A method of processing organochlorine waste by method of hydrogenolysis

 

(57) Abstract:

The invention relates to a method of processing organochlorine waste by method of hydrogenolysis. The process is conducted in the presence of heterogeneous catalysts containing palladium at 250-350C. the Hydrogenolysis is carried out in an environment of transformer oil AMT-300 or vaseline oil when it is 10-20-fold excess relative to the weight of organochlorine wastes. When the molar ratio of hydrogen : organochlorine waste, equal to 20-40 : 1, with the further separation of the gaseous products and recycle solvent containing unreacted waste. As a result of processing of organochlorine wastes receive the mixture of products whose disposal is not straightforward. table 1.

The invention relates to the technology of organic synthesis, in particular, to methods for organochlorine waste production.

A method of refining organochlorine waste method chlorinolysis (L. N. Zanaveskin, C. A. Averianov, Y. A. Traeger. Prospects for the development of processing methods halogenorganics waste. Regularities of catalytic hydrogenolysis galogensoderjasimi compounds. // USP, T. 65, No. 7, 1996).

However, the (up to 500-600oC) and is associated with the formation of large quantities of hydrogen chloride and carbon tetrachloride, production should be phased out under the Montreal Protocol in connection with the prohibition of the release of ozone-depleting products.

In addition, high-temperature chlorination followed by education (along with perchloroethane) highly toxic products: hexachloroethane, hexachlorobenzene and Hexachlorobutadiene. Burning them difficult, therefore a significant part of their being buried.

The closest way to the same destination to the claimed invention on the totality of symptoms is the method of processing organochlorine waste by method of hydrogenolysis in the presence of heterogeneous catalysts containing platinum group metals at a temperature of 250-350oC (L. M. Kartashov, T. C. Chernysheva, L. N. Zanaveskin, Y. A. Traeger, I. N. Prokhorov. Processing of organochlorine wastes method of hydrogenation. // Chemical industry, 1996, N 6).

For the reason that impede the achievement of specified following technical result when using the known method is:

- difficulty industrial the deposits on the surface of the catalyst carrier resinous and cocoabased the reaction products of the polymerization of unsaturated hydrocarbons, formed during gas-phase catalytic hydrogenolysis, and the need for repeated regeneration of the catalyst.

The task of the claimed invention to provide an industrial method for processing organochlorine wastes by catalytic hydrogenolysis.

One of the most acute problems of the creation and organization of low-waste, environmentally friendly production halogenoalkanes products is the processing and disposal of such facilities.

Unpleasant feature of organochlorine wastes is that they are all xenobiotics and nature has no natural means of dealing with them. At the same time, not every way of turning halogenorganics compounds can be used for recycling, which was discussed above.

The most versatile and promising method of processing organochlorine waste is considered hydrogenolysis, as this method best meets the requirements of the waste processing techniques, such as:

- renewable carbon-containing raw material or commercial value of the resulting products;

- the efficiency of the processing is composed as a result of processing waste highly toxic substances.

During implementation of the invention can be obtained by technical result, which is expressed in the possibility:

- processing of organochlorine waste on an industrial scale;

- processing a wide range of organochlorine products;

- obtain the target products, which can be returned to the process cycle.

The above technical result is achieved by the feature of the method of processing organochlorine wastes, namely, that the hydrogenolysis is carried out in an inert high-boiling hydrocarbon solvent for 10-20 times its excess in relation to the mass of chlorinated organic wastes and at a molar ratio of hydrogen and chloro-organic waste, equal to 20-40: 1, with the further separation of the gaseous reaction products by the known methods and recycling of unreacted waste solvent. As the inert high-boiling hydrocarbon solvent used liquid mixture alifaticheskih, aromatic and cyclic hydrocarbons with a boiling range of 250-350oC (transformer oil AMT-300, liquid paraffin).

Processing of organochlorine wastes guy is Itachi this process on an industrial scale, because the solvent to regenerate the catalyst by washing with the surface of the catalyst carrier resinous and cocoabased products.

