RU2071799C1 - Disposal of yperite, lewisite, and mixtures thereof - Google Patents

Abstract

FIELD: disposal of chemical weapon. SUBSTANCE: yperite, lewisite, and their mixtures interact at 80-90 C for 2-3 h under stirring with a formulation containing (in wt %): sodium hydroxide, 5-6; sodium carbonate, 5-6; monoethanolamine, 5-6; sulfonol, 0.1-0.15; water, the balance. Process is carried out with bubbling the reaction mixture with steam and maintaining formulation input 1 cu.dm per 100 g of substance being disposed. EFFECT: simplified procedure. 2 cl, 2 tbl

Description

 The invention relates to the field of defense industry, in particular, to resolving issues related to the neutralization of toxic substances: mustard gas, lewisite, and mixtures thereof. For terminals for destruction of stockpiles of long-term storage of OM data, the need to create a universal method for the neutralization of these substances is obvious.

 Currently, for the treatment of mustard gas, a “bleach slurry” treatment method is used, which is prepared by mixing bleach or DTSGK (DSGK) powder with water 1: 1 (instruction VF GSNIIOKhT, 1986, inv. 2330 NTB).

 A known method of neutralizing mustard gas with a mixture of concentrated nitric and sulfuric acids (ratio of acids, respectively, 3: 1 by volume). Reagent consumption: per 1 hour mustard gas 20 vol. mixtures of acids, neutralization time 6 hours (instruction VF GSNIIOKhT, 2330, 1986).

 Solutions of monochloramines are used to neutralize mustard gas on the surfaces of PPE and on exposed skin. Solutions of dichloramines in dichloroethane are used to neutralize mustard gas in organic solvents (Z. Franke. Chemistry of toxic substances. M. Chemistry, 1973).

 The method of neutralizing lewisite is reduced to its processing with concentrated (10 20%) aqueous solutions of sodium hydroxide. The completeness of neutralization of lewisite when interacting with a 20% aqueous solution of NaOH is achieved within 24 hours of contact with stirring in the case of an initial concentration of lewisite of 1 vol. for 100 hours alkali solution (Report VF GSNIIOKhT, 1990, inv.2392 NTB).

 Recommended for use is the method of neutralizing lewisite with clarified aqueous solutions of DTSGK (DSGK) 4 5% according to the "ah." The completeness of neutralization is achieved after 6 hours of contact with stirring at a ratio of lewisite: solution of 1: 100 (mass), respectively (report VF GSNIIOKhT, 1990, inv. 2392 NTB).

 Aqueous and aqueous-alcoholic solutions of monochloramines are used to neutralize lewisite on the surface of human skin (Means and methods of degassing, disinfection and decontamination. Sanitary treatment of people. M. Military Publishing House of the Ministry of Defense of the USSR, 1960).

In these methods of neutralizing mustard gas and lewisite is carried out at a temperature of 20 ± 3 ^o C.

 The closest to the invention in terms of essential features and purpose is a method of destroying lewisite, mustard-lewisite formulations (Conference on Disarmament. Basic Technological Aspects of the Destruction of Chemical Weapons, CD / CW / WP. 367, 07.10.91, p.3) ("Russian chemical journal ", journal of the Russian Chemical Society named after DI Mendeleev, vol. XXXVII, N 3, 1993).

This method involves carrying out a detoxification (neutralization) reaction of lewisite by reaction with a sulfur melt and subsequent burial of the resulting polymer product. The optimal process parameters: temperature 160 180 ^o C, time 30 40 min, the mass ratio of lewisite: sulfur is 1: 3. To mitigate the process in order to avoid strong boiling, phenol and salicylic acid are introduced into the melt.

The technology for destroying mixtures of mustard gas and lewisite with lewisite consists in fusion with sulfur mustard-lewisite formulations in the presence of N-methylpyrrolidone with the formation of a low-toxic sulfur alloy suitable for disposal. As a hydrophobic material, sulfur protects alloys from the dissolution of OM detoxification products by water and their subsequent release into the external environment. The washout of arsenic from a sulfur alloy does not exceed 6 • 10 ^-6 g / cm ² per day.

The method is one-stage, does not require expensive reagents. However, the method has several disadvantages:
high environmental burden due to the burial of a large amount of arsenic-containing waste, hence the need for the construction of waterproofed burial grounds;
irreversible loss of arsenic occurs during the burial of the alloy;
the impossibility of detoxification in this way of containers in which lewisite or mustard-lewisite formulations were stored;
high process temperature.

