RU2559632C2 - Process for destruction of long-term storage sulphur mustards with high oil content and long-term storage mustard-lewisite mixtures with high oil content - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to a process for destruction of sulphur mustards and can be used for the destruction of blister agents. A process for the destruction of long-term storage sulphur mustards with high oil content and long-term storage mustard-lewisite mixtures with high oil content by their reaction with dichloramine in aqueous medium under heterophase conditions in the presence of a phase transfer catalyst (N,N,N-trialkyl-N-benzyl-ammonium chloride), with the dichloramine amount of 10-15%; wherein the destruction process is resulted in the production of a co-catalyst due to the reaction between an alkali metal hydroxide and dichloramine.

EFFECT: effective method for destruction of long-term storage oily sulphur mustards and mustard-lewisite mixtures without using organic solvents, resulting in non-hazardous residual concentrations of toxic agents.

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Description

The invention relates to methods for the destruction of toxic substances of a blistering skin action of long storage - sulfur mustards and mustard-lewisite mixtures with a high resin content.

During long-term storage, sulfur mustard and mustard-lewisite mixtures are transformed into viscous or solid masses that have both hydrophilic and hydrophobic properties, containing gummy organic and inorganic compounds, as well as residual β, β′-dichlorodiethyl sulfide and β-chlorovinyl dichloro rosin in the capsule state (picture 1).

Figure 1 - The main transformation products of β, β′-dichlorodiethyl sulfide, presented in sulfur mustard for long-term storage

Sulfur mustard gas and mustard-lewisite mixtures of long-term storage are viscous and solid-phase masses containing β, β′-dichlorodiethyl sulfide and β-chlorovinyl dichlorarsin. The amount of resinous and solid substances in them is from 40% to 90%. The content of β, β′-dichlorodiethyl sulfide and β-chlorovinyl dichloroarsine dissolved and encapsulated in them is from 10% to 40%.

Existing methods for the destruction of mustard gas, based on the reactions of oxidation, oxidative chlorination and alkaline hydrolysis [Franke Z., Franke E. Chemistry of toxic substances. T. 1. - M .: Chemistry, 1973. - 440 p.] Do not allow detoxification of β, β′-dichlorodiethyl sulfide and β-chlorovinyl dichloroarsine contained in resinous precipitates, which are a mixture of polymers and sulfonium salts that are difficult to dissolve in existing degassing recipes.

These processes are characterized by high energy consumption and the formation of viscous, resinous reaction masses and wastes, which are significant technological disadvantages and impose restrictions on the use of these methods for the destruction of sulfur mustard and mustard-lewisite mixtures of long-term storage [Soborovsky LZ, Epstein G.Yu. . Chemistry and technology of military chemicals. - M .: State. Ed. defense industry, 1938. - S. 587; Franke Z., Franke E. Chemistry of toxic substances. T. 1. - M .: Chemistry, 1973. - 440 p.].

Methods that ensure the destruction of chloralkyl fragments of β, β′-dichlorodiethyl sulfide and the complete decomposition of β-chlorovinyl dichloroarsine, which use hydrolysis or dehydrochlorination reactions, are technologically justified and economically available when using alkaline reagents (alkalis, amines, amides).

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 and 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 chlorides or N, N, N-tributyl-N-benzylammonium chlorides, are used as a catalyst [Russian Patent No. 2041206, 07.07.92, publ. August 10, 1995]. The disadvantages of the proposed method for the destruction of sulfur mustard include the use of a flammable liquid (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 toxic substances of the skin-boiling effect of long-term storage is a method of destroying mustard gas of long-term storage in an amide medium (N, N-dimethylformamide) [Russia, patent No. 2191173, claimed 25.12.00; publ. 10/20/02]. The application of the method does not require the use of additional reagents (dimethylformamide is a solvent, and the product of its partial decomposition dimethylamine is an active alkaline active agent), however, the disadvantages of this method are:

- the use of combustible organic solvents;

- carrying out the reaction at a temperature of from 70 ° C to 130 ° C, necessary for the course of the dehydrochlorination process;

- the difficulty in ensuring the hydrodynamic regime during dissolution and destruction of mustard gas for long-term storage;

- the complexity of the method in the field and in emergency situations without creating technological installations;

- a wide range of content of β, β′-dichlorodiethyl sulfide in the reaction mass after the destruction of mustard gas for long-term storage (from 0.1 to 55.0 mg · ml ^-1 ).

