Amino-1,2,4-triazoles as a raw material for the fine organic synthesis industry (review).

AMINO-1,2,4-TRIAZOLES AS A RAW MATERIAL FOR THE FINE ORGANIC SYNTHESIS INDUSTRY (REVIEW) © V.N. Nazarov, PhD in technical sciences, D.V. Miroshnichenko, Doctor of Technical Sciences, A.A. Ivakh, B.V. Uspensky (NTU "Kharkov Polytechnic Institute", 61002, Kharkov, Kirpicheva st., 2, Ukraine) The review summarizes the information on the industrial use of 3- and 4-amino-1,2,4-triazoles - the basic raw material for the industry of fine organic synthesis. 3 and 4-substituted amino-1,2,4-triazoles have been used for a long time in the production of agricultural products, pharmaceuticals, dyes, high-energy materials, and anti-corrosion additives. Less well known is their use for the production of analytical reagents, flotation reagents, as well as for the production of heat-resistant polymers, products with fluorescent properties and ionic liquids, which are used in applied sciences, biotechnology, energy, and chemistry. The purpose of this communication is to consider in detail the participation of 3- and 4-amino-1,2,4- triazoles in the production and use of various agricultural and medical products. Descriptions and schemes of chemical reactions of existing production methods for the synthesis of 3- and 4-amino-1,2,4-triazoles, as well as some methods of obtaining these substances in laboratory conditions, are given. The two main areas of use of these amines and their derivatives: agriculture and medicine have been highlighted. It is shown that one of the most well-known branches of widespread use of 3- and 4- amino-1,2,4-triazoles in agriculture is the production of plant protection products. On the basis of these substances, the mass production of various insecticides, fungicides, plant growth regulators, retardants (means for suppressing the growth of stems and shoots), inhibitors of nitrification of nitrogen fertilizers is organized. The use of these amines in medicine consists in the production of known drugs on their basis, such as furazonal (has a pronounced antimicrobial effect, is effective against Staphylococcus aureus, dysentery bacteria, salmonellosis), thiotriazoline and cardiotril (cardiological drugs with anti-ischemic and membrane stabilizing effects) (platelet growth factor antagonist). Keywords: amino-1,2,4-triazoles, production, raw materials for synthesis, pesticides, pharmaceuticals. Corresponding author V.N. Nazarov, е-mail: р[email protected]

Production of road oil bitumens by the method of chemical modification of oil residues.

PRODUCTION OF ROAD OIL BITUMENS BY THE METHOD OF CHEMICAL MODIFICATION OF OIL RESIDUES © V.М. Gunka, PhD in technical sciences, Yu.V. Prysiazhnyi, PhD in technical sciences, Yu.Ya. Demchuk, PhD in technical sciences, Yu.M. Hrynchuk, PhD in technical sciences, Yu.V. Sidun, PhD in technical sciences, M.M. Bratychak, Doctor of Chemical Sciences (Lviv Polytechnic Naional University, 12 Stepan Bandera Str., 79013, Lviv, Ukraine) The article is devoted to obtaining road oil bitumen from oil residues by modifying them with relatively cheap low molecular weight organic substances. The proposed method relates to a chemical modification, which, in case of its industrial implementation, will allow avoiding the use of expensive physical modifiers. A 37 % aqueous solution of formaldehyde was used as low molecular weight organic substances (modifier / chemical reagent of the process) for chemical modification of tar; concentrated sulfuric acid (H2SO4) was used as a catalyst for the chemical modification of tar. As a feedstock for chemical modification, we used an oil residue - tar, selected at PJSC “Ukrtatnafta” (Kremenchug, Ukraine). The chemical modification with formaldehyde was carried out in hermetic stationary containers capable of operating under excess pressure. The photographs of the equipment are given. Since the ultimate goal of the work was to obtain road oil bitumen, then, analyzing the results of experimental studies, we focused on the quality characteristics of this particular product. At the same time, the most important quality indicators were determined, namely: the depth of needle penetration, softening temperature, ductility (extensibility), adhesion to glass (adhesion to glass), Fraas brittle temperature, penetration index. For tar, the following characteristics such as density, flash point in an open crucible, and a boiling point were additionally determined. As a result of the experiments, the fundamental possibility of obtaining road oil bitumen by the method of chemical modification of tar with formaldehyde was established. It was revealed that the process factors (formaldehyde content in the reaction mixture, catalyst content in the reaction mixture, temperature and duration) have a significant effect on the quality of the resulting product. Changing their values allows you to adjust the values of the quality characteristics of the resulting bitumen. Keywords: binders, bitumen, oil residue, modification. Corresponding author V.М. Gunka, e-mail: [email protected]

