromatography after addition of a mineral reducer (sodium thiosulfate).
  • Table 2 indicates that the destruction of 2-phenyl-2'-chlorodiethyl sulphide by perpropionic acid occurs rapidly, thus confirming the exceptional properties of perpropionic acid in the decontamination of toxic agents.

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  • Business, Economics & Management (AREA)
  • General Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Management (AREA)
  • Detergent Compositions (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Processing Of Solid Wastes (AREA)
  • Compounds Of Unknown Constitution (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Claims (16)

  1. Verwendung einer Säure, die aus Percarboxylsäuren mit C2 bis C4 ausgewählt ist, bei der Dekontaminierung von Werkstoffen, die mit organophosphathaltigen und/ oder schwefelhaltigen Verbindungen verunreinigt sind, wobei die Percarboxylsäure in Form einer organischen wasserfreien Lösung der Percarboxylsäure vorliegt.
  2. Verwendung nach Anspruch 1,
    gekennzeichnet durch
    die Tatsache, daß die organische wasserfreie Percarboxylsäurelösung derartig ist, daß sie durch Reaktion einer wässrigen Wasserstoffperoxidlösung mit einer entsprechenden Carboxylsäure, die mit Wasser mischbar ist, im Beisein eines Katalysators und eines organischen Lösungsmittels erhalten wurde, darunter möglicherweise dasjenige, welches die dauerhafte Beseitigung von Wasser aus dem Reaktionsmedium durch Azeotropdestillation ermöglichte.
  3. Verwendung nach einem der Ansprüche 1 oder 2,
    gekennzeichnet durch
    die Tatsache, daß die Percarboxylsäure Perpropionsäure ist.
  4. Verwendung nach Anspruch 3 abhängig von Anspruch 2,
    gekennzeichnet durch
    die Tatsache, daß die wasserfreie organische Perpropionsäurelösung Perpropionsäure als Produkt, Propionsäure als Reaktionsmittel, das nicht reagiert hat, Ethylpropionat als Lösungsmittel, sauerstoffhaltiges Wasser als Reaktionsmittel, das nicht reagiert hat, Schwefelsäure oder Borsäure als Katalysator und Dipicolinsäure als Stabilisator der erzeugten Persäurelösung enthält.
  5. Zusammensetzung, die für die Dekontaminierung von Werkstoffen verwendbar ist, die durch organophosphorhaltige und/oder organoschwefelhaltige Verbindungen verunreinigt sind,
    gekennzeichnet durch
    die Tatsache, daß sie aus einer wässrigen Lösung auf Basis von zumindest einer Percarboxylsäure mit C2 bis C4 oder den Percarboxylsäuren besteht, die in die Zusammensetzung in Form einer organischen wasserfreien Lösung eingeführt wurden.
  6. Zusammensetzung nach Anspruch 5,
    gekennzeichnet durch
    die Tatsache, daß die Percarboxylsäure oder Percarboxylsäuren in die Zusammensetzung in Form einer organischen wasserfreien Lösung der Percarboxylsäure eingeführt wurden, so daß sie durch Reaktion einer wäßrigen Wasserstoffperoxidlösung mit einer wäßrigen Wasserstoffperoxidlösung mit der entsprechenden Carboxylsäure, die mit Wasser mischbar ist, im Beisein eines Katalysators oder eines organischen Lösungsmittels erhalten wurde, darunter möglicherweise dasjenige, welches die dauerhafte Beseitigung von Wasser aus dem Reaktionsmedium durch Azeotropdestillation ermöglichte.
  7. Zusammensetzung nach einem der Ansprüche 5 und 6,
    gekennzeichnet durch
    die Tatsache, daß die Percarboxylsäure die Perpropionsäure ist.
  8. Zusammensetzung nach Anspruch 7 abhängig von Anspruch 6,
    gekennzeichnet durch
    die Tatsache, daß die Percarboxylsäure in die Zusammensetzung in Form einer organischen wasserfreien Lösung eingeführt wurde, welche die Perpropionsäure als Produkt, die Propionsäure als Reaktionsmittel, das nicht reagiert hat, Ethylpropionat als Lösungsmittel, sauerstoffhaltiges Wasser als Reaktionsmittel, das nicht reagiert hat, Schwefelsäure oder Borsäure als Katalysator und Dipicolinsäure als Stabilisator der hergestellten Persäurelösung enthält.
  9. Zusammensetzung nach einem der Ansprüche 5 bis 8,
    gekennzeichnet durch
    die Tatsache, daß die Percarboxylsäure oder Percarboxylsäuren als wässrige Lösung mit einer Konzentration von 3,78 × 10-4 bis 0,15 mol/l vorliegen.
  10. Zusammensetzung nach einem der Ansprüche 5 bis 9,
    gekennzeichnet durch
    die Tatsache, daß die wäßrige Lösung auf einen pH-Wert gepuffert ist, der zwischen 7 und 10 liegt.
  11. Zusammensetzung nach Anspruch 10,
    gekennzeichnet durch
    die Tatsache, daß die wäßrige Lösung auf einen pH-Wert gepuffert ist, der zwischen 9 und 10 liegt.
  12. Zusammensetzung nach einem der Ansprüche 5 bis 11,
    gekennzeichnet durch
    die Tatsache, daß sie ebenfalls zumindest eine tensioaktive kationische Substanz umfasst.
  13. Zusammensetzung nach Anspruch 12,
    gekennzeichnet durch
    die Tatsache, daß die tensioaktive kationische Substanz oder Substanzen vom quaternären Ammoniumtyp sind, der insbesondere durch die Formel (I) dargestellt wird:
    Figure imgb0007
     in der:
    - R1, R2 und R3, die identisch oder unterschiedlich sind, jeweils eine Alkylgruppe mit C1 bis C4 oder eine Hydroxyalkylgruppe mit C1 bis C4 sind;
    - R4 eine Benzylgruppe oder eine lineare oder verzweigte Alkylgruppe mit C11 bis C18 ist; und
    - X ein Halogen- oder Hydroxylradikal ist,
    oder durch die Formel (II):
    Figure imgb0008
     in der:
    - R eine lineare Alkylgruppe mit C16 ist; und
    - X1 ein Halogen ist.
  14. Zusammensetzung nach Anspruch 13,
    gekennzeichnet durch
    die Tatsache, daß die tensioaktive Substanz oder Substanzen ausgewählt sind unter:
    - Cetyl-Trimethyl-Ammoniumbromid;
    - Cetyl-Trimethyl-Ammoniumchlorid;
    - Cetyl-Dimethyl-Hydroxy-2-Ethyl-Ammoniumbromid;
    - Cetyl-Methyl-Bis-(Hydroxy-2-Ethyl)-Ammoniumbromid;
    - Benzyl-Trimethyl-Ammoniumbromid; und
    - Cetyl-Diaza-1,4-Bicyclo-[2.2.2]-Octyl-Ammoniumbromid.
  15. Zusammensetzung nach einem der Ansprüche 12 bis 14,
    gekennzeichnet durch
    die Tatsache, daß die tensioaktive Substanz oder Substanzen in einer Menge von 10 3 bis 0,1 mol pro Liter der Zusammensetzung vorhanden sind.
  16. Verfahren zur Dekontaminierung von Werkstoffen, die durch organophosphorhaltige Verbindungen und/oder organoschwefelhaltige Verbindungen verunreinigt sind,
    gekennzeichnet durch
    die Tatsache, daß es auf den verunreinigten Werkstoff die Zusammensetzung, so wie sie nach einem der Ansprüche 5 bis 15 definiert ist, durch Sprühen, als Pulver oder durch Waschen anwendet, oder daß der verunreinigte Werkstoff in einem Behälter durchtränkt wird, der die Zusammensetzung enthält, so wie sie in einem der Ansprüche 5 bis 15 definiert ist.
EP00971499A 1999-10-29 2000-10-25 Verfahren und vorrichtung zum zerstören von organischen phosphor- und/oder schwefelverbindungsschadstoffen Expired - Lifetime EP1237628B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR9913571A FR2800291B1 (fr) 1999-10-29 1999-10-29 Composition et procede pour la destruction de polluants organophosphores et/ou organosoufres
FR9913571 1999-10-29
PCT/FR2000/002967 WO2001030452A1 (fr) 1999-10-29 2000-10-25 Composition et procede pour la destruction de polluants organophosphores et/ou organosoufres

