Catalytic Conversion of Ethanol Into 1,3-Butadiene: Achievements and Prospects: A Review
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CATALYTIC CONVERSION OF ETHANOL INTO 1,3-BUTADIENE: ACHIEVEMENTS AND PROSPECTS: A REVIEW
P. I. Kyriienko, O. V. Larina, S. O. Soloviev, and S. M. Orlyk
UDC 544.478.1
The results of the studies of the processes of catalytic conversion of ethanol to 1,3-butadiene during the last decade are summarized. Modern ideas about the mechanisms of such processes are discussed. The influence of the composition and method of preparation, as well as the nature of modifying additives on redox and acid–base characteristics of the catalyst surface, which determine their activity and selectivity, is reviewed. Particular attention is paid to the conversion of ethanol–aqueous mixtures. The directions of further research for the implementation of the process of obtaining 1,3-butadiene from ethanol and ethanol–aqueous mixtures are outlined.
Keywords: ethanol; 1,3-butadiene; conversion of ethanol–aqueous mixtures; aldol condensation; MgO-SiO2; ZrO2-SiO2; rare earth elements.
INTRODUCTION The development of technological processes based on the “sustainable development” principles is one of the priorities of modern research in the field of chemistry and chemical technology [1]. Bioethanol is considered to be one of the most promising (semi) products of biomass processing for further use in industrial production of various value-added chemical products and motor fuels [2-7]. Significant investments in the technology of obtaining ethanol from non-food biomass contribute to the gradual reduction of its cost [3, 8-10]. One of the products that can be obtained directly from ethanol is 1,3-butadiene (BD) [4, 7, 11, 12]. BD is used in the production of synthetic rubbers, elastomers, and polymer resins [13]. BD is extracted from C4 fractions of steam cracking of oil in industry [14, 15]. Since the yield of butadiene depends significantly on the source raw material, the BD production is sensitive to market instability and new trends in the oil industry (for example, the use of shale gas), which can lead to a BD shortage [16, 17]. These factors resulted in an increased interest in the process of catalytic conversion of ethanol into BD (ethanol-to-butadiene process, ETB process) as an alternative to the oil-based process. V. M. Ipatiev was the first to show the possibility of obtaining BD from ethanol in the presence of a solid-phase catalyst in a stream at high temperature. The ETB process was implemented by S. V. Lebedev in industry and remained the main method of BD obtaining (Lebedev method) in Europe until the 60’s of the XX century [11, 19-21]. Initially, the ETB process was performed using a catalyst based on a mixture of zinc and aluminum oxides (ZnO-Al2O3), and later a more selective catalyst based on MgO-SiO2 was developed [11, 19, 22]. The composition of the catalyst and the technology of its production were of strategic importance; therefore, they were closed for publication. It is known only that the catalyst must contain dehydration and dehydrogenation components [20, 21, 23]. ________________________________________________________
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