MEASUREMENT OF THE CONTENT OF MONOETHANOLAMINE DURING THE CONTROL OF THE TECHNOLOGICAL PROCESS OF DESULFURIZATION AND IN THE ENVIRONMENTAL OBJECTS

The problem of cleaning coke oven gas from sulfur compounds, despite their recent decrease in the raw material base of coking, remains relevant in connection with the requirements to reduce sulfur dioxide emissions into the atmosphere. When using monoethanolamine for the purification of coke oven gas from sulfur compounds, production workers are faced with the problems of determining the exact concentration both in solutions and in coke oven gas and in environmental objects. The article provides an overview of the currently existing methods for the quantitative determination of the content of monoethanolamine in liquid and gaseous media. The results of studies of the possibility of their use in the conditions of by-product coke production are presented, directions of improvement of the known methods are determined in order to eliminate the influence of accompanying components inherent in by-product coke production (in particular, ammonia, amines, phenols, etc.), which distort the analysis results. The authors describe the methods of increasing the selectivity of analytical methods for determining the content of monoethanolamine in: – coke oven gas - based on the absorption of the test substance from coke oven gas by a solution of orthoboric acid, followed by its determination in a solution with pnitrophenyldiazonium; – the air of the working area under the conditions of by-product coke production - it was proposed to eliminate the negative effect of hydrogen sulfide and phenol using an absorber containing a sodium hydroxide solution located in front of the absorber with a hydrochloric acid solution for monoethanolamine (a revised measurement procedure with additions set out in accordance with the requirements of the current legislation in the field of metrology and established metrological characteristics, agreed by the Chief Sanitary Doctor of Ukraine). The directions of research necessary for the development of a method for determining the content of monoethanolamine in process waters of coke-chemical production are outlined. Keywords: desulfurization, monoethanolamine, content determination, selectivity, ammonia, p-nitrophenyldiazonium, coke oven gas, complex compound, color intensity, photometry, measurements. Corresponding author A.Yu. Martynova, e-mail: [email protected]

The selection of technological basis of deep processing of coal.

THE SELECTION OF TECHNOLOGICAL BASIS OF DEEP PROCESSING OF COAL © M.O. Gordienko (State Enterprise "Ukrainian State Research Coal Chemical Institute (UHIN)", 61023, Kharkov, Vesnina st., 7, Ukraine) The article is devoted to the analysis of the possibility of expanding the raw material base of thermal energy, as well as meeting the demand for motor fuels and chemical products through the thermochemical processing of coal, the reserves of which are large enough and available for extraction and transportation. Moreover, in contrast to technologies such as methanization and liquefaction, the most promising type of deep processing of coal seems to be its gasification. This process is carried out in sealed devices of high power according to the technologies that have a long history of improvement on an industrial scale by the world's leading companies. It was emphasized that Ukraine has significant reserves of low-calorie coal (constantly expanding due to waste of coal preparation), the thermochemical processing of which can significantly expand the domestic energy base. The basic principles of classification and technological foundations of existing industrial and industrial research installations for gasification of coal and similar materials are given. The basic diagrams and main parameters of the existing installations, which carry out the gasification process at temperatures below the melting point of the mineral (ash-forming) components of the raw material, are described - Sasol Lurgi and SES Gasification Technology (SGT). Based on the data on the world experience in the operation of thermochemical coal processing units, it is shown that low-temperature (carried out at a temperature below the melting point of the mineral ashforming components) gasification of various types of non-coking coal with certain technological solutions can be no less effective than more complex and expensive high-temperature technologies. There are grounds for believing that the efficiency of gasification with ash removal in a solid state can be further increased by using some of the technological capabilities available in coke production. Keywords: brown coal, non-coking coals, thermochemical processing, gasification, efficiency, degree of carbon conversion, energy carriers, synthesis gas, environmental safety. Corresponding author M.O. Gordienko, е-mail: [email protected]

