Catalysis and petrochemistry

Catalytic processing of organochlorine wastes into valuable monomers

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B.Stepasiuk¹, T.Haievska¹, O.Spaska¹, Yu.Bilokopytov ¹,
S.Boichenko^2,1, A.Yakovlieva^2,1

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¹National Aviation University, 1, Liubomyra Huzara ave, Kyiv, Ukraine 03058
²Ukrainian Research & Educational Center of Chemmotology and Certification of Fuel, Lubricants, Technical Liquids
Е-mail: 3962103@stud.nau.edu.ua, ximpolit@ukr.net, spaskaolena@ukr.net
, yurii.bilokopytov@npp.nau.edu.ua, chemmotology@ukr.net, a.v.iakovlieva@ukr.net

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ABSTRACT

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The paper is devoted to experimental development of method for 1,1,2-trichlorethane (TCE) dehydrochlorination (DHC). The economic and environmental issues of organic chlorinated compounds processing are described. The basic principle and possible products of TCE processing are presented. The DHC of TCE, which is one of the chlorinated organic wastes produced in the ethylene dichloride process, to vinylidene chloride (VDC) was carried out over over CaO, MgO supported on SiO₂ and modified with CsCl catalysts. This process was carried out in a continuous flow fixed-bed reactor. The prepared catalysts were characterized by surface area and base properties before/after reaction. The methodology for determining properties of catalyst is described. Laboratory activity test apparatus was developed, and the schematic diagram is presented in the paper. The method of determination of TCE concentration of was calculated from its partial saturation vapor pressure at a given temperature is presented. Encouraging results were obtained on the catalyst containing 10 % CsCl/CaO·SiO₂. The direction of the DHC reaction changed radically under described conditions: VDC was not formed at all and the major products were cis- and trans-1,2-dichloroethene. Interesting results were obtained with the catalytic system comprising 10 % (MgO-CsCl) (1:1) supported on SiO2. DHC of 2 % TCE/Ar at 302 °C proceeds quantitatively over 20 h with selectivity for VDC of more than 80%. These systems are suitable to study the factors providing the binding and removal of HCl from the reaction zone. A possible way to increase the selectivity for VDC is the creation of the conditions favoring the DHC of TCE into VDC by the radical mechanism, which was observed in experiments with 10% CsCl/CaSiO₃. The directions for future researches are formulated and described.

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KEYWORDS

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dehydrochlorination, 1,1,2-trichloroethane, vinylidene chloride, supported catalyst

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