RU2497564C2 - Method of destructing mustard agents - Google Patents

Abstract

FIELD: process engineering.

SUBSTANCE: invention relates to destruction of poison-gases, i.e. mustard agents. Proposed method comprises processing of mustard agent by composite mix of aqueous solution of alkaline metal hydroxide, quaternary tri-alkyl ammonium chloride compounds as interphase transfer catalyst and dichloramine as cocatalyst. Mustard agent decontamination is carried out under conditions of interphase catalyst in interaction of liquid-phase mix with heterophase mustard agents. Proposed method is suitable for in-field destruction of different-structure mustard agents and in emergency without application of special purposed and equipment.

EFFECT: destruction of mustard agents to residual concentration of 0,01 mg-ml^-1 without application of organic solvents.

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Description

The invention relates to methods for the destruction of toxic substances of a skin-boiling effect - sulfur mustards. The method is carried out by detoxification using aqueous solutions of alkalis, N, N-dichloroaryl sulfamide under interphase catalysis using a catalyst of N, N, N-triethyl-N-benzylammonium chloride (TEAC). The method allows for the detoxification (destruction) of sulfur mustards in laboratory and field conditions, in emergency situations, using aqueous formulations, eliminating the use of organic solvents and special equipment, is suitable for the destruction of sulfur mustards of various structures.

Known methods for the destruction of sulfur mustard (β, β'-dichlorodiethyl sulfide), based on the processes of oxidation and oxidative chlorination, are carried out using organic solvents and are characterized by the formation of significant amounts of viscous and resinous reaction masses and wastes, high energy consumption, which are significant disadvantages and limitations the application of these methods for the destruction of mustard gas [Soborovsky LZ, Epstein G.Yu. Chemistry and technology of military chemicals. - M .: State. Ed. defense industry, 1938. - P.587; Franke 3., Franke E. Chemistry of toxic substances. - M .: Chemistry, t.1, 1973. - S.440].

Technologically justified and economically affordable methods of detoxification of sulfur mustards include methods that use reactions using alkaline reagents. However, the use of mustard gas destruction methods based on alkaline hydrolysis is limited by the complexity of creating homogeneous reaction masses (the solubility of mustard gas in water at 20 ° C is 0.8 mass%) and the duration of the process.

Known methods for the destruction of mustard gas by treating it with an aqueous solution of alkali in a medium of dimethyl sulfoxide, at a temperature of 85 ° C to 110 ° C [Russia, patent No. 2139855, claimed March 31, 1998, publ. October 20, 1999] and with ultrasonic exposure [Russia, patent No. 2139856, claimed March 31, 1998, publ. October 20, 1999]. The disadvantages of the proposed methods for the destruction of sulfur mustard include the need to maintain a high temperature in the reaction zone, as well as the use of special technological equipment (ultrasonic baths, contactless mixing devices, etc.) that ensure a high rate of decomposition of mustard gas.

A known method of destroying sulfur mustard or its solutions in hexane with an aqueous alkali solution in the presence of a phase transfer catalyst at a temperature of from 20 ° C to 60 ° C and in the fluidized bed. Chlorides of quaternary ammonium compounds, for example, N, N, N, N-tetrabutylammonium or N, N, N-tributyl-N-benzylammonium chlorides, are used as a catalyst [Russia, patent No. 2041206, claimed 07.07.92, publ. August 10, 1995]. The disadvantages of the proposed method for the destruction of mustard gas include the use of flammable liquids (hexane) as a solvent, as well as the use of special technological equipment that ensures the creation of a fluidized bed (vibration mixer).

According to the set of features, the closest to the proposed method for the destruction of mustard gas is the method for the destruction of mustard gas with an aqueous solution of an alkali metal hydroxide in the presence of an interphase transfer catalyst (quaternary ammonium chloride), dimethyl sulfoxide (an organic solvent), benzyl alcohol (cocatalyst) at elevated temperature [Russia, Patent No. 2191173, claimed December 25, 00, publ. 10/20/02]. The disadvantages of this method are:

- the use of combustible organic solvents;

- carrying out the reaction with mandatory heating, necessary for the course of the reaction of the mustard detoxification - dehydrochlorination;

- limiting the use of the method for the destruction of sulfur mustards of various structures;

- the inability to use in the field and in emergency situations.

This method is adopted as a prototype.

The aim of the invention is to develop a method for the destruction of sulfur mustards and mixtures based on them, suitable for use in laboratory and field conditions, in emergency situations and for the degassing of infected containers, using aqueous alkaline formulations, without the use of organic solvents and special processing equipment.

This goal is achieved by the use of the composition [Russia, patent No. 2410101, claimed 01/27/11, publ. 01/27/11,], including alkali metal hydroxide, trialkylarylammonium chloride and N.M-dichloroaryl sulfamides, in the form of an aqueous formulation.