MECHANICAL STRENGTH OF COAL: METHODS OF DETERMINATION AND FACTORS OF INFLUENCE (REVIEW)

The article substantiates the importance and problems of determining of such an indicator of the quality of solid fossil fuels, as mechanical strength. The strength of coal depends on a large number of factors (viscosity, brittleness, properties of structural bonds, etc.), the change of which is impossible to take into account. Therefore, the strength of coal in the sample, piece, pack and formation must be represented by some integral index, which inevitably fluctuates around a certain average value and can be determined only approximately. The evaluation of the strength properties of coal should be carried out on the basis of mass tests using statistical methods that allow to calculate the average value and coefficient of variation. Since the strength dispersion is mainly due to the natural inhomogeneity of the coal, the excessive accuracy of the measuring instruments has almost no effect on the statistical characteristics. Laboratory methods of mechanical tests of mine samples, in comparison with full-scale, as a rule, are very accessible and, at qualitative performance of tests, are highly reliable. The properties of coal as an object of enrichment and use are largely related to its physical properties. The physical properties of coal and mineral impurities significantly affect the formation of the main parameters that characterize the particle size distribution and fractional composition, it`s changes during the mining, transportation and enrichment processes. The basic physical and mechanical properties of solid fuels from the point of view of their industrial processing have been listed, the review has been made of the most widespread methods of study of coals mechanical durability and the equipment used for these purposes. The main advantages and disadvantages have been summarized of these methods, as well as their relationship. The factors have been Indicated tinfluencing the mechanical strength of coal. The expediency of using existing methods from the point of view of informativeness for thesphere of its application has been estimated. The methods common in the coal processing industry are considered in more detail. Keywords: coal, solid fuel mining, mechanical strength, determination methods, influencing factors, grinding strength, crushing index. Corresponding author V.V. Koval, e-mail: [email protected]

THE USE OF HUMIC ACIDS FOR MODIFICATION OF BIODEGRADABLE FILMS MANUFACTURED ON THE BASIS OF POLYVINYL ALCOHOL AND HYDROXYPROPYLMETHYL CELLULOSE

The article is devoted to the problem of obtaining packaging materials that combine a high level of gas and / or moisture resistance and strength with the ability to quickly decompose without harmful effects on the environment. The purpose of the research described in the article is to study the possibility of making such a material, which, during the period of use, will not only be resistant to the effects of various bacteria, but even prevent their appearance, and upon burial it will be biodegradable. The initial components, namely polyvinyl alcohol, hydroxypropyl methylcellulose, and humic acids of coal origin (as antibacterial additives) were reasonably selected. The modifying effect of humic substances obtained from three different samples of low-grade Ukrainian coal has been studied. In the course of the studies performed, it was found that humic acids of different origins and with different characteristics have a specific effect on the processes of structure formation in solutions of polyvinyl alcohol and hydroxypropyl methylcellulose. In particular, it was shown that in polyvinyl alcohol and methylcellulose solutions with the addition of humic acids that do not contain particles of carbon residues of various degrees of dispersion, an increase in the formation of an ordered structure is observed. Micrographs of solutions of polyvinyl alcohol and hydroxypropyl methylcellulose with humic acids are presented. The peculiarities of the influence of humic substances on the processes of structure formation of solutions of polyvinyl alcohol and hydroxypropyl methylcellulose have been investigated in order to obtain hybrid environmentally friendly biodegradable polymer films. The corresponding experimental-statistical mathematical models have been developed, they describe the dependence of the conditional viscosity and conductivity of polyvinyl alcohol and hydroxypropyl methylcellulose on the content of humic acids, the duration of preparation and one of the characteristics of the raw materials used to obtain humic acids. The corresponding equations are given. Keywords: biodegradable polymer films, coal, humic acids, polyvinyl alcohol, hydroxypropyl methylcellulose, experimental statistical mathematical models Corresponding author Zhang Siaobin, e-mail: [email protected]

The central laboratory Coke Production of PJSC «ArcelorMittal Kryvyi Rih» in present-day condition.

