Boreskov, Georgii Konstantinovich
Boreskov, Georgii Konstantinovich
BORESKOV, GEORGII KONSTANTINOVICH
(b. Omsk, Russia, 20 April 1907; d.
Novosibirsk, Russia, 12 August 1984), physical chemistry, catalysis, chemical technology. Boreskov enriched contemporary science by developing catalysts for important chemical processes, some of which are fundamental for industry. He also developed the theoretical foundations for predicting catalytic action and scientifically selecting active catalysts. Together with Mikhail Gavrilovich Slin’ko, he forged a new direction in science: the mathematical modeling of catalytic processes. Moreover, he founded the Institute of Catalysis in Novosibirsk, one of the first scientific establishments in this sphere in the world, and in 2006 also one of largest, with branches in Omsk and St. Petersburg.
Georgii Konstantinovich Boreskov was born into a good family with a strong engineering tradition. His grandfather, Mikhail Matveevich Boreskov, a lieutenant-general in the Russian Army, was a famous military engineer with a number of inventions in the sphere of mine works. His father, Konstantin Mikhailovich Boreskov, was one of the first military aviators in Russia (after the October Revolution of 1917 he emigrated to Belgium). His mother, Ida Petrovna Dombren, was the daughter of a teacher at a gymnasium (secondary school). In 1916 his parents separated, and his mother left with the two children for Odessa, where she soon married another military engineer, Aleksandr Nikolaevich Paton, a colonel in the czarist army. After the start of the revolution of 1917, the stepfather joined the Red Army. Later, in 1937, he was repressed.
Odessa, Moscow, and Sulfuric Acid Catalysis. Boreskov received his education in Odessa. In 1924 he graduated from a professional secondary school there. From 1924 to 1929 he studied chemical technology at the Odessa Chemical Institute. After graduating from this institute he started working in the Odessa Chemical and Radiological Institute as a researcher in the catalysis laboratory, headed at that time by Ivan Evgrafovich Adadurov, who was famous for his work on the preparation of catalysts. In 1932 Boreskov was appointed head of the catalysis laboratory at the institute. Around that time (1930–1937) he held the Chair of Processes and Apparatuses of the Odessa Institute of Chemical Technology, where he taught courses on processes and apparatuses of chemical technology and also on kinetics and catalysis.
Boreskov began nonacademic work during the first five-year plan (in accordance with Stalin’s program for developing the country, the first five-year plan was started in October 1928). The major energies of this program were aimed at industrialization, and in particular at the development of heavy industry, for which immensely high goals were set. With respect to the chemical industry the largest capacity was allocated to the production of sulfuric acid. As it was a basis for many other chemical syntheses, production of sulfuric acid demanded highest priority. Boreskov’s work on sulfuric acid catalysis, which started in 1929 and was dedicated to these goals, succeeded in the development of a new catalyst and a new process.
The basic reaction in the industrial production of sulfuric acid is the oxidation of sulfurous anhydride. For this process a platinum catalyst was used in the 1920s and early 1930s, but it was quite expensive and sensitive to “poisoning” of the catalyst by contaminations. These drawbacks limited growth in production of this important chemical reagent. Perhaps following the example of Monsanto (USA), where vanadium-based catalysts had been introduced in 1925, Boreskov created two new highly effective composite catalysts named BOV (barium-tinvanadium) and BAV (barium-alumino-vanadium), which had better operational qualities than previous catalysts. These catalysts revolutionized the production of sulfuric acid. Cheap vanadium catalysts have high catalytic activity and are quite robust with respect to catalyst poisons, and thus took the place of platinum catalysts. Already by the end of the 1930s all plants in the Soviet Union were using the BAV catalyst. They gave rise to a whole generation of effective catalysts for a number of industrial oxidation processes.
In 1937 Boreskov received a master’s degree in chemical science without defending a thesis. The Ministry of Industry ordered the laboratory of catalysis to be moved to Moscow and placed under the Research Institute of Fertilizers, Insecticides, and Fungicides, where Boreskov continued to work as head of this laboratory until 1946. At the research institute work that was started in Odessa, work on vanadium catalysts for the production of sulfuric acid continued. For his research on sulfuric acid catalysis, Boreskov was given the title of USSR State Prize Laureate (1942) and was awarded the Prize of Honor (1944). This work is summarized in Kataliz v proizvodstve sernoi kisloty (Catalysis in the production of sulfuric acid, 1954), in which Boreskov explained the basics of his approach to developing catalysts for industrial application.
