RU2304009C2 - Method of reusing hopcalite used in cartridges for respirator box and in collective protection devices - Google Patents

Abstract

FIELD: poison gas protection devices.

SUBSTANCE: invention relates to technology of processing chemicals, in particular to reusing hopcalite, which is used in technical respiratory organ protection devices and also for removing carbon monoxide and gun-powder gases from the air. Method of invention consists in processing hopcalite to obtain products suitable for further utilization and comprises following steps: chemically treating ground hopcalite granules with aqueous ammonia solution at 75-85°C and vigorous stirring of reaction mixture for 2.5-3 h, cooling mixture to 25-30°C, and separating it by filtration into manganese compounds and aqueous copper ammine solution, which are subjected to further separate processing. Manganese compounds are processed through mixing them with nitric acid followed by boiling mixture, filtering solution, and drying to form manganese dioxide crystals, which are treated with sulfuric or phosphoric acid to obtain, respectively, manganese sulfate or copper ammine aqueous solution. To process aqueous copper ammine solution, at least one of the following techniques are utilized: evaporation of solution until beginning of the precipitation of copper hydroxide crystals followed by separation of crystals and calcination thereof to obtain copper oxide powder; addition of cotton cellulose and sodium hydroxide to aqueous copper ammine solution to form copper-ammine solution of cellulose, treatment of the latter with phosphorus and hydrazine-hydrate solution to obtain colloidal copper.

EFFECT: intensified and simplified method due to reduced number of steps, increased yield of valuable produce, and enabled production of chemicals for a wide application area.

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Description

The invention relates to a technology for the processing of chemicals, namely the disposal of hopcalite. Hopcalite is a catalyst used in industry and the military in technical means of protecting the respiratory system and purifying air from carbon monoxide, as well as powder gases.

For the prototype of the invention, the method of processing hopcalite was selected (A. Zavadsky et al. (RCTU) Environmental protection and rational use of natural resources in the operation of hopcalite. Advances in chemistry and chemical technology: Abstracts of the 15th International Conference of Young Scientists in Chemistry and Chemical Technology "MKHT-2001", Moscow, 2001. T. 15. Issue 5, M .: Publishing house of the Russian Chemical Technical University. 2001, p.29, Russian language chemist "Khimiya", 2002, No. 22, ref. No. 19 I.629) comprising successive stages: hydrothermal treatment, filtration, washing, extrusion, drying and calcination of the material with recovery the appearance of its properties at the level of 60 rel. % with subsequent use in production. The disadvantages of the method selected as a prototype include:

- the complexity of the organization of the production process;

- low percentage of recycled material;

- the lack of proposals for the processing of material after the second term of use;

- the impossibility of widespread use of processed products.

Hopcalite is a mixture containing 60 wt.% Manganese dioxide (MnO ₃ ) and 40 wt.% Copper oxide (CuO). Hopcalite is used in special and additional gas mask cartridges (OP-1 and OP-2). Cartridges are used in the presence of dangerous concentrations of carbon monoxide in the air (Brief chemical encyclopedia. - M .: 1961. - T.1). In addition, hopcalite is used in instruments for monitoring the content of carbon monoxide and mercury in the air (Grotti M. et al. Determination of manganese by graphite furnace atomin absorption spectrometry matrix effect control by multiple linear regression model. Spectrochim. Acta. B. 1999. Vol. 54, No. 5, p. 845-851. RZh “Chemistry”, 2001, No. 19, ref. No. 19 of G. 197). In industry, a GFG-based hopcalite catalyst (S. Kireev et al. Adsorption of water vapor on hopcalite. IX International Conference on Theoretical Issues of Adsorption and Adsorption Chromatography “Current State and Prospects for the Development of Adsorption Theory”, on the occasion of the 100th anniversary of the birth of Academician M. M. Dubinin, Moscow, April 24-28, 2001: Abstracts of reports, Moscow: Publishing House of the Institute of Physics and Chemistry, Russian Academy of Sciences, 2001, p. 68. Chemistry, 2001, Ref. ) is used to purify air from impurities of carbon monoxide (Voitovich VP and others. The study of some oxidation catalysts ok carbon monoxide by the method of differential thermal analysis. "Issues of chemistry and chemical technology. Rep. interdisciplinary scientific-technical collection", 1975, issue 37, p. 73-76. RZH "Chemistry", 1975, No. 18, Ref. No. 18 B 1119) and ozone decomposition (Popovich MP and others. Ozone decomposition on hopkalite "Vestnik MGU. Chemistry. 1985, vol. 26, No. 2, p.167-170. RZh" Chemistry ", 1985 G., No. 18, ref. No. 18 B 4256; MP Popovich and others. Decomposition in small concentrations of ozone on certain surfaces "Journal of Physical Chemistry" 1988. Volume 62, No. 1, p.133-138. РЖ “Chemistry”, 1988, No. 11, ref. No. 11 B 4316).

