IL208609A

IL208609A - Composition and process for the destruction of organophosphorus and/or organosulphur pollutants

Info

Publication number: IL208609A
Application number: IL208609A
Authority: IL
Original assignee: Arkema France
Priority date: 2008-04-30
Filing date: 2010-10-11
Publication date: 2013-12-31
Also published as: EP2271410A2; WO2009141548A2; WO2009141548A3; ES2374703T3; IL208609A0; ATE528050T1; JP5437363B2; JP2011522066A; CN102015035B; FR2930732B1; FR2930732A1; CN102015035A; EP2271410B1

Abstract

The invention relates to a decontaminating composition comprising: (i) perpropionic acid, (ii) dipicolinic acid, (iii) a salt of hydroxyethyldiethylphosphonic acid, (iv) a surface-active agent, and (v) an alkalinizing agent. The decontaminating compositions that are the subject of the invention have a high stability and high effectiveness, enabling a rapid destruction of the toxic organophosphorus or organosulphur agents.

Description

JVMM IN 1 ) it ts» »->ttii tj»»flm Ο>»ΊΙΝ ο βιη jm>¾mb T* riiii wan COMPOSITION AND PROCESS FOR THE DESTRUCTION OF ORGANOPHOSPHORUS AND/OR ORGANOSULPHUR POLLUTANTS ARKEMA FRANCE C.204594 COMPOSITION AND PROCESS FOR THE DESTRUCTION OP ORGANOPHOSPHORUS AND/OR ORGANOSULPHUR POLLUTANTS The invention relates to the decontamination of organophosphorus or organosulfur pollutants and/or toxic agents, in particular in the field of chemical warfare agents or in the field of agriculture, for example the decontamination of insecticides. It relates in particular to a novel decontaminating composition comprising two specific stabilizing agents, and also to a process for the destruction of these organophosphorus and/or organosulfur pollutants.

In the field of chemical warfare agents, there are currently many organophosphorus esters derived from phosphoric and phosphinic acids, such as Tabun, Sarin or Soman. These compounds have a high neurotoxicity owing to their phosphorylating capacity with respect to cholinesterases, the inhibition of which leads to death due to accumulation of acetylcholine in the organism.

Moreover, toxic organosulfur products, such as industrial sulfides or warfare agents of the vesicant family, for instance yperite, also exist. .

In the agricultural field, organophosphorus toxic compounds exist, such as organophosphates , amidophosphates, organoamidophosphates, phosphoro-thionates, phosphonothionates and phosphonoamido-thionates, used as insecticides and pesticides, and also organosulfur compounds of the R-S-R' type, R and R' representing, in particular, hydrocarbon-based radicals or halogenated hydrocarbon-based radicals.

Among the most well known organophosphorus compounds, compounds such as O, 0-diethyl-O-p-nitrophenyl phosphate (Paraoxon), 0, O-diethyl-O-p-nitrophenyl phosphono-thioate (Parathion) and 0, 0-diethyl-0- (2-isopropyl-4- methyl- 6-pyrimidyl) phosphorothioate (Diazinon) play a major role in agriculture as insecticides or as pesticides .

Moreover, the toxic organosulfur compounds, such as dichloro-2, 2 ' -diethyl sulfide or 2-phenyl-2-chlorodiethyl sulfide, are also very aggressive chemical agents, the stability of which enables them to persist on a contaminated area for several years, without experiencing any substantial decrease in toxicity.

The existence of large stocks of the products listed above is a problem. Their elimination involves in particular the use of decontaminating compositions to be applied to the products themselves or to the material or the individuals contaminated. The decontaminating compositions can be used as a replacement for or in combination with physical methods for displacement of toxic agents.

It is therefore important to be able to have, in particular in the case of intentional or accidental use of such compounds, a decontaminating composition capable of degrading the toxic products themselves and of rapidly and effectively decontaminating the materials contaminated with toxic agents.

The most effective compositions currently available are solutions of sodium hydroxide in an aqueous medium or in methyl glycol ( 1 , 2-propanediol ) in the presence of an amine, or of calcium hypochlorite; however, such solutions are corrosive with respect to fragile materials, and in particular light-metal alloys.