Boreskov married three times. He was married to his first wife, Zemenkova Ekaterina Petrovna, for ten years (1934–1944), and to Professor Nadezhda Petrovna Keêer from 1959 to 1973. His last wife, also a chemist, was Marina Vasil’evna Chaikina. Boreskov had four children: a daughter, Elena (1935); and three sons, Konstantin (1943), Vadim (1947), and Iuriiu (1961).
The Theory of Catalytic Action. In 1946, after Boreskov was granted the degree of doctor of chemical science for his thesis “Teoriia sernokislotnogo cataliza” (Theory of sulfuric acid catalysis), he was made head of the laboratory of technical catalysis in the Karpov Scientific Research Institute of Physics and Chemistry (Moscow), a position he served in from 1946 to 1959. Here Boreskov launched research on the development of the scientific basis for selecting and preparing catalysts and developing new catalytic processes. For this work Boreskov was granted a second USSR State Prize (1953), and in the same year he was given the Labor Red Flag Award.
In the course of detailed investigations of specific catalytic processes (oxidation of ammonia, hydrolysis of chlorobenzene, and others), the conditions of their realization, their reaction kinetics, and the chemical nature of the catalysts used, Boreskov formulated the task of defining the optimal characteristics of a catalyst—its internal structure, its form, and the size of its particles—as a major objective for increasing catalytic activity and the selectiveness of its action in various chemical reactions. “For increasing catalyst activity,” he wrote in “Mekhanism deistviia tverdykh katalizatorov” (The mechanism of action of solid catalysts, 1953), “it is necessary not simply to increase the internal surface, but also to create a certain cavernous structure of the catalyst’s particles to provide speedy input of reacting substances to the internal surface most remote from the particle’s periphery parts and speedy diffusion of reaction products from this site. For each catalytic process, depending on the process conditions, its kinetic behavior and the specific activity of the catalyst, an optimal porous structure can be established, that providesthe highest reaction rate” (1997 edition, p. 290). The choice of catalyst supports, the necessary thermal consistency for the catalyst, the distribution of active components, the preparation of the catalyst, and a number of other characteristics determined by the conditions of preparation—Boreskov reviewed all these aspects in developing a theoretic basis for preparing active catalysts, work that occupied him from 1950 to 1955. (These issues are covered in detail in Boreskov 1958a and 1964.)
Boreskov considered all his investigations in catalysis as a basis for solving the problem of predicting a substance’s catalytic action, because to his mind this was an important theoretical goal of this science.
The 1950s should be regarded as a turning point in the development of a science of catalysis. During these years, catalysis was transformed into a large independent area of science: In a number of countries, specialized institutes were organized, specialized journals were established, and regular international congresses on catalysis were held. During this time Boreskov’s views of the essence of catalytic action were being formed. As early as 1953 he presented a programmatic statement of his views on this issue at the All-Union Meeting on Heterogeneous Catalysis in the Chemical Industry (Moscow).
Boreskov first of all supported a chemical approach to catalysis, according to which the mechanism of catalytic action lies in the intermediate chemical interaction of catalyst with reacting substances. His research related mostly to heterogeneous catalysis, but it also played an important role in the development of the science of catalysis in general.
As is well known, in homogeneous catalysis the catalyst and reacting substances occur in one common phase, usually a liquid, in which catalyst and reacting substances are dissolved. In heterogeneous catalysis, the reaction takes place at the interface of two phases (the catalyst is in the solid state, but the reaction mixture is a gas or liquid). Because of the nature of heterogeneous catalysis, the discovery of the character of the intermediary chemical interaction in heterogeneous catalysis was quite complicated. A simple transfer of the concepts of homogeneous catalysis, which was often done in the study of heterogeneous catalysis, led to a situation where for a long time even quite famous scientists were of the opinion that the intermediary compounds represented a separate phase (such as oxides in the case of catalytic oxidation on metals). Boreskov proved this idea of an intermediary phase transition in heterogeneous catalysis to be false. He pointed to the role of intermediary compounds on the surface, in a so-called chemisorbed state (where absorption of a substance by a surface of some body occurs with the formation of a link between the substance’s molecules and the adsorbent).
