RU2240849C1 - Method for detoxification of yperite and mixtures thereof - Google Patents

Abstract

FIELD: poisonous gas disposal.

SUBSTANCE: method consists in bringing yperite or its mixture into contact with 75-95% aqueous monoethanolamine solution at weight ratio yperite (its mixture)/monoethanolamine 1:1.0-1.5) at 95-120^oC.

EFFECT: enabled effective and environmentally safe industrial-scale destruction of yperite due to increased productivity and essentially decreased amount of waste to be further processed.

7 cl, 5 ex

Description

The invention relates to the field of technology for the destruction of chemical weapons, in particular, mustard gas and its mixtures, in particular, with lewisite.

Recently, it has become urgent to develop new methods for the neutralization of chemical weapons on an industrial scale, ensuring the conversion of chemicals to a state that is irreversibly unsuitable for the production of chemical weapons.

Known methods for the thermal decomposition of toxic substances in furnaces with subsequent purification of exhaust gases and disposal of solid residues (Russian Chemical Journal, vol. XXXIX, No. 4, pp. 31-36, 37-42, application US 5711017 A, US 5527983 A, application FR 2737416 A1, patent DE 3028193 C2, RF patents 213874 and 2156631).

However, these known technologies are associated with the formation of a large amount of waste, including highly toxic dioxins, which pose a great environmental hazard to the environment, and, in addition, are highly energy-intensive.

A known chemical method for the destruction of mustard gas with aqueous solutions of alkalis (Russian Chemical Journal, vol. XXXVII, No. 3, p. 28, 1993). The disadvantages of this method in relation to the destruction of large quantities of mustard gas is the low rate of the hydrolysis reaction and the need for large quantities of degassing formulations.

A known method of thermochemical destruction of mustard gas, carried out by its interaction with ammonia at a molar ratio of 1: (4.0-6.0) and at a temperature of 400-500 ° C (patent RU 2169598 C2). The disadvantages of this method is the energy intensity and a significant amount of waste.

The closest in technical essence to the proposed method is a method of neutralizing mustard gas, lewisite and mixtures thereof by reacting with an aqueous solution of NaOH, Na ₂ CO ₃ , monoethanolamine and sulfonol at a temperature of 80-90 ° C (RU 2071799 C1, MKI ⁶ A 62 D 3 / 00, 01/20/97). The main degassing agent in this method is NaOH, monoethanolamine is used to lower the freezing point of the solution when it is used in the cold season, sulfonol and Na ₂ CO ₃ are used as a washing formulation. The process is carried out with mechanical stirring or steam sparging of the reaction mixture at a flow rate of 1 dm ^{3 of an} aqueous solution per 100 g of the neutralized substance, and a large amount of waste is generated, mainly inorganic salts and thiodiglycols. In the case of the processing of such aqueous wastes containing an excess of NaOH and inorganic salts in the form of carbonates and the resulting sodium chloride, a significant amount of so-called “melts” are formed by burning, which complicate the combustion process and require further burial.

According to the provision of the “Convention on the Prohibition of the Development, Production, Stockpiling and Use of Chemical Weapons and on Their Destruction” (TS OZKhO Publishing House, 2000), the destruction of toxic substances requires the irreversible transformation of chemicals into a state that is irreversibly unsuitable for the production of chemical weapons.

According to the Chemicals Appendix to the above-mentioned convention (section B, list 2, position 13) thiodiglycol is a mustard precursor and according to the abovementioned Annex (part VII, section A, position 3) its production as a chemical belonging to list 2 can be carried out in volume no more than 1 t / year.

Thus, the known method is environmentally hazardous for the destruction of large volumes of toxic substances and cannot be used for large-scale destruction of chemical weapons.

The objective of the invention is to develop an environmentally friendly method of neutralizing mustard gas or its mixtures, suitable for use on an industrial scale by increasing productivity and significantly reducing the amount of waste for subsequent disposal.

The problem is achieved by the interaction of mustard gas or its mixtures with a 75-95% aqueous solution of monoethanolamine with a mass ratio of mustard gas or its mixture: monoethanolamine, equal to 1: 1-1.5 at a temperature of 95-120 ° C.

Preferably, the reaction is carried out for 1-1.5 hours.

The proposed method is suitable for the disposal of not only mustard gas, but also its mixtures, which are mixtures of various mustards in any proportions, a mixture of mustards and lewisites in any proportions.

Mustard suitable for neutralization by the method according to the invention may include

β, β-dichlorodiethyl sulfide (mustard-1),

β-chloroethyl, β-chlorisopropyl sulfide (mustard-2),

β, β-dichlorodiisopropyl sulfide (mustard-3),

β, β-dichlorodiethylethylene disulfide (sesqui mustard),

as well as polymerization products formed during storage, and other impurities, in particular, free sulfur.