A known method for the destruction of sulfur mustards [Patent No. 2497564, Russia, filed November 7, 2011; publ. November 10, 2013], including treatment in an aqueous medium with a composite mixture of an aqueous solution of alkali metal hydroxide, chloride of quaternary trialkylammonium compounds as a phase transfer catalyst and dichloramine as a cocatalyst. As a disadvantage, it can be noted that the method does not allow the destruction of sulfur mustards and mustard-lewisite mixtures of long-term storage (with a high content of viscous, resinous and solid masses).

The aim of the invention is to develop a method for the destruction of sulfur mustard and mustard-lewisite mixtures of long-term storage with a high resin content in an aqueous medium using alkaline reagents, eliminating the use of organic solvents suitable for use in laboratory and field conditions, in emergency situations and for the degassing of surfaces of infected containers , without special technological equipment.

This goal is achieved by the destruction of sulfur mustard gas with long storage of high resins and mustard-levitic mixtures of long-term storage with a high resin content by a method that is carried out in an aqueous medium under heterophase catalysis in the presence of alkali metal hydroxide, phase transfer catalyst (N, N, N -trialkyl-N-benzylammonium chloride) and dichloramine, while the destruction process is accompanied by the formation of cocatalyst as a result of the interaction of alkali metal hydroxide and d Chloramine at boot dichloramine from 10% to 15%.

The destruction of sulfur mustard and mustard-lewisite mixtures of long-term storage is carried out at a ratio of the components of the reaction mixture, mass %:

 sulfur mustard or mustard-lewisite mixture long-term storage up to 10.0  water from 62.0 to 72.0  alkali metal hydroxide from 5.0 to 10.0  N, N, N-trialkyl-N-benzylammonium chloride up to 3.0  N, N-dichloroarylsulfamine from 10.0 to 15.0

The proposed method for the destruction of sulfur mustard gas and mustard-lewisite mixtures of long-term storage with a high resin content are 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. - 271 p., Franke Z. Chemistry of toxic substances. T. 2. - M .: Chemistry, 1973. - 162 p.];

- dehydrochlorination reaction of sulfur mustard [Tolstikov G.A., Shavanov S.S. 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];

- reactions characteristic of lewisite during alkaline hydrolysis [Franke Z. Chemistry of toxic substances. T. 2. - M .: Chemistry, 1973. - 162 p.].

The interphase transfer catalyst located in the reaction mixture accelerates the processes of water-alkaline destruction of sulfur mustard and lewisite [Demlov E., Demlov Z. Interfacial catalysis. - M .: Mir, 1987. - 485 p.]. N, N-Dichloroarylsulfamines (N, N-dichloramines — DHA-B, DHA-T, DHA-HB) and their alkaline degradation products act as a cocatalyst of the mustard destruction process (Example 4). Under these conditions, the reaction of hydrolysis and dehydrochlorination of mustard gas with aqueous solutions of alkalis, providing irreversible destruction of sulfur mustard and lewisite (in mustard-lewisite mixtures). The process of destruction of sulfur mustard and mustard-lewisite mixtures of long-term storage with a high resin content on the surface of the container is carried out by soaking.

Example 1. In a reaction flask with a capacity of 250 ml, 20.9 g of β, β′-dichlorodiethyl sulfide (resin and solid residues 44%), 150.0 ml of water, 16.0 g of sodium hydroxide, 5.0 g of triethylbenzylammonium chloride ( TEBAH) and 20.9 g DHA-B. The reaction mass is kept for 6-10 hours. An analysis is carried out for the content of sulfur mustard. The quality of destruction is confirmed by the method of chromatography-mass spectrometric analysis. The content of the active substance is less than 0.01 mg · ml ^-1 . With an increase in the retention time of the reaction mass to 18 h, the content of β, β′-dichlorodiethyl sulfide is less than 0.0005 mg · ml ^-1 .