In developing his theory of catalysis, Boreskov formulated a number of important determining factors of catalytic action. Fisrt, he allocated an important role to the chemical structure of the catalyst. The main task of catalysis theory is to establish a quantitative link between the chemical composition of a catalyst and its catalytic activity in some definite reaction. The catalytic activity of solid catalysts is measured by the rate of the reaction per unit volume or total catalyst mass. But as catalytic reactions usually proceed at the catalyst’s surface, in early 1940
Boreskov proposed using the notion of specific catalytic activity, determined by the rate of a catalytic reaction per unit of catalyst surface. This characteristic measure, determined mostly by the chemical composition of the catalyst allows the researcher to quantitatively describe a catalyst’s activity. In the early twenty-first century, specific catalytic activity is a common characteristic of catalysts without which quantitative description of their activity cannot be imagined.
Research from 1945 to 1953 showed that specific catalytic activity is relatively constant at different surface sizes and crystal sizes, and does not depend on the conditions of preparation of catalysts. This discovery was quite unexpected in the scientific community, but it played a decisive role in establishing new concepts of catalysis. The principle of constant specific catalytic activity entered into the science of catalysis as Boreskov’s rule (1953), for Boreskov had clearly defined the scope of its application. Practice has shown that for most industrial catalytic reactions proceeding at high temperatures, Boreskov’s rule can serve as a good basis for choosing catalysts. This discovery also established a new view of catalysis according to which catalysts and reacting substances are regarded as an integrated chemical system in which not only reagents but also the catalyst itself change.
Boreskov’s experiments showed that in catalytic reactions, surface atoms can shift in catalysts and also the ratio of catalytic components can change because of the interaction with reagents. This discovery, the so-called “principle of the influence of the reaction medium on the catalyst” was extensively proven (Boreskov, 1958b). In the 1960s Boreskov and his colleagues confirmed the effect of the reaction environment on the catalyst in numerous works. They established, that in the course of reactions, specific mechanisms of change in catalysts occurred relating either to changes of composition of the surface layer or to its structural reconstruction.
Much of Boreskov’s work in this direction from 1950 into the 1970s was connected also with the role of the bond energy of the reagents with the catalyst. Boreskov assumed that for separate groups of reactions, a limited number of links, or one link, of a reagent with a catalyst can have a decisive importance. In the course of examining concrete catalytic oxidation reactions, he chose the oxygen link to the catalytic surface as defining a class of reactions, and later (1971) he investigated the dependence between catalytic activity and the durability of this link in a number of reaction systems. He proved that there was a correlation between the catalytic activity and the energy of the oxygen link, not only for simple oxides but also for more complex compounds such as spinels, salts such as vanadates and molybdates, and mixed oxides. These established regularities were successfully used for choosing specific catalysts for a number of industrial processes.
This research also included Boreskov’s investigations of stages in the mechanisms of heterogeneous catalytic reactions. Does catalytic oxidation, for instance, occur through chemical conversion of the reagents (the so-called associative mechanism), or does it involve oxidation and reduction of the catalyst (which would mean an extra stage in the mechanism)? In the course of sophisticated and laborious experiments, it was shown that at high temperatures in most oxidation reactions, a multi-step mechanism predominates, but if the temperature is decreased, the associative mechanism prevails. Boreskov examined these regularities in detail in the late 1960s by looking at the example of the reaction of carbon monoxide with steam. Over an iron oxide catalyst the reaction followed a multi-step mechanism, yet at low temperatures with a cupric catalyst the mechanism became associative. These results were of fundamental importance for establishing the basic forms of catalytic action (Boreskov, 1973).
Use of tracer elements played an important role in Boreskov’s creation of the theory of catalytic action. For eleven years (1949–1960) Boreskov occupied the Chair of Isotope Separation and Application in the Mendeleev Moscow Institute of Chemistry and Technology. Here Boreskov (together with A. I. Gorbunov, V. V. Popovskii, Vitaly S. Muzykantov, and others) started work on clarifying catalytic reaction mechanisms and the reactivity of catalyst surfaces using hydrogen, oxygen, and nitrogen isotopes. The research was later continued within limits at the Institute of Catalysis founded by Boreskov. The tracer method itself was noticeably developed by this work.
