публикация №1632216355, версия для печати


Дата публикации: 21 сентября 2021
Публикатор: БЦБ LIBRARY.BY (номер депонирования: BY-1632216355)
Рубрика: ХИМИЯ
Источник: (c) Science in Russia, №5, 2011, C.28-31

Lithium (Li) is the lightest among metals. Nuclear engineering and materiel have always been its strategic users. Isotope 6Li is the only industrial source for the production of tritium as part of a thermonuclear charge. Lithium is also essential to the aviation industry. According to Academician Iosif Fridlyander, a metal scientist who has created lithium-magnesium alloys, half as light as aluminum with the same mechanical characteristics, their use would change radically the relation between the dead weight of aircraft and their useful load. Recently lithium batteries (household batteries, space technology facilities, submarine and electric car equipment) have gained recognition. The industry, which produces special brands of glass (for example, for television kinescopes and X-ray tubes), ceramics and light waveguides, is also a major consumer of this metal. Lithium-based compounds contribute to the production of multipurpose grease lubricants which preserve their properties in a wide temperature range of 0 to 1,200 ºC. Lithium is also used for air purification in submarines, spacecraft and other objects.


Over the last 10 years the consumption of lithium and its compounds has increased fourfold worldwide, thus making producers look for new raw material sources and master lithium production from different raw materials. However, Russia is not producing appropriate primary products, she is importing them. All the same, as Novosibirsk scientists Natalia Kotsupalo, Dr. Sc. (Technol.) and Alexander Ryabtsev, Cand. Sc. (Technol.)--both from the Ecostar-Nautech Company--and Academician Vladimir Boldyrev (Institute of Solids and Mechano-chemistry, the Siberian Branch of the Russian Academy of Sciences) say in their article published in the


Nauka v Sibiri (Science in Siberia) newspaper, the situation can be changed.


The history of the national lithium production dates back to the years of the Great Patriotic War. At that time, many scientists from academic research centers and higher schools in the European part of the country were evacuated to Novosibirsk. Among them was Ivan Lileev, Dr. Sc. (Technol.), one of lithium production pioneers in the USSR. He headed the light metal laboratory at the Chemical and Metallurgical Institute of the West Siberian Branch of the USSR Academy of Sciences (in 1964, the Institute of Physicochemical Principles of Mineral Processing, the Siberian Branch of the USSR Academy of Sciences; in 1980, the Institute of Solid State Chemistry and Mineral Processing, the Siberian Branch of the USSR Academy of Sciences; in 1997, the Institute of Solid State Chemistry and Mechanochemistry, the Siberian Branch of the Russian Academy of Sciences). Under his guidance the physicochemical principles of high-temperature processing of spodumene* concentrate were developed for the production of lithium compounds by sintering with limestone. Lithium hydroxide monohydrate was a primary product obtained by this method. To make it more cost-effective, a cement producing technology was developed on the basis of production wastes under the direction of Alexander Logvinenko, later on Dr. Sc. (Technol.); the Lileev research team was awarded a Stalin prize for this work. Besides, the scientific principles of spodumene concentrate processing were assumed as a basis of the first lithium mining and ore-


* Spodumene-a mineral of the subclass of chain silicates; spodumene concentrate, the basic raw material for lithium production before 1990s.--Ed.

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processing project, namely the Krasnoyarsk Chemical and Metallurgical Plant. In the mid-1950s the plant reached its full production capacity.


In 1959 to 1962 the production teams of the above institute and the Leningrad Institute of Silicate Chemistry (today the Grebenshchikov Institute of Silicate Chemistry affiliated with the Russian Academy of Sciences) headed by Lileev worked out and tested on a commercial scale an easier method of crude spodumene ore processing with aluminum and lithium double hydroxide being the end product. They also suggested methods of its using for the production of conventional lithium hydroxide monohydrate, aluminates and lithium metal. Unfortunately this technology has not been realized in practice.


Later on, due to the depletion of the national ore reserves, attempts were made to convert the lithium industry to raw material imported from Australia. But this alternative proved unprofitable. Then Lileev's technological concepts were adapted to ores of upland Altai. However, local deposits failed to produce a competitive Li as well.


In the meantime, hydromineral sources were developed extensively for the production of lithium abroad (USA and Chile). The hydrochemical technology proved to be more sound economically and cleaner ecologically as compared with the thermal one. Moreover, a major portion of lithium in world reserves is contained just in the hydromineral raw material (80 percent) and only 20 percent, in ores.


In the USSR, lithium brines were known mainly in the territory of Daghestan. But experts condemned the brine processing practice by evaporation in a reservoir after separation of associated elements (magnesium and calcium) as unprofitable.


Later on, the Ministry of Medium Machine-Building initiated follow-up research in mastering the above method and put Yuri Ostroushko in charge of the lithium problem in the USSR. He employed the services of leading organizations engaged in this research, including the Institute of Solid State Chemistry and Minerals Processing of the Siberian Branch of the USSR Academy of Sciences. Deposition of lithium from Daghestan natural brines was carried out by analogy with the process technology suggested by Lileev for Li recovery from solutions formed in thermal processing of crude ores at the final stage. The Siberian specialists developed the deposition methods of aluminum-lithium double compounds on a solid one-time sorbing agent. The primary product, tested by aluminum electrolysis at production facilities of the USSR Ministry of Nonferrous Industry, proved positive. Due to electricity saving the cost of 1 t of aluminum was substantially reduced.


With the participation of the industrial institutions, a package process technology was developed for the production of lithium and magnesium compounds and also salts of sodium, calcium and strontium, and it was checked later at pilot plants of the South Sukhokumsk oil field in Daghestan. This technology was incorporated in the design of the Daghestan pilot production enterprise. However, the project was not realized because of interdepartmental rivalry among its participants, namely, the Ministry of Nonferrous Industry, the Ministry of Medium Machine-Building and the Ministry of Chemical Industry. Each needed only one product for itself but ignored the interests of the other partners.