It is well known that nucleophilic compounds are effective products for eliminating toxic agents of the organophosphorus and organosulfur series. Thus, the hydroxyl anion in a strongly basic medium is capable of neutralizing these toxic agents. However, the effectiveness obtained is accompanied by strong aggressiveness with respect to the materials to be decontaminated.

Another approach consists in using, in a not very basic medium, or even a medium close to neutrality, peroxygenated compounds such as aqueous hydrogen peroxide solution, tert-butyl hydroperoxide, perborates and peracids, owing to both the nucleophilic and oxidizing properties thereof.

The various peroxygenated compounds are most commonly used in solutions containing surfactants of the quaternary ammonium type, which improve the contact between the peroxygenated reactant and the toxic agent during the decontamination.

The peroxides proposed at the current time in the decontamination of materials soiled with the various families of toxic agents, in particular Paraoxon? , and the sulfur-containing compounds, are in the form of aqueous solutions of linear peracids comprising a long carbon chain, of pH between 6 and 8, or of aqueous solutions based on industrial peracids such as magnesium monoperoxyphthalate or phthalimidoperhexanoic acid, these peracids being, in both cases, combined with surfactants, in particular of the quaternary ammonium salt type.

However, the first peracids are rarely commercially available at an industrial level and have a mediocre stability and a mediocre solubility, and the second peracids, although they are commercially available, are in solid form at ambient temperature, and have a mediocre stability at high temperature, and are not easy to handle when used.

Aqueous compositions based on C2 to C percarboxylic acids and on dipicolinic acid have been described in international application WO 01/30452 as a decontaminating agent. However, such compositions exhibit stability problems and use anhydrous percarboxylic acids obtained by an expensive process of azeotropic distillation.

An aqueous composition comprising a peroxidizing agent which may be a peracid, as a decontaminating agent, is described in patent application EP 0894512. Nevertheless, this type of composition has a relatively weak decontaminating effect.

There remains therefore a real need for new decontaminating compositions which have a greater stability than those mentioned above, and which have a great effectiveness, enabling rapid destruction of organophosphorus or organosulfur toxic agents.

The applicant has developed a composition which makes it possible to solve the above problems, and in particular has developed a composition which has excellent stability and excellent effectiveness, resulting in rapid destruction of the toxic agents.

The subject of the present invention is therefore, firstly, a decontaminating composition comprising: (i) perpropionic acid, (ii) dipicolinic acid, (iii) hydroxyethylidene diphosphonic acid (HEDP or salts thereof), (iv) a surfactant, and (v) a basifying agent.

Surprisingly, it has been noted that the composition as defined above is sufficiently stable to obtain sustained decontamination effectiveness.

Surprisingly, it has also been noted that the composition which is the subject of the invention, comprising perpropionic acid, exhibits a greater decontamination effectiveness than compositions comprising peracetic acid (examples 2 and 3) .

Preferably, the hydroxyethylidene diphosphonic acid salt is sodium hydroxyethylidene diphosphonate (HEDP) .

For the purpose of the present invention, the term "decontaminating composition" is intended to mean a composition that can be used for the decontamination of materials soiled with organophosphorus and/or organosulfur compounds or for the degradation of the toxic products themselves.

Advantageously, the perpropionic acid used is in the form of an aqueous solution, in particular as obtained by reaction of an aqueous solution of hydrogen peroxide with propionic acid, in the presence of a catalyst, such as sulfuric acid or boric acid. Such a preparation process is, for example, described in French patent application FR2462425. Unlike the anhydrous solutions of perpropionic acid that are described in French patent applications Nos FR2464941 and FR2519634, the aqueous solutions are obtained with a simple process, which does not implement a step of azeotropic distillation with toxic or inflammable organic solvents such as 1, 2-dichloroethane or cyclohexane.

Thus, the perpropionic acid used is in the form of an aqueous solution comprising: perpropionic acid as product, propionic acid as reactant which is not reacted, aqueous hydrogen peroxide solution as reactant which has not reacted, and sulfuric acid or boric acid as catalyst.