A separate place in Boreskov’s scientific work belongs to the paper “Sootnoshenie mezhdu molekuliarnost’iu i energiiami aktivatsii v priamom i obratnom napravleniiakh” (Correlations between Molecularity and Energies of Reaction Activation in Forward and Reverse Directions, 1945). Twenty-first-century kinetics of complex reactions cannot be imagined without this short, but fundamental work. The Horiuchi-Boreskov correlations deduced in this paper establish a connection between kinetic and thermodynamic characteristics of equilibrium reactions. Such correlations are widely used in the early 2000s in kinetic-research calculations.
Kinetic Research and Chemical Reactor Theory. According to Boreskov, the reaction mixture influences the rate of the catalytic reaction in two ways: first is its interaction with the surface of the catalyst, and second is its effect in changing the properties of the catalyst. Yet processes resulting from the influence of the reaction mixture upon the catalyst will not necessarily be stages in the catalytic reaction mechanism. It is also important that the durations of these two processes (the effects on the surface of the catalyst and on the properties of the catalyst) can substantially differ. Boreskov proposed a formula for calculating the rate of the catalytic reaction that took into consideration the contribution of both processes to the kinetics of the reaction (Boreskov, 1959). His kinetic equation (the 1960 variant of which bears the name “Boreskov-Ivanov equation”) is successfully used by technologists in their calculations.
Boreskov’s view, taking into account the interaction between the reaction environment and the catalyst, leads inevitably to the consequence that the kinetics of a heterogeneous catalytic reaction depends on the rate with which the catalyst’s surface is refreshed. Issues of nonstationary technology (where processes are conducted in conditions of varying flow rates, concentrations of reaction mixture, temperatures, etc.) were developed by Boreskov together with Yuri Shaevich Matros in the last years of his life (1977). During 1979 and 1980 he discovered, and for the first time realized, the oxidation of SO2 to SO3 in a non-stationary catalytic process in the production of sulfuric acid. In the 1990s in Russia there were six large plants using this type of process.
Boreskov’s kinetic researches were always aimed at solving two problems at once: revealing the mechanisms of catalytic processes and calculating the characteristics of the chemical reactors. As Boreskov wrote, “To prepare an active catalyst is half the work; the second half, which may be the most important, is to create a real chemical apparatus, a chemical reactor, in which this catalyst works” (1997, pp. 400–401). In the late 1950s and early 1960s Boreskov and Michail G. Slin’ko stepped forth as pioneers in the development of a new direction in science: mathematical modeling of chemical processes and reactors (Boreskov, 1961). This issue had already been briefly formulated (Boreskov, 1935), but realization of such mathematical modeling proved possible only after the appearance of analog and digital computers. The formation of this direction in the science of catalysis took place in an atmosphere of lively discussion. Boreskov and Slin’ko clearly brought out the impossibility of applying traditional methods of “similarity theory” for describing chemical processes.
The initial aim of mathematical modeling in catalysis was to facilitate the transition from laboratory research on reactions to the creation of industrial reactors. This approach based on equations describing chemical transformations, together with the equations for heat and mass transfer, gives a description of the process that is independent of the size of the system. A whole sequence of strict mathematical models (a kinetic model, a model of the catalyst’s particles, a model of the catalyst’s layer, a model of the contact apparatus, etc.) was worked out, and in accordance with it an industrial system was calculated. Solutions of the mathematical equations were obtained by computer. Applications of Boreskov’s methods in this direction turned out to be of substantial importance for understanding conditions for catalytic reactors to operate stably.