 The objective of the invention is to develop a method of neutralizing mustard gas, lewisite and their mixtures based on the new formulation, which has high power and versatility with respect to these substances, which will provide uniform conditions for neutralization. The method should ensure the generation of waste that can be disposed of and disposed of, which will reduce the environmental burden on the environment, and allow the disposal of arsenic. The method should be possible, if necessary, for the neutralization of containers from mustard gas, lewisite and mixtures thereof. The detoxification process should take place at a lower temperature to ensure the safety of the neutralization technology.

This is achieved by processing mustard gas, lewisite and mixtures thereof at a temperature of 80 90 ^o C for 2 3 hours with an aqueous formulation containing chemically active reagents: sodium hydroxide 5 6% wt. sodium carbonate 5 6% wt.), monoethanolamine 5 6% and surfactant sulfonol (sodium salts) of alkylbenzenesulfonic acids C ₁₁ C ₁₉ ) 0.1 ^o C 0.15% wt. The treatment is carried out with mechanical stirring or sparging with steam through the reaction mass.

 The following examples illustrate the invention.

 Example 1. Preparation of a neutralizing formulation.

500 g (500 cm ³ ) of water are placed in a reactor equipped with a stirrer and a reflux condenser, where 25 g of sodium hydroxide (GOST 2263-79), 25 g of sodium carbonate (GOST 5100-85) are added with stirring. After dissolution of the soda, add 0.5 g of sulfonol (TU 6-01-1612839-34-90) and the last serves 25 g of monoethanolamine (TU 6-02-915-84). The recipe is a clear, uniform liquid.

 Neutralization experiments were carried out on samples of long-term storage products. Samples of mustard gas contained: mustard gas 81 85% wt. with an admixture of stabilizers: tetramethyldiaminodiphenylmethane or aniline, or propylene oxide up to 2 2.5% wt. the rest is unidentified components.

 The lewisite samples contained α and b lewisite 87 90% wt. 3 7% wt. the rest is unidentified components.

 Mixed samples contained lewisite (α and β) up to 20 24% wt. mustard gas up to 52% wt. in the presence of aniline stabilizer up to 2% wt. the rest is unidentified components.

 Example 2. The neutralization of mustard gas.

In a reactor equipped with a stirrer, a thermometer, a reflux condenser, heating (water bath), 500 g of the prepared recipe are placed and 50 g of mustard gas is supplied from a dropping funnel with stirring, and heating is turned on. The reaction is carried out at a temperature of 80 ^o C for 2 hours. After 2 hours, a homogeneous spent solution is analyzed for residual mustard content according to the method of VF GSNIIOKhT, inv. 7573 M, 1991. The residual content of mustard gas is not more than 2.5 mg / dm ³ , which corresponds to the lower limit of determination by the method.

 Example 3. The neutralization of mustard gas.

A reactor of 500 g was placed in a reactor equipped with a thermometer and a reflux condenser and 50 g of mustard gas was fed. After adding mustard gas through a bubbler in the reaction mass serves steam. Sparging is carried out for 2 hours, maintaining the temperature at 80 ^o C. The spent solution is analyzed in the same way as in experiment 2. The amount of the spent solution increases due to steam condensation by 1.5 times in comparison with experiment 2.

The completeness of the neutralization of mustard gas according to experiments 2,3 was confirmed by the sanitary-toxicological control of the spent solutions (waste) on white mice according to GOST 12.1.007-76 when neutralizing the medium to pH 7. LD ₅₀ with intragastric application> 5000 mg / kg and with cutaneous application> 2500 mg / kg, which allows attributing waste solutions (waste) after removal of alkalinity to substances of hazard class IV.

 Example IV Neutralization of lewisite.

The experiment is carried out analogously to example 2, using lewisite. After 2 hours, the spent solution (waste) is analyzed for a residual lewisite content of 2 mg / dm ³ , which corresponds to the minimum detectable amount of lewisite according to the method of VF GSNIIOKhT, inv. 7541 M, 1991

 The spent mass (waste) is a homogeneous dark solution with a suspension of a fine crystalline black precipitate that does not adhere to the walls of the reactor. The amount of sediment is less than 0.01% by weight of the total spent mass.

 Example V. Neutralization of lewisite.

 The experiment is carried out analogously to example 2, using lewisite. After bubbling, the spent masses (waste) are analyzed according to example 4.