The decontaminating composition defined above can therefore comprise, in addition to compounds (i) to (v) : propionic acidr aqueous hydrogen peroxide solution, and sulfuric acid and/or boric acid.

Such compositions are water-soluble liquids, which makes the decontaminating composition which is the subject of the invention easy to use.

In one particular embodiment of the invention, the composition defined above is in the form of an aqueous solution. Thus, the subject of the invention is also an aqueous solution comprising a decontaminating composition as defined above.

The compositions which are the subject of the invention comprise a basifying agent. Preferably, the basifying agent is chosen from sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, sodium phosphate, potassium phosphate, ammonium phosphate, sodium silicates, potassium silicates, ammonium silicates, sodium borates, potassium borates and ammonium borates, and mixtures thereof. The basifying agent (s) make(s) it possible to adjust the pH of the compositions which are the subject of the invention. Advantageously, the compositions which are the subject of the invention have a pH above 7, preferably between 8 and 12, in particular between 8.5 and 9.5.

The compositions according to the invention can be buffered at a pH of between 7 and 10. When the composition which is the subject of the invention is a basic composition, the dipicolinic acid, the perpropioiiic acid and the HEDP can be in the form of their corresponding salts.

The compositions which are the subject of the invention can also comprise an alkaline buffer. For the purpose of the present invention, the term "alkaline buffer" is intended to mean both a single type of alkaline buffer and a mixture of alkaline buffers. The compositions according to the invention comprise an alkaline buffer such as an alkaline carbonate or an alkaline silicate, in particular potassium carbonate or sodium carbonate.

For the purpose of the present invention, the term "surfactant" is intended to mean an anionic, cationic, nonionic or amphoteric surfactant, used in a proportion of 0 to 25%, preferably 5% to 20% by weight, relative to the total weight of the composition.

As cationic surfactant, mention may be made of those of the quaternary ammonium type, and for example: - cetyltrimethylammonium bromide, - cetyltrimethylammonium chloride, - cetyldimethyl (2-hydroxyethyl) ammonium bromide, - cetylmethylbis (2-hydroxyethyl) ammonium bromide, - benzyltrimethylammonium bromide, and - cetyldiaza-1 , 4-bicyclo [ 2 . 2 . 2 ] octylammonium bromide.

These surfactants are known and most of them are commercially available. They can be prepared by the methods described by C.A. Bunton et al.r J. Am. Chem. Soc, 95, 2912 (1973) and by L. Horner et al., Phosphorus and Sulfur, 11, 339 (1981).

As nonionic surfactant that can be optionally used, mention may be made, for example, of: - alkoxylated fatty alcohols of formula: -[ (CH2)20]m-[CH2CH(CH3)0]n-H in which R is an alkyl or alkenyl containing from 8 to 22 carbon atoms, preferably 12 to 14 carbon atoms; n and mr independently, represent an integer from 0 to 50, of which the sum n + m > 1; - alkylpolyglucosides of formula R' ' ' - [glucose] n- in which R' ' ' is a C8-Ci6 alkyl and n is an integer from 1 to 3; - esters of reduced sugars, polyol esters and their ethoxylated derivatives, such as, for example, sorbitan monostearate, glyceryl monostearate or ethylene glycol monostearate, or ethoxylated sorbitan monostearate comprising 20 ethylene oxides; - ethoxylated alkylamides of formula: in which R is as defined above and r and s are integers from 0 to 15, of which the sum r + s > 1; - alkylpyrrolidones, the alkyl group of which is C6-C20 and mixtures thereof.

Preferably, the perpropionic acid is present in said aqueous solution at a concentration, for example, of from 0.05 to 4.5 mol/1.

In one preferred embodiment, the composition which is the subject of the invention comprises, by weight relative to the total weight of the composition: - 4% to 16% of perpropionic acid, - 0.1% to 2% of dipicolinic acid, - 0.5% to 5% of sodium hydroxyethyldiethyl phosphonate, - 5% to 20% of surfactant, - 2% to 20% of a basifying agent, and - 5% to 15% by weight of alkaline buffer.

The solutions which are the subject of the invention can also comprise at least one constituent chosen from a hydrotropic agent, such as urea, or the sodium cumene sulfonate, a viscosifying agent, such as xanthan gum, modified corn starch or hydroxyethylcellulose, or else an antifoam.

