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The target oriented conversion of hydrocarbon raw materials into necessary products in the presence of nanocomposite systems, in particular, those prepared based on materials with zeolite or zeolite like struc tures, is a priority trend in the development of present day petroleum chemistry. It is well known that penta sils and mesoporous zeolite like systems modified with Pt, Ga, and Gd exhibit high activity and selectiv ity in the aromatization, oligomerization, and alkyla tion of low molecular weight saturated and unsatur ated hydrocarbons [1][2][3][4][5][6]; the conversion of methanol into aliphatic and aromatic hydrocarbons [7,8]; the alkylation of benzene with propane [9] or isopropanol [10]; the dehydrodisproportionation [11] and dehy droalkylation of alkyl substituted С 7 -С 8 cyclohex anes with methanol [12, 13]; etc. However, there is almost no data on the use of these catalysts in the dehydrogenation reactions of hydrocarbons, in partic ular, ethylbenzene conversion into styrene, although other modified forms of different zeolite containing catalysts are widely used in reactions for the produc tion of styrene and its methyl derivatives by the dehy drogenation of ethylbenzene [14][15][16], the dehydra tion of methyl and dimethylphenyl carbinols [17,18], and the alkylation of alkenylbenzenes [19,20] and tol uene [21,22] with methanol.The butadiene method implemented with the par ticipation of oxide and zeolite containing catalysts [23][24][25][26] is currently considered an alternative method for expanding the range of raw materials for styrene production. This method is performed in the following two stages: the dimerization of butadiene to 4 vinylcy clohexene and the dehydrogenation of the latter to styrene. For the industrial implementation of this pro cess, it is necessary to develop catalytic systems that are more efficient and provide high selectivity at either of the stages because of the presence of considerable 1,3 butadiene resources in the pyrolysis products of petroleum fractions.The dehydrogenation of 4 vinylcyclohexene in the presence of well known catalytic systems occurs with the predominant formation of ethylbenzene [25,27] or a mixture of ethylbenzene and styrene with the pre dominance of the former [23,24]. In this case, the ratio between the resulting reaction products-ethyl benzene and styrene-depends on the time of catalyst operation and changes significantly in the course of the process.This work is the development of studies on the oxi dative dehydrogenation of 4 vinylcyclohexene and ethylbenzene in the presence of zeolites TsVM modi fied with Pt and Ga. Here, we report the main experi mental results of studying changes in the activity and selectivity of nanocomposite systems prepared based on these zeolites and carbon nanoparticles immobi lized in them in the test reaction. EXPERIMENTALThe experiments were conducted on a laboratory setup at 0.1 MPa. A 3 g sample (fraction of 0.5-1 mm) of a catalyst, which was granulated without a binding agent, mixed with quartz grains in a ratio ...
The target oriented conversion of hydrocarbon raw materials into necessary products in the presence of nanocomposite systems, in particular, those prepared based on materials with zeolite or zeolite like struc tures, is a priority trend in the development of present day petroleum chemistry. It is well known that penta sils and mesoporous zeolite like systems modified with Pt, Ga, and Gd exhibit high activity and selectiv ity in the aromatization, oligomerization, and alkyla tion of low molecular weight saturated and unsatur ated hydrocarbons [1][2][3][4][5][6]; the conversion of methanol into aliphatic and aromatic hydrocarbons [7,8]; the alkylation of benzene with propane [9] or isopropanol [10]; the dehydrodisproportionation [11] and dehy droalkylation of alkyl substituted С 7 -С 8 cyclohex anes with methanol [12, 13]; etc. However, there is almost no data on the use of these catalysts in the dehydrogenation reactions of hydrocarbons, in partic ular, ethylbenzene conversion into styrene, although other modified forms of different zeolite containing catalysts are widely used in reactions for the produc tion of styrene and its methyl derivatives by the dehy drogenation of ethylbenzene [14][15][16], the dehydra tion of methyl and dimethylphenyl carbinols [17,18], and the alkylation of alkenylbenzenes [19,20] and tol uene [21,22] with methanol.The butadiene method implemented with the par ticipation of oxide and zeolite containing catalysts [23][24][25][26] is currently considered an alternative method for expanding the range of raw materials for styrene production. This method is performed in the following two stages: the dimerization of butadiene to 4 vinylcy clohexene and the dehydrogenation of the latter to styrene. For the industrial implementation of this pro cess, it is necessary to develop catalytic systems that are more efficient and provide high selectivity at either of the stages because of the presence of considerable 1,3 butadiene resources in the pyrolysis products of petroleum fractions.The dehydrogenation of 4 vinylcyclohexene in the presence of well known catalytic systems occurs with the predominant formation of ethylbenzene [25,27] or a mixture of ethylbenzene and styrene with the pre dominance of the former [23,24]. In this case, the ratio between the resulting reaction products-ethyl benzene and styrene-depends on the time of catalyst operation and changes significantly in the course of the process.This work is the development of studies on the oxi dative dehydrogenation of 4 vinylcyclohexene and ethylbenzene in the presence of zeolites TsVM modi fied with Pt and Ga. Here, we report the main experi mental results of studying changes in the activity and selectivity of nanocomposite systems prepared based on these zeolites and carbon nanoparticles immobi lized in them in the test reaction. EXPERIMENTALThe experiments were conducted on a laboratory setup at 0.1 MPa. A 3 g sample (fraction of 0.5-1 mm) of a catalyst, which was granulated without a binding agent, mixed with quartz grains in a ratio ...
Dimerization of 1,3-butadiene was investigated in a closed batch system under high-pressure conditions. 4-Vinylcyclohexene was mainly produced without using any solvents or catalysts at temperatures of 150–215 °C. The conversion of 1,3-butadiene was significantly dependent on the temperature and pressure. 1,3-Butadiene was converted to 4-vinylcyclohexene at selectivity higher than 90 mol % with by-products of 1,5-cyclooctadiene and 1,2-divinylcyclobutane. Large charges of reactant are efficient in achieving high conversions of 1,3-butadiene. Use of solvents, which dilute the reactant and absorb the reaction heat, is not favorable in the present dimerization of 1,3-butadiene under pressured conditions.
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