How dehalogenate halogenated organic or organoelement compounds

 

(57) Abstract:

Usage: the invention relates to the field of organic and Organoelement chemistry, namely, the process of the removal of the halogen atom from various halogenated compounds. One of the important tasks of these processes is detoxification products, particularly harmful to humans and to the environment. These include wastes from chemical industries, especially polygalacturonase aromatic compounds (including dioxins and furans), and accumulated in warehouses and in natural conditions, is prohibited to the use of pesticides (herbicides, insecticides and other chemical materials. The inventive halogen-containing compound is mixed with a powder of a metal such as aluminum, magnesium, zinc, iron, manganese, etc. or alloys of metals such as titanium, aluminum, and titanium-Nickel alloys, after which originally locally thermally initiated chemical interaction of the components of the original mixture. The reaction proceeds with spontaneous heating in autothermal mode, resulting in a carbonaceous material and a metal halide, which can be easily separated by dissolving in water with the of the polluting gas discharge, contaminated wastewater and harmless end products of the reaction; small energy cost of the process; the simplicity of the technological design process, the ability to create a closed non-waste technology; high speed and completeness of the process; the use of available raw materials, the absence of catalysts and process for their regeneration; the possibility of further use in industry legkorazmyvaemykh reaction products. 3 C.p. f-crystals.

The invention relates to organic and Organoelement chemistry, namely, the processes of detachment of atoms of halogen from various halogenated compounds.

One of the important tasks of these processes is detoxification products, particularly harmful to humans and to the environment.

These include wastes from chemical industries, especially polygalacturonase aromatic compounds (including dioxins and dibenzofurans), accumulated in warehouses and in natural conditions is forbidden to use pesticides (herbicides, insecticides, and other chemical materials, such as polychlorinated biphenyls.

Environmental problems associated with the destruction of haloids is authorized sustainability in the natural environment, incomplete decomposition in the known processes hazardous waste disposal (incineration, landfill, chemical and biological decontamination), accompanied by the formation of harmful by-products.

It is known that due to the increased resistance of these compounds accumulate in the soil, they are found in aquifers used for drinking water, plants, plankton and food.

The mass application of number kaleidograph compounds in refrigeration, in the form of aerosols, in the manufacture of electronic materials and plastics leads to the destruction of the stratospheric ozone layer.

The destruction of the above compounds, as well as existing stocks of some types of chemical warfare agents represent a major scientific and technical challenge.

There is a method of decomposition halogenorganics compounds by oxidation in the presence of a catalyst consisting of a mixture of potassium halide and vanadium oxide at a temperature of 300-600o[1]

The method requires high energy costs, conduct special cleaning flue gases and catalyst regeneration.

There is a method of decomposition halogenorganics combustion are halogenated, carbon dioxide and water. The necessary adsorption of the formed galoidovodorodov.

The disadvantages of this method are: the possibility of formation of xenobiotics, including dioxins; the loss of the carbon component of the original product; the formation of a large number abgaznaya hydrochloric acid, which is the secondary waste; the need for large quantities of fuel; air pollution by combustion products, including carbon dioxide, greenhouse effect.

There is a method of decomposing halogenated hydrocarbon waste productions by burning in corrosion resistant furnaces in the presence of water vapor in a fluidized bed of catalyst consisting of oxides of silicon, aluminum, sodium and potassium [3]

Although this method provides a relatively complete combustion of various substances, and the escaping gases have a low chlorine content, it also has a number of disadvantages, namely high energy costs; expensive equipment; decontamination media and regeneration of the catalyst.

The main disadvantage of this method is the formation of chlorine, hydrogen chloride and dioxins in the combustion products, which inevitably contaminate OK is avodarto by contact with molten metals: aluminum, calcium, iron, zinc, rare earth elements [4] the chlorohydrocarbons injected into the flow of carrier gas in the lower part of the volume of molten metal.