The compositions may be in the form of a powder, a liquid, a gel or a suspension.

The compositions according to the invention are preferably used in an aqueous solution at a concentration of from 0.5% to 40% by weight of perpropionic acid relative to the total weight of the solution. They can also be used in the form of emulsions or of microe ulsions after dispersion in an organic, water-immiscible solvent such as, for example, aliphatic or aromatic, hydrocarbons, which are optionally chlorinated, for example toluene, xylene, methylene chloride and tetrachloroethylene.

They can be used manually or mechanically by sprinkling, painting, spraying, dipping,, impregnation. or any other operation enabling contact of said compositions with contaminated material or individuals.

The subject of the present invention is also a process for decontaminating organophosphorus or organosulfur toxic agents and/or pollutants, which comprises bringing said toxic agent and/or pollutant into contact with a composition as defined above.

Said organophosphorus or organosulfur toxic agent and/or pollutant may, for example, be, in the military field, an organophosphorus or organosulfur warfare agent, or in the agricultural field, an organophosphorus or organosulfur plant-protection agent, in particular an insecticide, or alternatively an industrial pollutant.

The subject of the present invention is also a process for decontaminating materials soiled with organophosphorus and/or organosulfur compounds, comprising the application to the soiled material of the composition as defined above, by projection, spraying or simple washing, or dipping said soiled material in a container containing the composition as defined above.

Owing to the pH of the compositions which are the subject of the invention, when soiled materials are decontaminated, said materials can be chosen both from hardened vehicles coated with polyurethane paints, nonhardened vehicles (glycerophthalic paints, surfaces with a high porosity, presence of elastomers) and from sensitive equipment (vehicle interiors, radios, electronic equipment) .

Owing to their low aggressiveness, these compounds can also be used for decontaminating individuals through contact with the skin.

The molar ratio of perpropionic acid relative to the pollutant is generally from 5 to 10 for organophosphorus pollutants (hydrolysis to phosphate) or from 3 to 5 for organosulfur pollutants (oxidation to sulfone) .

The subject of the invention is also a process for obtaining a decontaminating composition in accordance with the invention. This process comprises the following successive steps: a) obtaining a composition comprising perpropionic acid, dip colinic acid and hydroxyethylidene diphosphonic acid, b) dissolving the composition obtained in step a} in an aqueous composition comprising a surfactant consisting of an amine oxide, and a basifying agent.

In another embodiment of the invention, a process for obtaining a decontaminating composition comprises the following successive steps: a) obtaining a composition comprising perpropionic acid and dipicolinic acid, b) dissolving the composition obtained in step a) in an aqueous composition comprising a surfactant, a basifying agent, .a d a - hydroxyethylidene diphosphonic acid salt, and preferably sodium hydroxyethylidene diphosphonate .

By way of example, the hydroxyethylidene diphosphonic acid of the composition which is the subject of the invention can consist of the product sold by the company Solutia under the trade name Dequest 2010? , and the sodium hydroxyethylidene diphosphonate can consist of the product sold by the company Solutia under the trade name Dequest 2016? .

The following examples illustrate the present invention without, however, limiting the scope thereof. In these examples, the percentages are by weight unless otherwise indicated.

EXAMPLE 1 The perpropionic acid solution is prepared by mixing: 1000 g of propionic acid, 500 g of aqueous hydrogen peroxide solution at 70%, 25 g of sulfuric acid, 7.5 g of dipicolinic acid and 15 g of hydroxyethylidene diphosphonic acid (Dequest 20107 ) . The mixture is left to stir for 12 h at ambient temperature in order to obtain the equilibrium concentrations. The solution thus prepared contains: * The aqueous hydrogen peroxide solution is titrated with cerium (IV) sulfate.

** The total active oxygen is titrated by iodometry. The perpropionic acid is determined by a difference between the total active oxygen and the aqueous hydrogen peroxide. 370 g of the previously prepared solution are then mixed with: - 70 g of Barquat MS 100 (from Lonza} - 100 g of Glucopon7 , - 90 g of potassium hydroxide, - 190 g of potassium carbonate, and - 900 g of water, for decontamination application.