The way hydrogenolysis real organochlorine waste products of epichlorohydrin, perchloroethane and vinyl chloride in the liquid phase is carried out in a flow type reactor with a fixed bed of catalyst, Proektirovanie by well-known methods. As catalyst using alumina and activated carbon impregnated with salts of palladium and palladium content of 0.4-1.8 wt.% respectively.

Hydrogen and a solution or a solution and fine suspension of organochlorine waste 10-20-fold excess of the high-boiling solvent relative to the weight of organochlorine waste at a molar ratio of hydrogen: organochlorine waste 20-40:1 concurrent threads is served in the upper part of the reactor. The temperature of the process 250-350oC.

The reaction products are a mixture of chlorohydrocarbons in the solvent, unreacted hydrogen and vydelevshimsya hydrogen chloride is removed from the bottom of the reactor and subjected to separation of the known methods.

High-boiling ug the satisfactory results and great availability for experimental validation was used catalytic system based on palladium and aluminum oxide or activated charcoal.

The method is confirmed by examples.

Example 1. In a flow type reactor with a fixed bed catalyst containing 0.4% palladium on aluminum oxide serves organochlorine waste in the amount of 2.5 g/h (0,0187 mol/h) in an inert high-boiling solvent in the ratio of organochlorine waste:solvent 1:10.

As organochlorine waste use waste production of vinyl chloride of the following composition: 1,2-dichloroethane - 12,2%; high-boiling - 72,9%, including 1,1,2-trichloroethane - 42,4%, perchlorethylene by 14.4%, 1,1,2,2 - and 1,1,1,2-trichloroethane and 14.9% (Composition A).

As the inert high-boiling solvent used transformer oil AMT 300.

Hydrogen is fed into the parallel reactor in a molar ratio to organochlorine deviation equal to 1: 40. The hydrogenolysis is carried out at a temperature 295-300oC.

Conversion of the original chlorohydrocarbons is 88,7%.

The composition of the obtained products: ethane, and ethylene - 0.35 g/h (0,012 mol/h); ethyl chloride and vinyl chloride - 0.28 g/h (0,0045 mol/h) of hydrogen chloride 1,67 g/h (0,045 mol/h); unreacted waste - 0,20 (0,0015 mol/h).

Example 2. Analogously to example 1, the hydrogenolysis is carried out at a temperature of 250o<>/P>Example 4. Analogously to example 1, during use as a catalyst activated carbon content of 1.8% palladium.

Example 5. Analogously to example 1, the hydrogenolysis is carried out at 20-fold excess of hydrogen.

Example 6. Analogously to example 1, is subjected to hydrogenolysis organochlorine waste products of epichlorohydrin following composition (Composition B): dichloropropan - 36,4%, dichloropropene - 13,5%, monochloropropane - 18,5%, trichlorpropane - 26,0%, high-boiling (osmole) is 5.6%.

Example 7. Analogously to example 1, is subjected to hydrogenolysis waste of perchloromethane of the following composition (Composition B): hexachlorobenzene - 35,5%, Hexachlorobutadiene - 36,3%, hexachlorethane at 24.1%, osmole of 4.1%.

The results of the examples are given in the table.

The use of the proposed method of processing organochlorine waste by method of hydrogenolysis gives it an industrial scale.

Unlike the method of disposal of waste organochlorine production (prototype), where the process was used waste pre-clarified, the preferred method involves the processing of real waste in a wide range of both composition and Peabody organochlorine waste is the option of turning them into a mixture of products, disposal of which is not straightforward.

A method of processing organochlorine waste by method of hydrogenolysis in the presence of heterogeneous catalysts containing palladium at 250 - 350oC, wherein the hydrogenolysis is carried out in an environment of transformer oil AMT-300 or vaseline oil during its 10 - 20-fold excess relative to the mass of chlorinated organic wastes and at a molar ratio of hydrogen : organochlorine waste, equal to 20-40 : 1, with the further separation of the gaseous products and recycle solvent containing unreacted waste.

 

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