Structure and the catalysis mechanism of oxidative chlorination in nanostructural layers of a surface of alumina

Abstract

On the basis of X-ray diffraction and mass spectrometric analysis of carrier γ-Al2O3 and catalysts CuCl2/CuCl on its surface, the chemical structure of the active centers of two types oxidative chlorination catalysts applied and permeated type of industrial brands “Harshow” and “MEDС-B” was investigated. On the basis of quantum-mechanical theory of the crystal, field complexes were detected by the presence of CuCl2 cation stoichiometry and structure of the proposed model crystal quasichemical industrial catalyst permeated type MEDС-B for oxidative chlorination of ethylene. On the basis of quantum-mechanical calculations, we propose a new mechanism of catalysis crystal quasichemical oxidative chlorination of ethylene reaction for the catalysts of this type (MEDС-B) and confirmed the possibility of such a mechanism after the analysis of mass spectrometric studies of the active phase (H2 [CuCl4]) catalyst oxidative chlorination of ethylene. The possibility of the formation of atomic and molecular chlorine on the oxidative chlorination of ethylene catalyst surface during Deacon reaction was displaying, which may react with ethylene to produce 1,2-dichloroethane. For the active phase (H [CuCl2]), catalyst offered another model of the metal complex catalyst oxidative chlorination of ethylene deposited type (firm ‘Harshow,’ USA) and the mechanism of catalysis of oxidative chlorination of ethylene with this catalyst.

D-sorbitol-induced phase control of TiO2 nanoparticles and its application for dye-sensitized solar cells

“…S3 ). The remarkable performance of the DSSC fabricated with the anatase TiO 2 electrode might originate from its crystal phase, morphology, and high electrical conductivity and mobility ( Table S1 ) 43 . Contrary, due to the presence of several stacking faults and dislocations, electrode with rutile TiO 2 nanocrysyallites demonstrated lower conductivity and low dye intake capacity and thereby, smaller light harvesting capacity and lower DSSC performance 44 .…”

Features of the structure active centers of industrial catalysts for the oxidative chlorination of ethylene

“…They react in the form of corresponding salts of cuprum with the dustable hydroxyl groups of the carrier -γ-Al2O3 by reactions (№. 9 and 10), thus forming complex compounds on the surface, which subsequently catalyze the reaction of OCE in 1.2-DCE as shown earlier by [6]. At the same time, relatively large amounts of K and La do not positively influence the work of the catalyst X1 Harshow [13][14].…”

“…14-15) which are predominantly in a different form on the surface of the catalysts. Taking into account the foregoing, it can be argued that the structure of active centers on the surface of the catalysts X1(Harshow) and MEDC-B is confirmed, and determines the mechanism of the reaction of EOC for each of the selected catalysts differ from each other and was described by us earlier [6]. Thus the definition nanostructure catalyst surface OCE determine the conversion of raw materials, as well as yield and selectivity of the process and lead to fewer byproducts, organochlorine waste that will improve the environmental and economic component of the industrial process in the production of 1.2-DCE and VCM in global scale [14].…”

“…Namely two types of catalysts were considered -deposited catalyst X1 of the firm «Harshow», with copper chlorides supported onto an alumina surface, and permeated MEDC-B catalyst located in the internal pores of the support of the firm «SudChemie Catalyst». СuСl2 interactions with γ-Аl2О3 surface groups (≡Аl-ОН) lead to complex compounds formation with surface metal complexes reacting with ethylene, hydrogen chloride, and oxygen was proposed the authors of the article in previous publications [6]. For a catalyst X1, the mechanism of formation of surface structures during its production is as follow:…”

“…С2Н4 + 3НСl + О2  С2Н3Сl3 + 2Н2О (6) According to well-known authors [4], chlorine copper undergoes such transformations in this chemical process:…”