EXAMPLE 2 The reactivity as a function of time, of the formulation prepared in example 1, is tested in 1 decontamination on Paraoxon' .

In a stirred glass reactor, 1.8 g of the formulation prepared in example 1 are added to 50 mg of Paraoxon7. The initial decontaminant /toxic agent molar ratio is therefore 5.8. T minutes after the addition, a sample is taken and the reaction is stopped by adding an excess of sodium thiosulfate. 8 ml of water saturated with NaCl, 10 ml of 50/50 ethyl acetate/hexane and 0.1% of dibutyl sebacate (internal standard) are then added to the sample. The organic phase is removed and dried over sodium sulfate and the residual Paraoxon7 is quantitatively determined by gas chromatography.

This procedure is repeated after various aging times for the formulation prepared in example 1.

The results are summarized in the following table: EXAMPLE 3 (not in accordance with the invention) The perpropionic acid-based formulation described in example 1 was compared with a similar formulation based on peracetic acid. The 39% peracetic acid solution is prepared according to a procedure identical to example 1, replacing the propionic acid with acetic acid, and then the same amounts of the other constituents are added.

The resulting formulation is tested with Paraoxon7 according to the procedure described in example 2. The initial decontaminant/toxic agent molar ratio is 6.8. The results are given in the following table: These examples therefore show the advantage of the perpropionic acid-based formulation compared with the peracetic acid-based formulation for the decontamination of organophosphorus toxic agents.

Claims

1. A decontaminating composition comprising: (i) perpropionic acid, (ii) dipicolinic acid-, (iii) hydroxyethylidene diphosphonic acid or a salt thereof, (iv) a surfactant, and (v) a basifying agent.

2. The composition as claimed in claim 1, characterized in that the hydroxyethylidene diphosphonic acid salt is sodium hydroxyethylidene diphosphonate .

3. The composition as claimed in either one of claims 1 and 2, characterized in that the basifying agent is chosen from sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium silicates, potassium silicates, ammonium silicates, sodium borates, potassium borates and ammonium borates, and mixtures thereof.

4. The composition as claimed in any one of the preceding claims, characterized in that it also comprises an alkaline buffer, preferably chosen from an alkaline carbonate and an alkaline silicate .

5. The composition as claimed in any one of the preceding claims, characterized in that it also comprises a nonionic surfactant.

6. The composition as claimed in any one of the preceding claims, characterized in that the perpropionic acid is present at a concentration of from 0.05 to 4.5 mol/1.

7. The composition as claimed in any one of the preceding claims, characterized in that it is buffered at a pH of between 7 and 10.

8. The composition as claimed in any one of the preceding claims, characterized in that it comprises, by weight relative to the total weight of the composition: - 4% to 16% of perpropionic acid, ' - 0.1% to 2% of dipicolinic acid, - 0.5% to 5% of sodium hydroxyethyldiethyl phosphonate, - 5% to 20% of surfactant, - 2% to 20% of a basifying agent, and - 5% to 15% of alkaline buffer.

9. A process for decontaminating organophosphorus or organosulfur toxic agents and/or pollutants, which comprises bringing said toxic agent and/or pollutant into contact with the composition as defined in one of the preceding claims.

10. A process for obtaining a decontaminating composition as claimed in any one of claims 1 to 8, characterized in that it comprises the following successive steps: a) obtaining a composition comprising perpropionic acid, dipicolinic acid and hydroxyethylidene diphosphonic acid, b) dissolving the composition obtained in step a) in an aqueous composition comprising a surfactant consisting of an amine oxide, and a basifying agent.

11. A process for obtaining a decontaminating composition as claimed in any one of claims 1 to 8, characterized in that it comprises the following successive steps: a) obtaining a composition comprising perpropionic acid and dipicolinic acid, b) dissolving the composition obtained in step a) in an aqueous composition comprising a surfactant, a basifying agent and a hydroxyethylidene diphosphonic acid salt, and preferably sodium hydroxyethylidene diphosphonate. For the Applicants REINHOLD COHN AND PARTNERS By : ·*) lift