The disadvantages of this method are: the high cost of energy associated with the need of heating source of the metal to the melting temperature and maintain it in the molten state; in the way degradable compound is injected with a carrier gas, which significantly complicates the instrumentation process and significantly narrows the range of compounds that can be subjected to dehalogenation; the method is also inherent in all of the major disadvantages inherent in the metallurgical process, namely, the destruction of the furnace lining, the problem of slag formation, occupational hazards and other

It should also be noted that this method for the reaction of dehalogenase requires a constant supply of external energy, while in the proposed method, a supply of external energy is required only in the form of short-term local heat pulse, which only triggers the reaction of interaction haloesters connection with a powder of a metal or alloy, and then the process proceeds in autothermal mode, bol is the person reaction dehalogenase is carried out in the liquid phase (molten metal), while in the proposed method, the reaction dehalogenase solid phase and the metal is used in powder form.

In the proposed method, we destroy the product is a component of the initial powder mixture, while in the method prototype it is introduced into the melt by means of a carrier gas, which not only complicates the instrumentation process and creates serious environmental problems for the detoxification of exhaust gases, but also limits the range of halogenated products to be destroyed.

The aim of the invention is to develop an environmentally-friendly way to dihalogenoalkane toxic halogenated organic and Organoelement compounds.

The proposed method is that halogenated compounds are mixed with a powder of a metal such as aluminum, magnesium, zinc, iron, manganese, etc. or an alloy of metals, for example, titanoalyuminidnykh or titanocene alloys, after which the mixture, regardless of its volume, is heated at one point (local initiation) before spontaneous autothermal reaction, for example, touching a hot electricity metal wire. The reaction proceeds which may be easily separated by dissolving in water with subsequent evaporation.

If the reaction proceeds too vigorously, in the initial mixture further added to 300 wt. diluent, for example, activated carbon, carbon black, metal oxide, silicon dioxide, reaction products, etc.

Distinctive features of the proposed method are: the use of metal powder or powders of metal alloys, conducting the reaction in the solid phase, with a minimum expenditure of external energy needed only a point terminationone reaction.

Advantages of the proposed method are: environmental friendliness of the process, namely, the absence of polluting gases, contaminated wastewater and harmless end products of the reaction; small energy cost of the process; the simplicity of the technological design process, the ability to create a closed non-waste technology; high speed and completeness of the process; the use of available raw materials, the absence of catalysts and process for their regeneration.

Due to the fact that the reaction products are salts of the respective metals and carbon materials easily shared with each other, we might see further use in the industry is more. The resulting homogeneous mixture was poured into a vertically positioned reactor open type and condense. Download reactor conduct or air, or in a weak current of inert gas fed into the lower part of the reactor, after which the mixture is ignited by a touch of fiery electricity metal wire. Starts an exothermic reaction, extending from top to bottom height of the reactor. To prevent rapid reaction and release of products in the initial mixture in some cases add up to 300 wt. inert diluent, which can be used metal oxides, activated carbon, carbon black, silica or the reaction products. After completion of the reaction the reactor was cooled down to room temperature and unload. The reaction products are washed with water or dilute (10%) acids. In the process of evaporation of the filtrate secrete salt source of metals, and in the washed and dried residue detect the presence of a halogen with high-quality samples Beylshtein.

Example 1. The mixture 2,48 g hexapetala and of 0.58 g of iron powder ("carbonyl") grind in a mortar and condense in the reactor vertically located a quartz tube with an internal diameter the PRS serves a weak stream of nitrogen. Then compacted mass of ignited by touching a hot wire. Is exothermic reaction: its front is moved to the bottom of the reactor for a few seconds. The resulting tribromide iron stands out from the reacting system in the form of brown vapor and condenses on the inner surface of the cooled glass cap. Remaining in the reactor black friable mass was washed with 3 ml of 10% hydrochloric acid, then twice with 5 ml of distilled water and dried. Dry black powder weighs 0.11 g, does not contain halogen and burns in the air without a trace.

Example 2. In the conditions of example 1 interaction is subjected to a mixture of 3.65 g of sodium salt of trichloroacetic acid and 1.70 g of iron powder. The process proceeds with a strong self-heating. The mixture darkens, increasing in volume to about half. After treatment 15 ml of 10% hydrochloric acid, two washes with 5 ml of methanol and drying black with graphite shimmer powder did not contain chlorine and weighed to 1.05, In the process of evaporation of the filtrate quantitatively the resulting iron chloride (II).