After the warranty period expires or as a result of the expiration of the specified storage period, a significant amount of hopcalite is formed that must be disposed of. The problem of utilization of hopcalite has not yet been solved (Zavadsky A.V. et al. (RCTU) Physical and chemical changes in hopcalite during catalytic destruction of ozone. Current problems of theoretical and experimental chemistry: Abstracts of the 3rd All-Russian Conference of Young Scientists. Saratov, 3-5 Sept., 2001. Saratov: Publishing House of Saratov, State University. 2001, p.25-26. RZH "Chemistry", 2002, No. 19, ref. No. 19 N. 4), which leads to unjustified material costs and, as a result, increased environmental load on the biosphere.

The objective of the present invention is the intensification of the process due to the introduction of chemical processing of hopcalite, which allows to increase the yield of useful products and to ensure the receipt of chemicals with a wide range of uses.

The solution is achieved by processing the crushed hopcalite granules with an aqueous solution of ammonia during heating and vigorous stirring, followed by separation of the reaction products. In the proposed process, chemical transformations occur that allow the separation of newly formed chemicals. The hopcalite processing scheme is shown in the drawing.

The interaction of copper oxide with an aqueous solution of ammonia forms a water-soluble complex compound of copper in accordance with the reaction:

CuO + 4NH ₄ OH → [Cu (NH ₃ ) ₄ ] (OH) ₂ + 3H ₂ O.

The process is accompanied by staining the solution in a bright blue color.

Manganese oxide does not interact with aqueous ammonia under specified process conditions. Manganese compounds of the composition MnO ₂ , MnO ₃ , Mn (OH) ₂ , insoluble in the resulting solution, are present in suspension.

Manganese compounds are separated from the solution by filtration. The filtered precipitate is washed with water and dried in air. In the future, the precipitate can be used to obtain purified manganese dioxide, manganese sulfate and a solution of manganese phosphate in accordance with the methods presented below.

A solution containing copper ammonia can be used to produce copper oxide, a copper-ammonia solution of cellulose or colloidal copper in accordance with the procedures presented below.

Thus, all the chemicals obtained can be used as intermediates for the preparation of copper and manganese compounds suitable for further use.

Processing hopcalite according to the proposed method allows to simplify the process by reducing the number of stages and changing the conditions for their implementation, as well as expand the possibilities of using products obtained as a result of disposal.

HOPCALIT PROCESSING TECHNIQUE.

Granulated hopcalite is ground in porcelain until a homogeneous powder is obtained.

108 g of chopped hopcalite to be processed are placed in a beaker. Add 1420 ml of a 25 wt.% Aqueous ammonia solution. The mechanical stirrer is turned on and the contents of the beaker are heated to a temperature of 75 ° C. Keeping the temperature within 75 ... 85 ° C, the reaction mixture is kept for 2.5 ... 3 hours with vigorous stirring.

Then the mixture is cooled to a temperature of 25 ... 30 ° C and filtered.

The solution obtained in an amount of 1485 ml, is a bright blue liquid containing 11.5% of the complex salt [Cu (NH ₃ ) ₄ ] (OH) ₂ .

The precipitate is washed on the filter with distilled water (3 portions of 150 ml), removed from the filter and dried in air. Obtain 76.2 g of powder from dark brown to black. The composition of the powder is a mixture of manganese dioxide, manganese (III) oxide and manganese hydroxide.