Example 2. In a metal cylinder with β, β′-dichlorodiethyl sulfide, in an amount of 25.0 g, with a basic substance content of 22% (resin and solid residues 78%), 100.0 ml of water, 12.0 g of potassium hydroxide are placed , 3.0 g TEBAH and 16.0 g DHA-T. The reaction mass is kept for 6-10 hours. An analysis is carried out for the content of β, β′-dichlorodiethyl sulfide. The quality of destruction is confirmed by the method of chromatography-mass spectrometric analysis. The content of β, β′-dichlorodiethyl sulfide is less than 0.01 mg · ml ^-1 . With an increase in the retention time of the reaction mass to 18 h, the content of β, β′-dichlorodiethyl sulfide is less than 0.001 mg · ml ^-1 .

Example 3. In a reaction flask with a capacity of 250 ml, 15.9 g of a solid-phase mustard-lewisite mixture (resin and solid residues - 90%, shelf life more than 20 years), 150.0 ml of water, 16.0 g of sodium hydroxide, 5, 0 g TEBAH and 26.0 g DHA-B. The reaction mass is incubated for 6-10 hours. A mustard analysis is carried out. The quality of destruction is confirmed by the method of chromatography-mass spectrometric analysis. The content of β-chlorovinyl dichloroarsin is less than 0.01 mg · ml ^-1 , and β, β′-dichlorodiethyl sulfide is 0.008 mg · ml ^-1 .

Example 4. 15.9 g of β, β′-dichlorodiethyl sulfide, 150 ml of water, 16 g of sodium hydroxide, 5 g of TEAC are placed in a 250 ml reactor. The reaction mass is kept for 6-10 hours. An analysis is carried out for the content of sulfur mustard. The quality of destruction is confirmed by the method of chromatography-mass spectrometric analysis. The content of β, β′-dichlorodiethyl sulfide is more than 10 mg · ml ^-1 . With an increase in the retention time of the reaction mass to 18 h, the content of β, β′-dichlorodiethyl sulfide is less than 5 mg · ml ^-1 .

Example 5. In a 250 ml reaction flask, 18.0 g of β, β′-dichlorodiethyl sulfide (resin and solid residues 44%), 150.0 ml of water, 12.0 g of sodium hydroxide, 5.0 g of triethylbenzylammonium chloride ( TEBAH) and 28.0 g DHA-T. The reaction mass is kept for 6-10 hours. An analysis is carried out for the content of sulfur mustard. The quality of destruction is confirmed by the method of chromatography-mass spectrometric analysis. The content of the active substance is less than 0.001 mg · ml ^-1 . With an increase in the retention time of the reaction mass to 18 h, the content of β, β′-dichlorodiethyl sulfide is less than 0.0005 mg · ml ^-1 .

The method allows the destruction of sulfur mustard and mustard-lewisite mixtures of long-term storage with a high resin content in laboratory and field conditions, in emergency situations, eliminates the use of organic solvents and special equipment. The method is convenient for destroying the unrecoverable residue of sulfur mustard and mustard-lewisite mixtures of long-term storage with a high resin content in containers, transport and technological equipment.

Thus, the proposed method for the destruction of sulfur mustard and mustard-lewisite mixtures of long-term storage with a high resin content using aqueous solutions of alkalis, N, N-dichloroarylsulfamine, catalyst N, N, N-trialkyl-N-benzylammonium chloride reduces their content in the reaction mass to a concentration of not more than 0.01 mg · ml ^-1 while maintaining the reaction mass from 6 to 10 hours and not more than 0.0005 mg · ml ^-1 with increasing incubation time of the reaction mass to 18 hours. Toxicological assessment obtained reaction masses prov dilas toxicometry methods GOST 2.1.007-76 and indicates that they belong to class III hazard.

Claims (1)

The method of destroying sulfur dioxide mustard for a long time with a high resin content and mustard-lewisite mixtures for a long storage with a high resin content in a method that is carried out in an aqueous medium under heterophase catalysis in the presence of an alkali metal hydroxide, phase transfer catalyst (N, N, N-trialkyl- N-benzylammonium chloride) and dichloramine, while the destruction process is accompanied by the formation of cocatalyst as a result of the interaction of alkali metal hydroxide and dichloramine when loaded with dichlorams at from 10% to 15%.