Chemical and Technological Researches Department.

Leonid M. Shkaraputa, Doctor of Sciences (Techn.), Professor.

Address: 50, Kharkivs'ke Shosse, Kyiv-160, 02160, Ukraine.
Tel/fax: 559-66-47, 559-98-00.
E-mail: lnsh@mail.kar.net

Scientific directions:

Development of the scientific basis of industrial production of bioorganic, organic and petro-chemical synthesis produ cts.

Chemical and technological research department was found in 1977. The main orientation and aims of the whole research work are as follows: the development of the scientific basis of industrial pro-duction of bioorganic, organic and petrochemical synthesis products. These tasks were defined by Victor S.Gutyrya, Academician, Vladimir T.Sklyar, Doctor of Sciences, Professor, Leonid N. Shkaraputa, Doctor of Sciences, Professor. The impossibility and absurdity of mere transference of laboratory synthesis conditions into industrial production was taken into account when determining the scientific orientation. The creation of mathematical models authentically describing chemical conversion regularities is the only way of choosing the methods of rational ecologically-safe production and determining the problems of scaling, optimization and apparatus. The staff of the department pays a great deal of attention to the per-forming of chemical interaction mechanism analysis, kinetic, thermodynamic, thermophysic and hydro-dynamic regularities investigation, creation and investigation of process mathematical models, parameters optimization. Problems of automatization technological scheme development, production technological regulations, rational apparatus design, plant creation and developing are also paid attention to.
The research workers of the department were first to ascertain that electrophylic addition of chlorine to olefins in water may proceed according to associative mechanism as well as the dissociative one. The criterion of differentiating of areas of bi- and three-molecular cooperation was found. From the point of view of elementary chemical acts, correlations which describe speed of chlorohydrination products formation were fixed, the conditions that enable to define the current concentration of olefines as a function of conductivity of reactionary mixture and to considerably simplify determination of kinetic constants were found. The expressions that describe adequately the regulations of chlorohydrination were offered, the algorithm of optimization and calculation of the nonstationary modes were developed, the original methods of receipt of 3-chlor-4-oxy- and 3,4-dichlorotholane-1,1-dioxides were offered. The original methods of chlorohydrination and sulfating were developed. The twin-screw reactor-mixer mathematical description that implies conformities to regulations of transporting, warming-up, crystallization and actually chemical transformation of reagents mixture, in the conditions of continuous evacuation of one of ingredients, was first formulated. The researches conducted enabled to develop and test successfully the technological processes of receipt of high-efficient substances for treatment of cotton fabrics of "LUR" and "DIMOS" under experimental and industrial conditions.
The department specialists have investigated the terms of reverse emulsions functioning in tech-nological processes targeted at oil recovery intensification. The effective stabilizers of emulsions of "ES-2", "ES-4", "BES-1" were offered, the technology of directed emulsion and acid treatments of the by-face areas, technology of mining holes muffling by reverse emulsions on the basis of "ES-2" emulgator were developed. The thermophysical and thermochemical properties of reagents, thermodynamic and kinetic regularities of interaction between deep blue tailings of SFA and dextramine were studied, the adequate mathematical models of processes in different types of reactors were designed, the optimization was performed, technological regulations were developed, the production of 5000 t of "ES-2" and "ES-4" on Drohobytch oil refinery was set up and mastered. The real economic effect exceeded 30 million soviet roubles.
The department has conducted a large scale work to choose the alternative raw material and to develop compounding and technological processes of receipt of composition binders from irrationally used substances and by-products of oil refining (oil slurry, sour gudrones, asphalt-extract mixtures (AES), gudrones, wastes of rubbers, et al) for road building and cokechemistry. The ways of quality indexes adjusting were found and effective alloying admixtures and accessible catalysts which enable to obtain binders without traditional air oxidation were offered. Compoundings of binders were acknowledged to be inventions. It was shown that the use of cavitation influence not just improves radically the components mixing but due to highenergy influence enables to speed up chemical processes at the receipt of binders 4-12 times by compounding and oxidation. The dependences between geometry of supercavitational mixer, modes of circumfluence and term of oxidation were investigated, the mathematical model of supercavitational mixer and engineering method of its calculation was created.
The technological production processes of high-quality compositional binders "БШВ", "КВАГУ", "КВАГУ-Б" were developed and inculcated on Krementchuk oil refinery for road building and briquetting of coal for cokechemistry with the productivity up to 200 thousand of tons per year. The use of gudrone, AES, sour gudrone and oil slurry, allowed to improve the ecological situation. The employees of department executed research on the receipt of travelling binders from oil products with high maintenance of paraffins and wastes which had accumulated on territory of Drogobych oil refinery. The department designed compounding of high-quality travelling binders "КВ", and also compounding of liquid emulsive composition binders "КВЖ", that are used for macadam blackening and sheeting receipt by mixing on the road. The original technological process was offered. On Drohobytch oil refinery the industrial production of binders with production rate of 20 thousand tons a year for road building was mastered.