Heading the Institute of Catalysis. In 1957 the Soviet government decided to develop science in Siberia. A large scientific center was organized in Novosibirsk, the Siberian branch of the USSR Academy of Sciences, under which the Institute of Catalysis was established in 1958. Its founder and director was Boreskov, who served in the latter capacity from 1958 to 1984. At almost the same time (1959), Novosibirsk State University was founded. Its main task was to prepare specialists for the scientific center. Boreskov organized and served as chair of the Department of Catalysis and Absorption in the university from 1960 to 1984. In 1958 he was elected corresponding member of the Academy of Sciences, and in 1966 a full member. In 1967 Boreskov was given the title of Hero of Socialist Labor for his outstanding achievements in the development of chemical science and industry and for his active participation in the creation of the Siberian Branch of the Academy of Sciences. Over the next two decades he was given the State Prize of the Ukrainian Soviet Socialist Republic (1970) and two Lenin Prizes (1975, 1982).
Within the framework of the institute, Boreskov managed to broaden considerably the practical scope of his work. He created catalysts for obtaining acrylonitrile (a monomer for production of synthetic fibers), as well as for the production of acrylic acid and acrolein from propylene, for converting carbon monoxide, and for obtaining formaldehyde, monomers of synthetic rubber, and other substances. An important direction was his development of catalytic methods of cleaning the exhaust gasses of industrial processes, and for waste water purification. At Boreskov’s initiative, the specialized engineering firm, called Siberia, was created in 1970 with a pilot-plant facilities for a quick transfer of the institute’s results to industry.
Boreskov was interested in nontrivial approaches to catalysis and technology. He was the first in the world (1931) to propose a method of carrying out catalytic processes in a fluidized bed. In the early twenty-first century fluidization is a method for realizing large-capacity catalytic processes. As a promising new approach to catalysis, Boreskov considered the application of fluidization in processes of burning fuel (at lower temperatures). In 1980–1982 the institute, under Boreskov’s supervision, developed catalytic heat generators (with an efficiency factor of 80%–90%) in which coal is burned with catalysts in conditions of fluidization.
Boreskov was elected a foreign member of East German Academy of Science and an honorary member of New York Academy of Science. He also received honorary degrees from some foreign universities. From 1972 to 1976 he was the president of International Catalysis Congress. In 1993 the Institute of Catalysis was renamed the Boreskov Institute of Catalysis.
WORKS BY BORESKOV
“Fisiko-khimicheskii raschët kontaktnykh apparatov” [Physico-chemical calculation of catalytic reactors]. In Sbornik trudov Ukrainskogo nauchno-issledovatel'skogo khimicheskogo instituta tresta “Ukrkhim” v Odesse. Collected Works of the Ukrainian Chemical Scientific Research Institute of the “Ukrkhim” Trust in Odessa, vol. 1: Tekhnologiia sernoi kisloty[Technology of sulfuric acid], 8–48. Odessa, Russia: 1935.
“Sootnoshenie mezhdu molekuliarnost’iu i nergiiami aktivatsii v priamom i obratnom napravleniiakh” [Correlations between molecularity and energies of reaction activation in forward and reverse directions]. Zhurnal fizicheskoi khimii 19, no. 1–2 (1945): 92–95.
“Mekhanism deistviia tverdykh katalizatorov” [The mechanism of action of solid catalysts]. In Akademik Georgii Konstantinovich Boreskov: Ocherki, materialy, vospominaniia, edited by Valentin N. Parmon. Novosibirsk, Russia: Institut kataliza SO RAN, 1997. Originally published in 1953.
Kataliz v proizvodstve sernoi kisloty [Catalysis in the production of sulfuric acid]. Moscow: Goskhimizdat, 1954.
“Nekotorye voprosy teorii podbora katalizatorov” [Some theoretical issues in choosing catalysts]. In Problemy fizicheskoi khimii, vol. 1: Trudy Nauchno-issledovatel'skogo fiziko-khimicheskogo instituta im. L. Ia. Karpova. Moscow: Goskhimizdat, 1958a.
“Vzaimodeistviie katalizatora i reaktsionnoi sistemy” [Interactions of catalyst and reaction systems]. Zhurnal fizicheskoi khimii 32, no. 12 (1958b): 2739–2747.
“Vliianie vzaomodeistviia reaktsionnoi sistemy i katalizatora na kinetiku kataliticheskikh reaktsii” [The influence of the interaction between the reaction system and catalyst on the kinetics of catalytic reactions]. Zhurnal fizicheskoi khimii 33, no. 9 (1959): 1969–1975.
