Catalyst for hydrogenation of carbon tetrachloride

 

(57) Abstract:

Usage: chloroform is a valuable intermediate in organic synthesis and is used as a solvent. The chlorinated paraffin wax are used as plasticizers and flame retardants for polymeric materials, in particular of polyvinyl chloride. the essence of the invention: a catalyst for hydrogenation of carbon tetrachloride higher paraffins use the product of the interaction of copper chloride (1) with caprolactam or dimethylformamide in the media, the content of chloride of copper is 1 to 7% by weight. from the media. In preferred embodiments, as the carrier using silica gel, and the mass ratio of copper chloride and dimethylformamide or caprolactam at drawing is 1 : (50 - 200) 1 table. 2 C.p. f-crystals, 1 table.

The invention relates to catalysts for the hydrogenation of carbon tetrachloride (Chu). Hydrogenation of Chu is an important issue in connection with the signing of the Montreal Convention and the related agreements, effectively banning the use of Chu as in derivatives of freons, and as a solvent. As a result, in Russia and abroad there are large reserves of Chu produced in the recycling process chlorine is tion is currently the most promising direction of its proper disposal.

A known catalyst for the hydrogenation of Chu molecular hydrogen - palladium, rhodium or ruthenium on a carrier - to ensure the efficient hydrogenation of Chu under a pressure of 80 ATM at 250oC [1]. The disadvantage of the catalyst is that in the process with his participation by the equation

CCl4+H2_ CHCl3+HCl

in stoichiometric quantities to spent Chu is formed of low-value product - abhazy hydrogen chloride. In addition, the use as catalysts of expensive platinum group metals complicates and increases the cost of technology.

The closest to this is the catalyst for the hydrogenation of Chu action methane - metallic zinc [2]. The catalyst is free from the disadvantage noted above, as the source of hydrogen can be used methane and together with chloroform produces methyl chloride, are useful, though limited, as an intermediate in organic synthesis. Scarce platinum metals in this case are also not used. The disadvantage of the catalyst, however, is the inability to use, other than methane, sources of hydrogen. As shown by our experiments (see comparative example in this application), activity and selek is, the term when used as a source of hydrogen higher paraffins along with chloroform are the most valuable products of the chlorinated paraffin wax. Catalysts, providing effective course of this process up to the present time, are not described in literature.

The objective of the invention is to provide a catalyst that enable effective hydrogenation of Chu effect of higher paraffins.

The problem is solved by a catalyst for the hydrogenation of Chu - product of the interaction of copper chloride (I) with dimethylformamide (DMF) or caprolactam (CL) on the media when the content of copper chloride 1-7 wt.% from the media. In the preferred embodiment, as the carrier using silica gel when the mass ratio of CuCl/DMF or CuCl/CL in the process of deposition of the catalyst on the carrier 1:(50-200).

It should be noted that the catalyst is not a stoichiometric compound with a specific formula, the efficiency is determined by the combination of the above features (using DMF or CL, and the mass ratio of copper and DMF (or CL) during application).

The technical essence of the invention consists in using as the catalyst the Hydra is tion enables use as a hydrogen-containing raw material of higher paraffins, when this is achieved the high selectivity of the process according to chloroform, and along with chloroform obtained valuable organochlorine products - chlorinated paraffin wax, which are widely used as flame retardants and plasticizers in polymer materials.

The invention is illustrated in examples 1-10. Comparative example 11 demonstrates the impossibility of achieving the goal when using the known catalyst is metallic zinc.

The use of chloride of copper in quantities above or below the selected interval is impractical: the reduction leads to a significant reduction in the conversion of the reactants, and the increase does not give a measurable positive effect and only increases the consumption of salt of copper.

Example 1. Obtaining a catalyst.

In a round bottom flask, equipped with stirrer, reflux condenser attached to the end of glycerin bolt and hose inert gas (nitrogen) was placed 80 ml of chloroform, 20 g of caprolactam and 0.4 g of copper chloride (I). Include a stream of nitrogen and the mass is stirred at the boiling temperature of the solvent for 2 hours While there is a partial dissolution of copper chloride and the solution becomes green. Then to rastvorennoi temperature and evaporated under vacuum of 15-20 mm RT. Art. on a rotary evaporator to dryness. Thereafter, the catalyst was kept under vacuum at 200oC for 2 hours Get loose greyish-green powder, suitable for use in the hydrogenation.

Analysis of the solution after separation of the catalyst shows almost complete precipitation of copper chloride on the carrier. A specific method for the elemental analysis of the amount of organic components on the carrier is not constant and varies within the range that meets the molar ratio of copper:DMF (or CL) from 0.6 to 2.5 (in this example, it amounted to about 0.9). This shows that the catalyst is not stekhiometricheskom complex, and is a mixture of several complexes of copper. Because the correlation between the amount of organic matter and the activity of the catalyst is not detected, the latter cannot be regarded as an essential feature of the invention and further examples are not given.

The catalyst is stable in contact with the atmosphere and can be stored in a sealed container without special precautions without loss of activity for at least a month.

The catalyst based on CL get similarly. Replacement of chloroform on drri attempts to use a solvent of some type, for example acetone, the catalyst activity sharply, not less than two times reduced. Carrying out the deposition of copper chloride in a chlorinated solvent in the absence of DMF or CL does not obtain an active catalyst.

Example 2. Testing of catalytic properties.

In a thick-walled glass reactor add 2 g of the catalyst obtained according to example 1, 6 g Cho and 1.4 g of n-decane. The reactor is sealed and heated to 180oC for 8 hours and Then the reactor is cooled to (-30oC) reveal, is separated by decantation of the solid catalyst and the contents analyzed first chromatographic, and then the method of gravimetric analysis. Get the following results, %: conversion of Cho 32, the conversion of the Dean of 75, the selectivity of the conversion of Chu in chloroform 98,5, the number of products osmola 1. Weight analysis removed by vacuum evaporating device products fraction of chlorinated paraffin wax containing the data of chromatographic analysis of a mixture of mono-, di - and trichloromethane shows a chlorine content of 25%. The chlorinated paraffin wax are transparent bending slightly yellowish liquid and can be used directly or as an intermediate to produce a marketable chloroparaffin CP-470 content is ichno.

The results of the experiments presented in the table.

Example 11 (comparative). The process is conducted as described in example 2, but as a catalyst for using 0.5 g of metallic zinc. After opening screen get black thick gummy mass. Analysis of the part, which is soluble in an excess of acetone, shows that the conversion of Cho is about 20%, Dean - around 60%, the main products are heavy unidentified substances, the output of chlorinated paraffin wax small. Among light products detected chloride, chloroform, methylene chloride and unidentified impurities. Evaluation of selectivity in the chloroform gives the value of the order of 50%. It is clear that the achievement of this goal with the use of metallic zinc as a catalyst impossible.

In summary, the proposed catalyst for the first time enables the hydrogenation of Chu higher paraffins with high selectivity for the chloroform, and together with chloroform formed a valuable organochlorine product - chloroparaffin.

1. Catalyst for hydrogenation of carbon tetrachloride higher paraffins, characterized in that it is a product of the interaction of copper chloride (I) with caprolactam or digitiform the>

2. The catalyst p. 1, characterized in that as the media it contains silica gel.

3. The catalyst PP.1 and 2, characterized in that the mass ratio of copper chloride and dimethylformamide or caprolactam at drawing is 1 : 50 to 200.

 

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