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EP1237628A1 EP1237628A1 (de) 2002-09-11
EP1237628B1 true EP1237628B1 (de) 2008-05-14

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EP (1) EP1237628B1 (de)
AT (1) ATE395106T1 (de)
AU (1) AU1034401A (de)
CA (1) CA2389081C (de)
DE (1) DE60038896D1 (de)
FR (1) FR2800291B1 (de)
WO (1) WO2001030452A1 (de)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004080543A2 (en) 2003-03-12 2004-09-23 Queen's University At Kingston Method of decomposing organophosphorus compounds
FR2930732B1 (fr) * 2008-04-30 2010-05-14 Arkema France Composition et procede pour la destruction de polluants organophosphores et/ou organosoufres
JP6423365B2 (ja) 2013-12-20 2018-11-14 三井化学株式会社 半芳香族ポリアミド樹脂組成物およびその成型品

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2464947A1 (fr) * 1979-09-07 1981-03-20 Ugine Kuhlmann Procede de fabrication d'acides percarboxyliques
FR2519634B1 (fr) * 1982-01-13 1986-09-12 Ugine Kuhlmann Perfectionnement aux procedes de synthese des acides percaboxyliques
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.
GB9213059D0 (en) * 1992-06-19 1992-08-05 Laporte Esd Ltd Compositions
FR2761080B1 (fr) * 1997-03-21 2002-07-19 Quadrimex Composition a base de peracides pour le nettoyage, la desinfection et la decontamination de surfaces souillees par des agents toxiques

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EP1237628A1 (de) 2002-09-11
AU1034401A (en) 2001-05-08
FR2800291B1 (fr) 2004-07-09
ATE395106T1 (de) 2008-05-15
FR2800291A1 (fr) 2001-05-04
CA2389081A1 (fr) 2001-05-03
WO2001030452A1 (fr) 2001-05-03
CA2389081C (fr) 2009-12-22

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