Example 3. In the conditions of example 1 are subjected to the interaction of a mixture of 2.55 g of para-dibromobenzene with, 0.6 g of hexapetala, 0.36 g of magnesium powder brand MPF-4 and 0.75 g of oxide may in a few seconds. Black loose product leaching allocate to 2.57 g of magnesium bromide. Dried filter residue has a negative test for halogen and weighs 0,77 g

Example 4. The product of the interaction of trichloride arsenic activated carbon (AC) is obtained by addition of 1.35 g AsCl3to 1.12 g of granulated AU, pre-late harvested for 20 min at 300-310oWith the water-jet vacuum pump and chilled in an environment of natural gas. In the process of interaction observed strong heating of the mixture. Pounded in a mortar in the absence of moisture, the mixture 2,43 g of this product with 0.28 g of magnesium powder brand MPF-4 fire in a quartz reactor under the conditions of example 1. Energetic solid-phase reaction is completed within a few seconds. Of the reaction mixture was fotogramas about 0.03 g of arsenic deposited on the cold surface. The resulting black mass of water was extracted with 1.06 g of magnesium chloride. Test for halogen in the carbon balance is negative.

Example 5. 1,80 g svejeporublennogo and cooled in a closed vessel powder gamma alumina impregnated with 1.10 g of performativity. The resulting mass is triturated in a mortar with a mixture of powders of 0.35 g of aluminum and 0.14 g of magnesium was placed in a porcelain crucible abysia. The black mass of the product is not soluble in water and organic solvents, 3,31,

Example 6. of 0.91 g of tetrachloroethylene caused by 0,89 g of silicon dioxide, mixed and triturated in a mortar with 0.28 g of magnesium powder. Then under the conditions of example 5, the mixture is ignited. The reaction proceeds vigorously with the glow and noise. The resulting voluminous black mass of water extracted magnesium chloride, weighing after evaporation of 1.05 g In the dried solid residue of the presence of the halogen is not found.

Example 7. 0.74 g technical 2,2(R,R-dichlorophenyl)-1,1,1-trichloroethane (DDT) after grinding in a mortar with 0,064 g of magnesium ignited under the conditions of example 1 in the crucible. There is a rapid combustion of the mixture with a small emission of particulate flakes. Black friable mass with hot water wash 0.25 g of magnesium chloride. In nerastvorim solid residue chlorine is absent.

Example 8. In the conditions of example 1 in a reactor initiate thermal reaction in a mixture of 1.30 g of gamma-hexachlorocyclohexane (lindane), of 0.47 g of powdered zinc (zinc dust), 0.16 g of magnesium powder and 1.2 g of silica gel with a particle size of 40 to 100 μm. With the beginning of the process in the upper part of the reactor is observed aptasia flame. Of the solid product of the reaction water was removed of triptorelin mixed with 0.50 g of aluminium powder and in the conditions of example 1 initiate an exothermic reaction, accompanied by a bright glow. There is partial ablation of aluminum fluoride. Black solid residue after washing with water and drying weighs 1,00,

Example 10. Film of polyvinyl chloride (PVC) with a thickness of about 100 μm, containing distributed therein magnesium powder (0.16 g and 0,033 g, respectively), obtained by pouring in a flat glass Cup suspension of magnesium in 10 ml of a solution of PVC in tetrahydrofuran. The dried material is ground and pound in a mortar with additional amounts of magnesium (0.01 g) and magnesium oxide (0.05 g). In the conditions of example 1 initiate an exothermic reaction. Black loose product water wash 0.14 g of magnesium chloride. In the carbon balance of the chlorine is not contained.

Example 11. 1.70 g of sodium salt of trichloroacetic acid, 0,92 g of zinc dust and 0.50 g of carbon black after grinding in a mortar processed under the conditions of example 1. During the reaction occurs in a strong heating of the mixture. From 3,15 g black friable reaction product 10 ml of N2O extracted 1.85 g of zinc chloride. Carbon residue does not contain chlorine and is used as a diluent source mixtures.

Example 12. In the conditions of example 1 initiate an exothermic reaction in a mixture of 1.50 g of hexachlorethane is camping in a few seconds. After washing with water and drying loose black balance the weight of 0.90 g, qualitative test for halogen negative.