METHOD OF ALLOCATION OF Manganese Dioxide

Example 1. 38.1 g of powder (a mixture of manganese dioxide, manganese (III) oxide and manganese hydroxide) obtained at the stage of processing hopcalite, is placed in a glass chemical reactor equipped with a mechanical stirrer and reflux condenser. 170 ml of 50% nitric acid (ρ = 1.31) are added. Turn on a mechanical stirrer and heat. Cold water is supplied to the refrigerator. With vigorous stirring, the contents of the reactor are boiled for 3.5 hours.

Heating is stopped, mixing is turned off and the mixture is kept at room temperature for at least 24 hours.

The solution was transferred from the reactor to the filter and filtered.

The filtered solution is returned to the reactor. Add 160 ml of distilled water. Mixing and heating are included. Bring the solution to a boil. 45.8 g of potassium chlorate are added in small portions to the boiling solution. In this case, an intensive formation of a solid phase is observed. After the addition of all potassium chlorate, boiling is continued with stirring for 1.5 hours.

Heating is stopped, mixing is turned off. Cool the contents of the reactor to room temperature and incubate for 2 hours. The contents of the reactor are transferred to a filter and filtered. The precipitate is washed on the filter with distilled water (2 portions of 100 ml), then 75 ml of 5% aqueous ammonia solution and again with distilled water (2 portions of 100 ml). The washed precipitate is removed from the filter and dried in air.

Received in an amount of 34.2 g of manganese dioxide - small crystals of black color.

Example 2. 38.1 g of powder is treated with nitric acid under the conditions of example 1. The filtered solution is evaporated. Evaporation is carried out before the start of the crystal precipitation process. The resulting mixture is cooled and maintained at a temperature of 5 ... 10 ° C for 10 ... 12 hours.

The precipitate formed is sucked off on a Buchner funnel. The resulting crystals are placed in a desiccator and incubated over sodium hydroxide for 1 day to remove residual nitric acid.

Then the crystals are crushed and placed in a muffle furnace and kept at a temperature of 200 ° C for 6 hours.

Obtain 32.1 g of an amorphous powder of manganese dioxide of a dark gray color.

Manganese dioxide isolated in examples 1 and 2 can be used as desiccants, a depolarizer in electrical elements, a pigment component, a glass brightener, an oxidizing agent in hydrometallurgy to obtain manganese-containing compounds.

METHODOLOGY FOR PRODUCING MANGANIAN SULPHATE

65 g of manganese dioxide, isolated by the previously presented method, are triturated in a porcelain bowl until a fine powder is formed. The powder is transferred to a beaker and 34.5 ml of sulfuric acid (ρ = 1.833) is added with stirring. Mix the contents of the glass thoroughly until a homogeneous mixture is obtained.

The resulting mixture is transferred to a porcelain cup and placed in a muffle furnace. Incubated for 1 hour at a temperature of 300 ° C. Then it is cooled and 15.5 ml of sulfuric acid are added. Calcined for 1.5 hours at a temperature of 700 ° C.

125 ml of distilled water are added to the chilled pitch and triturated thoroughly. Then stand for 0.5 hours and decanted. The operation of adding water, grinding and decantation is repeated three times.

The resulting aqueous solutions are combined. Evaporate to remove about 2/3 of the volume. The residue is maintained at a temperature of 5 ... 10 ° C for 4 ... 5 hours. The precipitate formed is sucked off on a Buchner funnel. The resulting crystals were washed with 50 ml of ethanol cooled to 5 ° C.

117 g of manganese sulfate isolated are burgundy crystals.

Manganese sulfate is used in textile and porcelain production, as micronutrient fertilizers or as an electrolyte to produce manganese-containing compounds.

METHOD OF OBTAINING MANGANIAN PHOSPHATE SOLUTION

25 g of manganese dioxide, isolated according to the previously presented method, are triturated in a porcelain dish until a fine powder is formed. The powder is placed in a thin layer in a quartz tube equipped with electric heating. Manganese dioxide powder is held in a stream of carbon monoxide at a temperature of 250 ... 300 ° C for 5.0 ... 5.5 hours.

The powder is cooled and transferred to a box filled with nitrogen. Finely ground powder and 67.5 ml of 75% phosphoric acid are mixed in a porcelain beaker. Withstand 8 ... 12 hours, periodically mixing.