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The work on calcium- and magnesiumrich chloride brines, as a rule, associated with oil and gas fields of Eastern Siberia, ushered in a new stage in hydromineral raw material processing in Russia. In this case, the lithium chloride concentration is higher than in Daghestan. But owing to the very high concentrations of magnesium and calcium, the production of lithium carbonate is laborious and expensive. For many years the obtaining of competitive commercial products based on this raw mineral was considered impossible. A new process technology was needed.


Vladimir Boldyrev, the then director of the institute, suggested the intercalation method for selective sorption of lithium ions from brine. The point is that water molecules, cations and anions, which are present in the brine, can infiltrate some compounds having a layered crystal lattice. One can select a compound in which the space between the layers would be sufficient to let in smaller ions while keeping off larger cations. It was decided to use layered aluminum-containing compounds for this purpose. A special laboratory of hydro-chemical processes was set up at the institute under Natalia Kotsupalo, and substantial assistance was provided by a petroleum geologist Academician Andrei Trofimuk. Taking part in this work were also young scientists Vitaly Isupov and Alexander Nemudry (today both Doctors of Chemistry). Their experiments confirmed the truth of Boldyrev's hypothesis.


The special-purpose science and production Ecostar-Nautech Company was set up in 1993 for non-conventional hydromineral primary sources of lithium, namely, chloride, calcium and magnesium brines. It was staffed by research workers of the Institute of Solid State Chemistry and Minerals Processing and also enterprises of the Russian Ministry of Nuclear Energy in Novosibirsk. They created a multi-use granulated sorbent based on the chlorine-containing double hydroxide of aluminum and lithium (DHAL-C1) and turned to an industrial enrichment technology of Siberian Platform brines for obtaining a lithium concentrate. The corresponding equipment was tried out at pilot units. Optimized simultaneously was the technology of obtaining lithium carbonate for chemical sources of current and high-purity water-free lithium chloride for metal and alloy production.


Owing to the work alone, already in 1998 the Ecostar-Nautech company turned to the construction of a pilot enterprise with an annual output of 800 t of lithium hydroxide monohydrate based on Irkutsk Region brines. Besides, it was planned to use it as a proving ground for process optimization and subsequent construction of an industrial complex on the neighboring Kovyktinsk gas condensate field. However, the decision taken by the Russian Ministry of Nuclear Energy early in the 2000s on the transfer of the lithium industry to imported lithium carbonate killed both this project and the technology of processing the domestic lithium-bearing hydro-mineral raw material.


The production process suggested by Ecostar-Nautech company proved necessary for the processing of brines found in other countries of the Asian continent. For example, the process was realized in the Tsing Hai province of China using lithium-bearing lacustrine

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brines of the chloride magnesium type widespread in that country. A large quantity of sorbent was produced, and lithium sorption enrichment on a commercial scale was demonstrated. For this purpose, a sorption-desorption module was manufactured and installed to the design of Ecostar-Nautech. Proceeding from test results, the project investors decided to build a production plant with an annual output of up to 12,000 t of lithium concentrate.


Thus, there is a real possibility of launching a profitable commercial output of lithium products based on both calcium chloride (Russia) and magnesium chloride (China) brines and expanding the world raw materials base by using new non-conventional sources of the hydromineral raw material.


The integration project "Lithium of Russia" of the Siberian Branch of the Russian Academy of Sciences provides for the use of other sources of the hydromineral raw material apart from the deeplaid brines of the Irkutsk Region. They include diamond deposits of the Republic of Sakha (Yakutia). According to the Institute of the Earth Crust in Irkutsk, up to 900 kg of lithium is taken out daily together with drainage brines of the Udachnaya kimberlite pipe. Using sorption enrichment, up to 1,500 t of lithium carbonate can be recovered annually without well drilling for brine. Clearly, the production of lithium carbonate from brines of the Siberian Platform can compete with world producers on the American continent. The economic assessment made by Ecostar-Nautech and the Institute of Economics and Management of Industrial Production of the Siberian Branch of the Russian Academy of Sciences*, shows that capital investments for brine studies are considerably lower than for mining and ore processing, and the profit from the realization of end products is 1.5-2 times higher, because apart from lithium carbonate one can produce also bromine, as well as magnesium and calcium salts, and magnesia binding materials.


A large scope of research work in the synthesis of new materials using lithium carbonate and also double compounds of lithium and aluminum produced from non-conventional sources of raw material was carried out under the direction of RAS Corresponding Member Nikolai Lyakhov, head of the "Lithium of Russia" project. This work provided for the synthesis of high-disperse lithium aluminates by mechanical activation, solid-state electrochemical cells with oxide electrodes, and the synthesis of cathode materials used in storage battery production. This problem gains special importance in the light of a package of documents on setting up the first Russian enterprise of rechargeable lithiumion cells in Novosibirsk as signed by representatives of the Rosnanotech Corporation and the Chinese Thunder Sky Company in Beijing in 2010.


Research data obtained by the Siberian scientists open up great opportunities for using non-conventional raw materials in the production of primary lithium products. This will give incentives for innovation techniques in the area of lithium materials widely used in modern technology.


N. Kotsupalo, A. Ryabtsev, V. Boldyrev, Role of Siberian Scientists in Creation of Lithium Production, Nauka v Sibiri (Science in Siberia), No. 14, 2011


Illustrations supplied by Ecostar-Nautech Company


See: V. Kuleshov et al, "Siberian Outpost of the Economic Science", Science in Russia, No. 4, 2007.--Ed.

Опубликовано 21 сентября 2021 года

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