Hundreds of thousands of tons of binders "БШВ", "КВАГУ", "КВАГУ-Б", "КВ" and "КВЖ" were produced. The exploitation of road sheeting with "КВ" binders proved their competeable quality if compared to the sheeting on the basis of the best bitumen of the "БНД" brand. Industrial realization of technological processes of compositional binders receipt with the use of supercavitational apparatus allows to decrease a capital investment 20-50 times and to reduce the time of settings creation one- or two-fold, to reduce energy consumption 3-5 times, to utilize sour gudrones, oil slurry, wastes, and practically to eliminate harmful emissions in the atmosphere.
The experience of work with byproducts and wastes of oil refining enabled to offer facilities to curb dust formation in the area of Chernobyl atomic electrostation accident in May, 1986. For dust suppression on roads and territories it was recommended to apply oil slurry and wastes of oil refining accumulated on oilprocessing factories. Under conditions of Chernobyl accident the expedience of oil slurry use was proved. The mobile layer of soil particles saturated with oil products which prevents dust formation, even if it is destructed by wheels of trucks, was formed. The specifications on oil slurry and recommendations on its use for dust suppression were developed. In may-june 1986 with participation of employees of the department more than 10 thousand tons of slurry were used.
On the instructions of the Ukraine Ministry for Chernobyl the original synthetic detergent and decontamination substance for decontamination and laundering in cold water (from +5 С) was designed to be applied at Chernobyl atomic electrostation. The production technology was developed, the experimental lot of the new synthetic detergent and decontamination substance was produced and directed for use to the JSC "Complex".
The department has offered the alternative sources of raw materials for the receipt of technological oils used in steel wire drawing. The original technological material which operating indexes surpass the standard indexes 1,5-2 times was obtained, the technological production process was developed at Dnepropetrovsk Metize and Industrial Union, the material was successfully tested.
On the order of the Ministry of Installation and Constructing the principal provisions on obtaining of hydrophobic sheeting for cardboard paper air-channel for the use in heating and vent systems were developed. The original compounding and method of the sheeting receipt from unutilized wastes was developed, its sufacing technology on cardboard paper pipes was created. The experimental lot of the air-channel was successfully tested.
Research and development of emulgators and inhibitors continued in compounding and technologies elaborating of corrosion inhibitors of oil production equipment. Compounding of inhibitors of oil production equipment for environments without hydrogen sulphide, the "Дорад-11", and with hydrogen sulphide, the "Дорад-1ВЦ" were designed based on the research results of correlations dependence of acid and amine groups, hydrophile and lypophile system balance and the type of the environment. The operating characteristics surpass drastically the characteristics of the known inhibitors and cost 2 times less. The interaction regularities of deep blue tailings of SFA with polyethylene-polyamines, ethylenediamine, aminontrile were studied, and the technological processes of receipt of inhibitors were developed on Drohobytch oil refinery. The "Дорад-1ВЦ" inhibitors lots were tested at "Buzuluknafta", their high efficiency was proved. Tests at Poltava revealed the expedience of "Дорад-11" application.
In 1992 the development of experimental-industrial production technology of HIV treatment preparation, the analogue of azidotimidine ("Теозидин") was set up. The methods of stage-by-stage control were developed, optimization of "Теозидин"synthesis stages on the glucose-desoxyribosetimidine- "Теозидин" route was realized. The timidine competeable to the Fluke timidine was obtained. The preclinical study of "Теозидин"was conducted, its identification tests were developed, its specific action and margin toxicity were studied. The conclusion is "the inhibiting activity of the domestic preparation is equal to that of Retrovir", and "we may ascertain the similarity of symptomatic exposures of corresponding reactions to margin toxic influence of the AZT ("Теозидин") substance and Retrovir remedy". The State Scientific and Research Institute "Khimfarmproekt" realized the preproject analysis of "Теозидин" research and industrial production location. The raw materials base was investigated, the production concept was agreed, the principal technological schemes were developed, expedience of production location at the Cherkassy plant of Chemical Reagents was shown, the basic chemical-technological indexes were stated and the consent of plant headoffice to locate experimental-industrial productions of "Теозидин" was got. It was shown that the cost of 1 kg of "Теозидин", synthesized exceptionally on the imported raw material, will not exceed 5,0-5,6 thousands of the US dollars. While the cost of 1 kg of Retrovir, produced by firm "Velkom", equaled 14,5-14,8 thousands of US dollars and the cost of "Тимазид", produced by the Russian association "AZT" made up 6-10 thousands of US dollars for 1 kg. Thus, the production of domestic "Теозидин"should save Ukraine from 2 to 9 thousands of US dollars for every kilo of the preparation.
The rational synthesis of AIDS treatment preparation D4T was developed, the methods of process control were proposed, the technological regulations were developed, the laboratory settings were created, the sample of D4T for preclinical tests was designed, antiviral activity of the preparation was studied.