THE CENTRAL LABORATORY OF COKE PRODUCTION AT PJSC «ARCELORMITTAL KRYVYI RIH» IN PRESENT-DAY CONDITIONS © O.P. Chernousova, N.V. Mukina (Coke Production of PJSC «ArcelorMittal Kryvyi Rih», 50095, Dnipropetrovsk region, Kryvyi Rih, Kryvorizhstal str., 1, Ukraine), A.Yu. Martynova, PhD in Technical Sciences (State Enterprise "Ukrainian State Research Coal Chemical Institute (UHIN)", 61023, Kharkov, Vesnina st., 7, Ukraine) The article discusses the scientific and methodological organization of analytical control at the coke production of PJSC "ArcelorMittal Kryvyi Rih" (CP AMKR), as well as the results of ongoing scientific and methodological measures to ensure confidence in the results of measurements carried out in the central laboratory (CL CP AMKR). Thus, the CL CP AMKR was one of the first in the industry to put into use the test installation "KARBOTEST", which allows without the involvement of third parties to carry out important laboratory research and enables the laboratory staff to quickly develop recommendations for optimizing the composition of coal charges and improving the quality of coke. The unit is designed to test the coking process of coal mixtures and certain grades of coal concentrates under temperature conditions similar to those in coke oven batteries. CL CP AMKR introduces express methods for the analysis of chemical coking products and was one of the first to introduce a refractometric method for determining the mass fraction of distillate up to 180 ° C in crude benzene. The use of this method can significantly reduce the measurement time, avoiding the cumbersome distillation procedure, and reduce the sample volume for analysis from 100 cm3 to a few drops. In order to ensure the uniformity, quality of measurements and tests, the CL on an ongoing basis takes part in interlaboratory comparative tests of almost all types of raw materials and products entering and produced by it. These are the products that are stable over time in terms of their quality indicators, for example, coal coke, as well as products whose individual indicators can change over time (crude benzene, coal tar, etc.). Keywords: measurement, quality control, coal concentrates, coke, chemical products, qualification confirmation, experimental coking, uncertainty, interlaboratory experiment, accreditation. Corresponding author A.P. Chernousova, е-mail: [email protected]

CONTACT ANGLE OF COAL WETTING WITH WATER

It is known that in the process of coking a compacted coal charge during its ramming in an industrial ramming-loading-pushing machine, the moisture of the charge plays the role of a compaction agent. On the basis of this, the authors put forward a reasonable assumption that the higher the ability of coal grains to hydration, the stronger the contact between them and, accordingly, the greater the density of the formed rammed coal cake. Therefore, the determination of the ability to hydrate the surface of coal used in the charge for ramming is of both theoretical and practical importance. For the numerical determination of this indicator, the authors have chosen the contact angle of wetting, determined by the method of "sessile drop" of water on a carbon substrate. The article presents the results of a study of the ability of various brands of coal to hydrate. The article describes the characteristics of the studied grades of coal and their contact angle of wetting with water (Ɵ) after 1, 2 and 3 minutes of keeping the drop on a polished surface. Since according to the literature data, the organic mass of coal is hydrophobic, and mineral impurities, as a rule, are hydrophilic, the authors investigated the degree of influence of the "ash content of coal" (Аd ) indicator on the value of Ɵ. To determine the influence of the wetting angle and the internal moisture content of coal after 14 hours of moisture saturation in water (Wins) on the strength (ϭss) of the rammed sample, the corresponding graphical dependence was determined. The data obtained indicate that any significant relationship between Аd and Ɵ is absent, the correlation coefficient is insignificant (r = 0.28). Thus, the predominant factor in the hydration of cleaned coal is the properties of its organic matter. The correlation between Ɵ and the yield of volatile substances Vdaf and the content of vitrinite Vt is also insignificant – the correlation coefficient is up to 0,43 and 0,50 respectively. A close relationship of the contact angle was found with the reflection coefficient of vitrinite Ro (r = 0.72), the internal moisture content of coal after 14 hours of saturation in water, Wins (r = 0,65), and the shear strength of the rammed coal sample ϭss (r = 0,68). Keywords: coal, ability to hydration, contact angle of wetting, organic mass of coal, mineral impurities, density, strength. Corresponding author V.M. Kuznichenko, e-mail: : [email protected]

Reduction of corrosive activity of operating oil in the benzene department Coke Production of PJSC «ArcelorMittal Kryvyi Rih».