Example 13. A mixture of powders of 0.83 g of 2,4,5-trichlorophenolate sodium and 0.16 g of magnesium was placed in a porcelain crucible with a volume of 3 ml and set on fire. In the crucible appears glow, which can be maintained for 7-8 C. During the reaction of the crucible is allocated voluminous black mass of cylindrical form, break up as a selection. The total weight of the product of 0.95, Water extraction from him allot of 0.61 g of magnesium chloride. The chlorine reaction of this carbon balance is negative.

Example 14. In the conditions of example 13 initiate thermochemical reaction in a mixture of powders of aluminum (0.15 g) and magnesium (0.07 g) and 0.59 g of silica gel with a particle size of 40-60 microns, which from a solution in methylene chloride pre-applied to 0.89 g of meta-bis(trichloromethyl)benzene. After a few seconds of intense burning process is completed. The resulting black friable mass is washed with water and dried. The weight of her 0.84 g, test for halogen content is negative.

Example 15. In the conditions of example 1 ignite a mixture of 2.8 g of hexachlorobenzene, 0.71 g of magnesium and 10.5 g of magnesium oxide. The reaction ends after a few seconds. After the halogen negative.

Example 16. 1.70 g dainoringa complex of tin tetrachloride [SnCl42C9H7N] pound in a mortar in the absence of moisture with 0.25 g of magnesium powder. Fire compacted in a crucible a mixture of the technique described in example 1. Weight gradually over 10 seconds, darkens and increases in volume. Released vapor condenses, the condensate does not contain chlorine and is autognosis the quinoline. The weight of the solid product 1,50, From his water extraction extract 0.95 g of magnesium chloride.

Example 17. A mixture of 2,4,5-trichlorophenolate sodium (3,07 g) with 0.45 g of powder titanomagnievoe alloy PTU (fraction 60 -200 μm), reinforced air and placed in the reaction crucible is ignited under the conditions of example 1. During vigorous reaction releases a significant amount of vapor, which absorb, passing through a cooled trap with activated carbon. Gain absorber of 2.10 g (94% of theoretical amount of the mixture of the chlorides of titanium and aluminum). The reaction product is black in color after washing with water and drying had a negative reaction to chlorine.

Example 18. In the conditions of example 17 conduct the reaction mixture powders 2,88 g trichloracetate sodium and titanium alloy (88,3 wt.) with Nickel (11.6 wt.) in the form of a fraction with a particle size of 40-100 μm. Pnom carbon residual chlorine was not detected.

Example 19. Loose gelatinous mass obtained by the swelling 1.45 g of polyvinylidenechloride in 3 ml of chloroform, and pound in a mortar with 1.01 g of zinc dust. The resulting mass is heated for 25 min at 100oWith the water-jet pump vacuum, then placed in a porcelain crucible and initiate thermal reaction conditions of example 1. In the resulting black product after washing with hot water and drying chlorine is not detected.

Example 20. The mixture 1,79 g hexachlorobenzene, 1.19 g of powder of manganese (20-100 µm) and of 0.60 g of magnesium oxide is ignited under the conditions of example 1. On completion of the exothermic reaction black loose a homogeneous mass is washed with 5% hydrochloric acid, water, acetone and the residue is dried. Get to 0.47 g of dry product containing no chlorine.

Example 21. In the conditions of example 1 in a reactor initiate thermal reaction in a mixture of 1.30 g of gamma-hexachlorocyclohexane (lindane), of 0.47 g of powdered zinc (zinc dust), 0.16 g of a powder of magnesium and of 1.93 g black reaction product obtained in example 8. With the beginning of the process in the upper part of the reactor is observed aptasia flame. From the solid reaction product with water remove the chlorides of zinc and magnesium, after evaporation and drying of the combined weight of 1.44,

1. How dehalogenate halogenated organic or Organoelement compounds by decomposition at elevated temperature processing their metal compound, characterized in that the metal oedipina use the powder of the metal or alloy of metals and the process is conducted with an initial local thermal initiation in autothermal mode.

2. The method according to p. 1, characterized in that the quality of the metal used is aluminum, magnesium, iron, zinc or manganese.

3. The method according to p. 1, characterized in that as the alloy metals used titanium-aluminum or titanium-Nickel alloys.

4. The method according to p. 1, wherein the process is conducted in the presence of an inert diluent in an amount up to 300 wt. for example, a metal oxide, or activated carbon, or soot, or silicon dioxide, or the reaction products.

 

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