126.3 g of a gray solution are obtained. The resulting solution is used to deposit a protective film of manganese phosphate on the metal surface to prevent corrosion.

COPPER OXIDE ALLOCATION TECHNIQUE

450 ml of a solution of copper ammonia obtained at the stage of processing hopcalite, evaporated before the precipitation of the crystals. Then the mixture is cooled and incubated for 12 hours at a temperature of 5 ... 10 ° C.

The resulting precipitate of copper hydroxide is sucked off on a Buchner funnel and washed with 135 ml of distilled water. The resulting crystals are placed in a muffle furnace and incubated at a temperature of 750 ° C for 2 hours.

Get 23.5 g of copper oxide - brown powder. It can be used as a component of electrolytes in electroplating, insecticide, pigment for glass, ceramics, enamels or for the production of copper-containing compounds.

METHOD OF PRODUCING COPPER-AMMONIA CELLULOSE SOLUTION

The method used according to the recipe presented in the monograph: Pakshver A.B. Copper-ammonia fiber technology. M. 1947.

500 ml of the copper ammonia solution obtained in the hopcalite processing step is evaporated in vacuo to obtain 125 ml of a concentrated solution. The solution was transferred to a beaker. While stirring with a mechanical stirrer, 14.2 g of cotton pulp is added. Intensive stirring is continued for 1 hour.

Add 40 ml of 10% sodium hydroxide solution. Stirred for 1 hour at a temperature of 40 ... 46 ° C. Cool.

195 g of a viscous mass of a copper-ammonia cellulose solution is formed, which is used in industry for the production of cellulose hydrate fiber.

METHOD OF OBTAINING COLLOIDAL COPPER

The work uses a solution of copper ammonia obtained at the stage of processing hopcalite.

A solution of phosphorus in diethyl ether is prepared in a separate bowl. A sample of 1.2 g of white phosphorus is finely ground, poured with 5 ml of a 5% solution of nitric acid and incubated for 1 day, shaking occasionally. Then the nitric acid solution is drained and washed with phosphorus in 2 portions of 5 ml of distilled water. 5 ml of a 10% aqueous solution of urea are added to phosphorus and placed in a mechanical mash. Shake for 4 ... 6 hours. The urea solution is drained. 10 ml of diethyl ether are added to phosphorus. Shake on a mechanical plate until complete dissolution of phosphorus. Transfer the solution to a vessel of dark glass. 100 ml of diethyl ether are added. Shake. The prepared solution of phosphorus in diethyl ether is stored in a carefully sealed vessel of dark glass.

5 ml of a solution of copper ammonia is placed in a beaker. 450 ml of distilled water are added and mixed thoroughly. The solution is brought to a boil and 10 ml of a 1% hydrazine hydrate solution are added dropwise to the boiling solution. In this case, discoloration of a bright blue solution is observed. Then add 100 ml of a pre-prepared solution of phosphorus in diethyl ether. The solution turns yellow and then red. When storing the solution, a black precipitate forms slowly. The precipitate in the air turns green.

Claims (1)

The method of disposal of hopcalite used in gas cartridge cartridges and collective protective equipment, which consists in processing it to obtain products suitable for further use, characterized in that the processing includes the following stages: chemical treatment of the crushed granules of hopcalite with an aqueous solution of ammonia at a temperature of 75-85 ° C with vigorous stirring of the reaction mixture for 2.5-3 h, cooling the mixture to 25-30 ° C and separation by filtration into manganese compounds and an aqueous solution of ammonia copper with their further separate processing, while the processing of manganese compounds is carried out by mixing them with nitric acid, boiling the mixture, filtering the solution and drying to obtain crystals of manganese dioxide, which are treated with sulfuric or phosphoric acid to obtain respectively manganese sulfate or a solution of manganese phosphate, and For processing an aqueous solution of copper ammonia, one of the methods is used: evaporation of the solution before the precipitation of crystals of copper hydroxide, followed by their removal and by pouring to obtain a copper oxide powder; adding cotton cellulose and sodium hydroxide to an aqueous solution of copper ammonia to produce a copper-ammonia cellulose solution; treating the aqueous solution of copper ammonia with phosphorus and a hydrazine hydrate solution to obtain colloidal copper.