Mustard gas may include

5.0-98.0 wt.% Mustard-1,

0-34.5 wt.% Mustard-2,

0-35.0 wt.% Mustard-3,

0-5.5 wt.% Sesqui mustard, and

2-20.0 wt.% Polymerization products and other impurities.

Mixtures of mustard gas with lewisite, the so-called “double” mixtures suitable for neutralization by the method according to the invention, may include

9.0-17.5 wt.% Mustard-1,

8.5-34.5 wt.% Mustard-2,

14.0-35.0 wt.% Mustard-3,

0-5.5 wt.% Sesqui mustard,

7.5-21.5 wt.% Β-chlorovinyl dichloroarsin (α-lewisite),

1.0-3.75 wt.% Β, β-dichlorodivinylchloroarsin (β-lewisite),

2.5-9.0 wt.% Arsenic trichloride, and

3.5-25.5 wt.% Polymerization products and other impurities.

According to the proposed method, it is also possible to neutralize mixtures of mustard gas with lewisite in dichloroethane, the so-called “triple” mixtures, including

16.5-34.0 wt.% Mustard-1,

4.0-7.0 wt.% Mustard-2,

0-11.0 wt.% Mustard-3,

8.0-22.0 wt.% Sesqui mustard,

13.0-20.0 wt.% Α-lewisite,

3.0-5.5 wt.% Β-lewisite,

1.5-6.0 wt.% Arsenic trichloride,

14.0-20.0 wt.% Dichloroethane, and

5.5-11.5 wt.% Polymerization products and other impurities.

The process is carried out in a reactor equipped with a stirrer, a reflux condenser and a thermometer, into which an aqueous solution of monoethanolamine is pre-loaded and mustard is dosed with mustard gas or its mixture in a mass ratio of 1: 1-1.5, or mustard is pre-loaded with mustard or its mixture and then dosed with stirring monoethanolamine aqueous solution. The components are kept at a temperature of 95-120 ° C for 1-1.5 hours. In this case, the completeness of degassing by mustard gas and lewisite of 1.0 × 10 ^-2 - 5.0 × 10 ^-4 wt.% Is achieved. The resulting reaction mass is easily mobile and well transported.

In contrast to the known methods, the interaction of mustard gas with monoethanolamine according to the invention results in the formation of non-volatile, low-hazard thiazane hydrochlorides belonging to the fourth hazard class, for example,

the interaction of β, β-dichlorodiethyl sulfide (mustard-1) with monoethanolamine produces N-2-hydroxyethylthiazane hydrochloride,

the interaction of β-chloroethyl, β-chlorisopropyl sulfide (mustard-2) with monoethanolamine produces N-2-hydroxyethylmethylthiazane hydrochloride,

the interaction of β, β-dichlorodiisopropyl sulfide (mustard-3) with monoethanolamine produces N-2-hydroxyethyl dimethylthiazane hydrochloride,

in the interaction of β, β-dichlorodiethylethylene sulfide (sesqui mustard) with monoethanolamine, β, β-dihydroxyethyl aminoethylethylene disulfide hydrochloride is formed.

The completeness of the neutralization of mustard gas was determined by gas chromatography and confirmed by the sanitary-toxicological control of the reaction products obtained in white mice and rats according to GOST 12.1.007-76 g.

With intragastric administration of detoxification products LD ₅₀ > 5000 mg / kg, with cutaneous application LD ₅₀ > 2500 mg / kg, which allows the waste to be classified as the fourth hazard class according to GOST 12.1.007-76 g.

According to the proposed method, an increase in productivity is achieved, the amount of waste is significantly reduced and the interaction time is reduced.

The invention is illustrated in more detail by the following examples, in which mustard was used for detoxification, as well as a mixture of mustard with lewisite.

Example 1

In a reactor equipped with a stirrer, reflux condenser, thermometer, dropping funnel, heating (glycerin bath) and a sampler, 120 g of an 80% aqueous solution of monoethanolamine are placed, heating is turned on and 100 g of mustard from a dropping funnel are metered with stirring at a temperature of 90-120 ° C. At the end of dosing, the reaction mass is maintained with constant stirring and a temperature of 120 ° C for 1 hour.

After one hour, a liquid mobile reaction mass is obtained and analyzed for residual mustard content using gas chromatography with mass spectral detection in accordance with the methodology of FSUE GosNIIOKhT No. 5651, 2002. The residual mustard content is 5.0 × 10 ^-4 wt.% .