With M. G. Slin’ko. “Modelirovanie kataliticheskikh protsessov” [Modeling catalytic processes]. Vestnik AN SSSR 10 (1961): 29–35.
“Nauchnye osnovy podbora i prigotovleniia katalizatorov” [The scientific basis of the choice and preparation of catalysts]. In Nauchnye osnovy podbora i proizvodstva katalizatorov, edited by N. P. Keier. Novosibirsk, Russia: Redak tsionno-izdatel‘skii otdel Sibirskogo otd-niia AN SSSR, 1964.
With V. V. Popovskii and V. A. Sazonov. “The Correlation between the Catalytic Activity of Oxide Catalysts and Oxygen Bond Energy.” In Proceedings of the Fourth International Congress on Catalysis, Moscow, USSR, 23–29 June 1968, vol. 1. Budapest, Hungary: Akadémiai Kiadó 1971.
“Stadiinye mekhanizmy v kataliticheskikh reaktsiiakh okisleniia” [Stages in the mechanisms of catalytic oxidation reactions]. Problemy kinetiki i kataliza 15 (1973): 27–39.
“Associative Mechanism of Oxidation Reactions on Oxide Catalysts.” In The Second Japan-Soviet Catalysis Seminar: New Approach to Catalysis, Oct. 1–3, 1973. Tokyo: 1973.
With Yuri Shaevich Matros, O. V. Kiselev, and G. A. Bunimovich. “Osushchestvlenie geterogennogo kataliticheskogo protsessa v nestatsionarnom rezhime” [Conducting a heterogeneous catalytic process in a transitional regime]. Doklady AN SSSR 237, no. 1 (1977): 160–163.
“O katalize i Institute kataliza: Itogi i perspektivy” [About catalysis and the institute of catalysis: Results and perspectives]. In Akademik Georgii Konstantinovich Boreskov: Ocherki, materialy, vospominaniia, edited by Valentin N. Parmon. Novosibirsk, Russia: Institut kataliza SO RAN, 1997.
Geterogennyi kataliz [Heterogeneous catalysis]. Edited by K. I. Zamaraev. Moscow: Nauka, 1986. Completed by his associates.
Kataliz: Voprosy teorii i praktiki [Catalysis: Issues of theory and practice]. Edited by G. I. Panov. Novosibirsk, Russia: Nauka, 1987. A collection of selected works of Boreskov.
Bebikh, I. G., V. S. Muzykantov, et al. Georgii KonstantinovichBoreskov. Materialy k biobibliografii uchenykh SSSR, vyp. 70 [Materials for bibliographies of USSR scientists, vol. 70]. Moscow: Nauka, 1982. Basic aspects of his scientific career are reviewed in detail. Includes a bibliography to 1981 of Boreskov’s more than 800 articles and discoveries.
Hall, Homer J. “Soviet Research in Catalysis: Lack of Consumer Demand Is Major Drawback to Development of Industrial Catalysis in USSR.” Industrial and Engineering Chemistry 62, no. 3 (1970): 33–40.
Kal’ner, Veniamin D., ed. Iz istorii kataliza: liudi, sobytiia, shkoly [From a history of catalysis: People, events, schools]. Moscow: Kalvis, 2005.
Parmon, Valentin N., ed. Akademik Georgii KonstantinovichBoreskov: Ocherki, materialy, vospominaniia [Academician Georgii Konstantinovich Boreskov: Articles, materials, reminiscences]. Novosibirsk, Russia: Institut kataliza SO RAN, 1997. Contains Boreskov’s autobiography and essays and reminiscences of scholars, employees, journalists, and close relatives. Also includes a list of publications with Boreskov’s name that appeared after his death (1985–1989).
Turkevich, John. “Boreskov Georgii Konstantinovich.” In SovietMen of Science: Academicians and Corresponding Members of the Academy of Sciences of the USSR. Princeton, NJ: Van Nostrand, 1963.
———. “Boreskov Georgii Konstantinovich.” In Chemistry in the Soviet Union. Princeton, NJ: Van Nostrand, 1965. Zaitseva, Elena A., and Ernst Homburg. “Catalytic Chemistry under Stalin. Science and Scientists in Times of Repression.” Ambix 52 (2005): 45–65.