Transition Metal Phosphides (Ni, Co, Mo, W) for Hydrodeoxygenation of Biorefinery Products (a Review)
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sition Metal Phosphides (Ni, Co, Mo, W) for Hydrodeoxygenation of Biorefinery Products (a Review) M. A. Golubevaa, *, E. M. Zakharyana, and A. L. Maximova aTopchiev
Institute of Petrochemical Synthesis, Russian Academy of Sciences, Moscow, 119991 Russia *e-mail: [email protected] Received May 26, 2020; revised May 29, 2020; accepted June 11, 2020
Abstract—The active use of transition metal phosphides in catalysis commenced at the beginning of the 2000s primarily in hydrodesulfurization and hydrodenitrogenation reactions. Owing to an increased interest in biomass-based feedstocks the intensive use of phosphides in hydrodeoxygenation reactions started in the first part of the 2010s. In earlier reviews devoted to phosphides, which were published before the 2010s, no information pertaining to hydrodeoxygenation is available. This review addresses monometallic phosphides of such transition metals as nickel, cobalt, molybdenum, and tungsten and covers their structure, synthesis, and properties. Transition metal phosphides are promising catalysts for hydroprocesses. They possess both metal active sites and acid sites, and, therefore, demonstrate activity not only in hydrogenation but in a number of acid-catalyzed processes. The review concerns the hydrodeoxygenation reactions of higher fatty acids and their esters; vegetable oils; and bio-oil and its model compounds. The hydrotreatment of vegetable oils and their derivatives over phosphides makes it possible to obtain hydrocarbons, which can be used as diesel fuel components or as a pure fuel. Using the hydrodeoxygenation of bio-oil model compounds catalyzed by phosphides partially or fully deoxygenated products may be obtained; however, the hydrotreatment of bio-oil itself did not provided positive results so far and calls for further research. Keywords: transition metal phosphides, hydrodeoxygenation, biomass, bio-oil, vegetable oils DOI: 10.1134/S0965544120100047
Transition metal phosphides became widespread at the end of the 19th century. In 1873 the German scientist C. Rammelsberg studied salts of hypophosphorous acid and showed that the decomposition of cobalt and nickel hypophosphites is accompanied by the formation of phosphates and phosphides of corresponding metals [1]. A year later R. Schenk obtained nickel phosphide by boiling nickel chloride and phosphorus in an alkaline solution [2]. In 1885 P. Kulish developed a method to obtain a mixture of nickel and nickel phosphide by passing phosphine through a solution of ammonium nickel salt. In 1931 R. Scholder and H. Heckel isolated fairly pure nickel phosphides of composition Ni5P2 and Ni2P from a mixture of phosphides precipitated from acidic solutions of nickel salts by hyphosphite solutions. In 1932 C. Grieb and R. Jones synthesized nickel phosphide by the reaction of phosphorus with nickel carbonyl vapor at 50°C [3]. In 1950 a team of American researchers obtained alloys containing nickel and cobalt phosphides by electrodeposition from solutions [4]. Transition metal phosphides were first used as heterogene
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