Example 2

In the reactor described in example 1, 100 g of mustard gas was placed and then an aqueous 95.0% solution of monoethanolamine was dosed from a dropping funnel and heating was turned on. At the end of dosing, the reaction mass is maintained with constant stirring and a temperature of 100 ° C for 1.3 hours. The result is a liquid mobile reaction mass and determine the residual content of mustard gas according to the above method. The residual content of mustard gas is 4.3 × 10 ^-4 wt.%.

Example 3

The method is carried out according to example 1, however, the interaction is subjected to a mustard-lewisite mixture comprising 17.5 wt.% Mustard-1; 30.5 wt.% Mustard-2; 11.2 wt.% Sesqui mustard; 19.2 wt.% Α-lewisite; 5.5 wt.% Β-lewisite; 4.6 wt.% Arsenic trichloride, as well as 11.5 wt.% Polymerization products. Use a 75% aqueous solution of monoethanolamine, the mass ratio of the mixture to monoethanolamine is 1: 1.5. At the end of dosing, the reaction mass is maintained with constant stirring and a temperature of 95 ° C for 1.5 hours. The result is a liquid mobile mass.

The residual content of mustard gas is 3.3 × 10 ^-4 wt.% And lewisite - 3.3 × 10 ^-2 wt.%.

Example 4 (comparative)

In a reactor equipped with a stirrer, reflux condenser and thermometer, 500 g of a neutralizing solution including 5 wt.% NaOH, 5 wt.% Na ₂ CO ₃ , 6 wt.% Monoethanolamine and 0.5 wt.% Sulfonol and water are placed, and with stirring, 50 g of mustard gas from a dropping funnel is dosed and heating is turned on. The reaction is carried out at a temperature of 80 ° C for 2 hours. As a result of the interaction, an aqueous solution of the reaction mixture is obtained, 10 times the amount of the starting product and, in addition, containing thiodiglycols, which are a mustard precursor and are listed in list 2, which does not allow us to recognize this method as environmentally friendly and suitable for large-scale use.

The residual content of mustard gas is 2.2 × 10 ^-3 wt.%.

Example 5 (comparative)

The method is carried out according to example 4, however, to prepare a neutralizing solution using only 6.0 wt.% Monoethanolamine, sodium hydroxide, sodium carbonate and sulfonol are excluded. As a result, the conversion reaches only about 30% within 20 hours.

Thus, the method of neutralization of mustard gas proposed according to the invention provides an effective and environmentally friendly destruction of mustard gas and can be used at industrial facilities for the destruction of chemical weapons.

Claims (8)

1. The method of neutralizing mustard gas or its mixtures by interacting with an aqueous solution of monoethanolamine when heated, characterized in that the interaction is carried out with a 75-95% aqueous solution of monoethanolamine in a mass ratio of mustard gas or its mixture: monoethanolamine, equal to 1: 1,0- 1.5, at a temperature of 95-120 ° C. 2. The method according to claim 1, characterized in that the interaction is carried out for 1-1.5 hours 3. The method according to claim 1 or 2, characterized in that the mustard mixture is a mixture of mustard-1, mustard-2, mustard-3, sesqui mustard and the polymerization products formed during storage. 4. The method according to claim 3, characterized in that the mixture comprises 5.0-98.0 wt.% Mustard-1; 0-34.5 wt.% Mustard-2; 0-35.0 wt.% Mustard-3; 0-5.5 wt.% Sesqui mustard and 2.0-20.0 wt.% Polymerization products. 5. The method according to claim 1 or 2, characterized in that the mustard mixture includes mustard-1, mustard-2, mustard-3, sesqui mustard, α-lewisite, β-lewisite, arsenic trichloride, polymerization products formed during storage . 6. The method according to claim 5, characterized in that the mixture comprises 9.0-17.5 wt.% Mustard-1; 8.5-34.5 wt.% Mustard-2; 14.0-35.0 wt.% Mustard-3; 0-5.5 wt.% Sesqui mustard; 7.5-21.5 wt.% Α-lewisite; 1.0-3.75 wt.% Β-lewisite; 2.5-9.0 wt.% Arsenic trichloride, as well as 3.5-25.5 wt.% Polymerization products. 7. The method according to claim 1 or 2, characterized in that the mustard mixture includes mustard-1, mustard-2, mustard-3, sesqui-mustard, α-lewisite, β-lewisite, arsenic trichloride, polymerization products formed during storage and dichloroethane. 8. The method according to claim 7, characterized in that the mixture comprises 16.5-34.0 wt.% Mustard-1; 4.0-7.0 wt.% Mustard-2; 0-11.0 wt.% Mustard-3; 8.0-22.0 wt.% Sesqui mustard; 13.0-20.0 wt.% Α-lewisite; 3.0-5.5 wt.% Β-lewisite; 1.5-6.0 wt.% Arsenic trichloride; 5.5-11.5 wt.% Polymerization products; 14.0-20.0 wt.% Dichloroethane.