The completeness of neutralization of lewisite in examples 4,5 is also confirmed by the sanitary-toxicological control of the spent solutions according to GOST 12.1.007-76 with cutaneous application LD ₅₀ > 2500 mg / kg (hazard class IV), with intragastric application 3150 mg / kg (hazard class III ), which is explained by the presence of arsenic.

 Example VI

 The experiments are carried out analogously to examples 2,3, using mustard-lewisite mixtures.

Analysis of the residual content of mustard gas and lewisite is carried out according to the methods of VF GSNIIOKhT, inv. 7573 M, 7541 M, 1991. The residual content of mustard gas is 2.5 mg / dm ³ , lewisite 2.0 mg / dm ³ . According to the sanitary-toxicological assessment, the spent solutions are characterized by: LD ₅₀ with a cutaneous application> 2500 mg / kg (IV class of danger), LD ₅₀ with an intragastric application of 4200 mg / kg (III class of danger), which is explained by the presence of arsenic compounds.

 Table 1 shows the data of experiments to determine the parameters of the method of neutralizing mustard gas, lewisite, and their mixtures with the aqueous alkaline proposed formulation.

Thus, the completeness of neutralization of mustard gas, lewisite and their mixtures is achieved according to the table in experiments 8, 10, 11, 14, 16, 17, 20, 22, 23, which corresponds to the course of reactions under the action of water-alkaline formulations for 2 3 hours at a temperature of 80 90 ^o C with the initial contamination of the reaction mass up to 100 g / DM ³ .

 Reducing the time (experiments 9, 15, 21), lowering the temperature (experiments 7, 13, 19), increasing the infection (experiments 12, 18, 24) do not lead to the achievement of complete neutralization.

 An increase in time (experiments 10, 16, 22), an increase in temperature (experiments 8, 14, 20), a decrease in the initial amount of OM (experiments 11, 17, 23) lead to the desired results, and are not accompanied by an excess consumption of reagents and energy.

 The data of experiments to determine the composition of a single water-alkaline formulation for the neutralization of mustard gas, lewisite and their mixtures according to the regime of the proposed method are given in table 2.

 From the table it follows that the composition of the aqueous-alkaline formulation corresponding to the content of sodium hydroxide in water 5 6% wt. sodium carbonate 5 6% wt. monoethanolamine 5 6% wt. and sulfonol 0.1 0.15% wt. to the greatest extent contributes to the completeness of the neutralization of mustard gas, lewisite and their mixtures according to the proposed regime (experiments 2,3,4,5,6, 25, 34, 43). The decrease in the content of any component in the aqueous solution does not lead to the complete neutralization (experiments 26, 28, 30, 32, 35, 37, 39, 41, 44, 46, 48, 50). The increase in the content of components in the solution does not significantly increase the efficiency of neutralization (experiments 27, 29, 31, 33, 36, 38, 40, 42, 45, 47, 49, 51).

 Thus, the proposed method of neutralizing mustard gas, lewisite and their mixtures has versatility (the use of a single formulation and common process conditions).

 Compared with the prototype, the process is carried out at a lower temperature. The generated wastes are homogeneous alkaline liquids. According to the sanitary-toxicological control according to GOST 12.1.007-76, they are classified as substances of hazard class IV III (experiments 2,3,4,5,6).

 According to preliminary data, the liquid wastes of mustard detoxification are microbiologically destroyed or can be destroyed by burning.

 Arsenic-containing wastes are possible for disposal of arsenic or further destruction according to current technologies.

 One of the options that confirm the possibility of using the method for neutralizing containers is to use not only mechanical stirring at the time of detoxification, but also steam sparging, which facilitates the task of creating technology for the neutralization of large containers: barrels, tanks.

Claims (2)

 1. The method of neutralizing mustard gas, lewisite and mixtures thereof, characterized in that the neutralization is carried out by interacting with a formulation containing components in the following ratio, wt. Sodium hydroxide 5.0 6.0
Sodium Carbonate 5.0 6.0
Monoethanolamine 5.0 6.0
Sulfonol 0.1 0.15
Water Else
at a temperature of 80 90 ^o C for 2 3 hours 2. The method according to p. 1, characterized in that the interaction is carried out with mechanical stirring or by sparging with steam the reaction mixture, and the consumption of the formulation is 1 DM ³ per 100 g of neutralized substance.

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