The mustard gas is degassed under interfacial catalysis using an N, N, N-triethyl-N-benzylammonium chloride catalyst, in the following component ratios, wt.%:

sulfur mustard up to 10.0 alkali metal hydroxide from 5.0 to 10.0 N, N, N-triethyl-N-benzylammonium chloride up to 3.0 N, N-dichloroarylsulfonamide 10.0 to 15.0 water from 60.0 to 85.0

The proposed method for the destruction of sulfur mustard is based on chemical reactions proceeding in a heterophase medium:

- reactions characteristic of sulfur mustards in alkaline hydrolysis and oxidative chlorination [Alexandrov V.N., Emelyanov V.N. Toxic substances. - M .: Military Publishing House, 1990. - P.271, Franke 3. Chemistry of toxic substances. T.2. - M .: Chemistry, 1973. - P.162];

- dehydrochlorination reaction of sulfur mustard [Tolstikov GA, Shavanov SS. Interphase catalysis in the synthesis of organochlorine compounds, some aspects of the mechanism and industrial application // Kinetics and catalysis. - 1996. - T.37. - S.686-691].

The phase transfer catalyst in the reaction mixture accelerates the decomposition of sulfur mustard [Demlov E., Demlov 3. Interfacial catalysis. - M .: Mir, 1987. - 485 p.]. N, N-Dichloroarylsulfonamides (N, N-dichloramines - DHA-B, DHA-T, DHA-HB) and their alkaline degradation products act as a cocatulizer of the mustard destruction process. The sequence of adding reagents to water (alkali metal hydroxide, N, N, N-triethyl-N-benzylammonium chloride, N, N-dichloro-arylsulfamide) allows you to use the thermal effects of the ongoing physico-chemical processes to carry out the destruction of mustard gas without additional heating of the reaction mass . The hydrolysis and dehydrochlorination reactions of mustard gas, occurring under the influence of alkalis, provide irreversible destruction of mustard gas under these conditions. The detoxification process of sulfur mustard, containers contaminated with sulfur mustard, is carried out in the soaking mode.

Example 1. 15.9 g of β, β'-dichlorodiethyl sulfide, 150 ml of water, 16 g of sodium hydroxide, 5 g of TEBAH and 12.9 g of DCA-T are placed in a 250 ml reactor. The reaction mass is kept for 6-10 hours. Analyze the content of mustard gas. The quality of detoxification is confirmed by chromatography-mass spectrometric analysis. The mustard content is less than 0.001 mg · ml ^-1 .

Example 2. In a metal cylinder with residues β, β'-dichlorodiisopropyl sulfide in an amount of 35 g, with a basic substance content of 22%, 100 ml of water is placed. 8 g of caustic soda, 3 g of TEBAH and 6 g of DHA-B. The reaction mass is kept for 6-10 hours. Analyze the content of mustard gas. The quality of detoxification is confirmed by chromatography-mass spectrometric analysis. The content of β, β'-di-chlorodiisopropyl sulfide is less than 0.001 mg · ml ^-1 .

Example 3. In a reactor with a capacity of 250 ml, 15.9 g of β, β'-dichlorodiethylsulfide, 150 ml of water, 16 g of sodium hydroxide, 5 g of TEAC are placed. The reaction mass is kept for 6-10 hours. Analyze the content of mustard gas. The quality of detoxification is confirmed by chromatography-mass spectrometric analysis. The content of β, β'-dichlorodiethyl sulfide was more than 10 mg · ml ^-1 .

Thus, the proposed method for the destruction of sulfur mustards using aqueous solutions of alkalis, N, N-dichloroaryl sulfamide, catalyst N, N, N-triethyl-N-benzylammonium chloride, detoxifies sulfur mustards to their content in the reaction mass of not more than 0.001 mg · ml ^-1 . Toxicological evaluation of the reaction masses after detoxification by the proposed method indicates that they belong to the third class of toxicity.

The method is economical, suitable for the destruction of sulfur mustards of various structures, applicable in laboratory and field conditions, in emergency situations, we implement without creating a technological scheme and the use of special equipment, as well as for the degassing of containers contaminated with sulfur mustards, surfaces of laboratory cabinets, various chemical equipment .

Claims (1)

A method for destroying sulfur mustards, comprising treating in an aqueous medium a composite mixture of the composition: an aqueous solution of an alkali metal hydroxide, chlorides of quaternary trialkylammonium compounds as an interphase transfer catalyst and cocatalyst, by the interaction of a liquid phase mixture with heterophasic sulfur mustards, characterized in that the destruction is carried out using dichloramine and products of its alkaline hydrolysis as a cocatalyst.