Unfortunately, due to incomprehension of the importance of the attained results on technology development of domestic HIV inhibitors by the Committee on AIDS governing body (prof. Kordyum V.A., Spivak M.Ya.) the financing of development of experimental-industrial production of AZT and D4T was halted which put an end to a very important branch of activity. The State Russia award received in year 2000 by Kononov O.V. (the ex-employee of the department) for designing the Russian analogue of AZT testifies the great potential of this activity.
At the beginning of 1980s potassium (1,1-dioksotiolan-3-il)dithiocarbamate was synthesized, in a synthetic aspect it was the analogue of tetramethyltiuramdisulphide. The compound was called "Сульфокарбатион-К" (СКК). Only few out of thousands of the compounds synthesized pass biological, toxicological and ecological tests, are economically competeable and are used in practice. It is a long and complex process, which requires around 800-1000 man-years, 30-40 millions of the US dollars. Within the development the transformation of reagents by amination of 3-tiolen-1,1-dioxide was studied. It was proved that the limiting stage of process is the receipt of 2-tiolen-1,1-dioxide. The original catalysts of amination process which allowed to speed up the reaction 6-8 times, to boost output and selectivity were offered. The kinetic regularities, the thermal effects of reactions, the thermophysical characteristics of the reaction mass were investigated, the adequate mathematical model of process was created. Optimum parameters were found: the process duration shrinked from 28-48 hours to 2-4 hours, the pressure was reduced from 25-30 to 3-5 atm, the issue of ammonia recycle was set. The experimental verification proved that the product yield increased from 76-80% to 93-98 %, and the selectivity - from 76-86 % to 95-99 %.
The attempts to synthesize even small lots of "Сульфокарбатион-К" showed the unfitness of the known ditiokarbamining methods to preparation industrial production due to low yield, considerable toxicity of target product and big wastes volume. The conditions for high selective receipt of dithiocarbamates were stated, the expedience of programmable entrance of initial ingredients into the reaction area was proved. The researches conducted enabled to revise the understanding of mechanism of amines and carbon bisulphide joining. The regularities of ditiokarbamining in the reactor with variable mass were described. The issue of optimum distribution of reagents introduction was set. The original methods of СКК receipt were developed, the complex of the model settings which enables to produce up to 20 tons of СKK a year was projected and mastered. Preparation was applied at the territory of nearly 800 thousands of hectares. "Сульфокарбатион-К" is registered as the protectant for seeds of sugar beets, wheat, corn, barley, rape, buckwheat, millet and potato sprouts. It is highly efficient; the methods of СКК use were acknowledged as inventions. The Ministry of Agrarian Policy has defined the need for preparations of this group ( 3000 tons). Introduction of СKK resulted into investment of over 200 thousands of US dollars into Ukraine. World famous Japanese companies "Sankio Ko Ltd" and "Sumitomo Corporation" have officially recognized that "Сульфокарбатион-К" is competeable with one of their best developments - protectant Tachigaren. Preparations of such class have never been developed in the USSR and independent Ukraine.
Modification of CKK allowed to synthesize high-efficient antimycotik, the medical preparation "Теобон-дитиомикоцид", and to develop the technological process of its receipt. The researches of untoxicity and specific activity conducted have shown that it is much safer than the majority of antimycotics and antiseptics, that it represses the malignant fungi Candida albicans, Candida tropicalis, Trichophyton rubrum, Microsporum canis, ..., and a number of bacteria of intestinal and coccal groups. The clinical researches of preparation proved that it is safer and more effective than the known klotrimazol and mikozolon, it enables to shorten the treatment term by 25 %. The Ministry of Health of Ukraine has registered the substance "Теобон-дитиомикоцид" and the two ready medical forms on its basis (ointment and powder for solution preparation). The production of ointment "Теобон-дитиомикоцид" was mastered, about 10000 packs of preparation were produced.
Application of extruded poliolefine sheetings is one of the perfect means of passive anticorrosive defence. Their distinguish advantage is high physic-mechanical, dielectric and anticorrosive properties. However, the isolating sheeting is surfaced on a "hot" pipe (150-220 С). The employees of the department have designed original materials which enable to surface the extruded polyethylene sheeting at 15-20 С. It was proved in vitro that adhesion to steel of the developed sheeting exceeds the norms of DSTU 4219, GOST R 51164 and DIN 30670, the transitional specific resistance surpasses the norm three times (3,4 1010 Ohm м2), the radius of sheet detachment during cathode polarization makes up 2-3 mm, while the norm is up to 11 mm, resistance to blow exceeds 5 J/mm of sheeting thickness. Thus, the characteristics of the developed "cold" surfacing sheeting are at the level of the world's best samples.

All the laboratories are equipped with modern apparatus - chromatographs, polarographs, spectrophotometers, a.c. bridges, ets. The staff of the department developed, designed and built the model plants complex which makes it possible to work through technological processes and to produce enlarged experimental batches of preparation total volume of which is 10-250 l in vacuum and under pressure of 100 kgf/cm2, in a wide range of temperatures. There are plants for making of heat-carriers, distillation, vacuum and atmospheric rectification, suspensions division on centrifuges and filters. The complex is equipped with sanitary columns to exclude unhealthy waste.

The research workers of the department have published 3 monographs, 270 articles, more than 60 authors' certificates were received, 2 Doctors and 8 Candidates of Sciences are prepared.