REDUCTION OF CORROSIVE ACTIVITY OF OPERATING OIL IN THE BENZENE DEPARTMENT OF COKE PRODUCTION OF PJSC «ARCELORMITTAL KRYVYI RIH» © I.I. Sikan, R.V. Karenov, N.V. Mukina, S.N. Solonko (Coke production of PJSC «ArcelorMittal Kryvyi Rih», 50095, Dnipropetrovsk region, Kryvyi Rih, Kryvorizhstal str., 1, Ukraine), L.P. Bannikov, PhD in technical sciences (State Enterprise "Ukrainian State Research Coal Chemical Institute (UHIN)", 61023, Kharkov, Vesnina st., 7, Ukraine) This paper analyzes and formulates the optimal technological solutions to reduce the corrosiveness of the absorption oil. The problem of reducing the corrosiveness and the ability of the absorbing oil to form the precipitates becomes especially actual in view of the introduction in the technological scheme of a new tube furnace ThyssenKrupp (Germany) for heating the absorption oil in the benzene section. All major work has now been completed at this facility, and soon the new furnace will be commissioned, which should significantly improve the regeneration of the absorption oil. Research of quality indicators of fresh oil and potentiodynamic testing of its water extracts has been fulfilled. To verify that the tube furnace tube material meets the requirements, a spectral analysis of a sample of the damaged tube was performed. The suspended solids of the circulating oil were observed under a microscope at a magnification of ×250. It was revealed that recycled absorption oil can lose quality as a result of tube furnace wear, frequent stoppages for repairs and watering of oil with coke oven gas condensate in scrubbers. Exit from the state of watering occurs during the operation of the distillation department due to "steaming" in the column. As a result, the concentration of salts in the oil occurs and, as a result, its corrosiveness increases. Oil watering in the distillation column occurs when the heating temperature drops. Before starting a new tube furnace, it is advisable to renew the entire working volume with fresh oil with preliminary flushing of the equipment. This will make it possible not to water it in the future during the smooth operation of the distillation and to maintain the proper quality of the absorption oil. Keywords: capture of benzene hydrocarbons, absorbing oil, distillation column, regeneration, tubular furnace, corrosiveness, survey, watering, suspended particles, aggregation. Corresponding author I.I. Sikan, е-mail: [email protected]

Raw material base for coking of the Coke Production of PJSC "ARCELORMITTAL KRYVYI RIH" in the period from 2017 to 2021.

RAW MATERIAL BASE FOR COKING OF THE COKING PRODUCTION OF PJSC "ARCELORMITTAL KRYVYI RIH" IN THE PERIOD FROM 2017 TO 2021 © N.V. Mukina (Coke-chemical production of PJSC "ArcelorMittal Kryvyi Rih", 50095, Dnepropetrovsk region, Kryvyi Rih, Krivorozhstal st., 1, Ukraine), D.V. Miroshnichenko, Doctor of Technical Sciences (NTU "Kharkiv Polytechnic Institute", 61002, Kharkiv, st. Kirpicheva, 2, Ukraine) The article presents the data on coal components that were used in the charge for coking coke oven batteries №№1-4 (bulk coal charge) and №№ 5, 6 (tamped coal charge) of the coke-chemical production of PJSC "ArcelorMittal Kryvyi Rih" in the period from 2017 to 2021, as well as averaged information on some quality indicators of the produced coke. In general, the coal raw material base of the enterprise for the last five years has been of a stable inter-basin nature with a predominance of coals from the USA, Kazakhstan, and the Russian Federation. It is shown that, as the tamping technology suggests, moisture content, bulk density and content of classes less than 0.16 and less than 3.0 mm in coal charges supplied to the coal waste plant. №№ 5, 6 are significantly higher than the values of similar indicators of coal charges supplied to the numbers 1-4. Along with this, due to the use of coals of a certain quality, ash content, total sulfur content and the thickness of the plastic layer in coal charges supplied to the coal bunker №№ 1-4, is slightly higher than similar indicators of coal charges supplied to the boiler №№ 5, 6. In total, during 2017-2021, the composition and quality indicators of the coal charge for the production of coke at the boiler plant №№ 1-4 practically did not change, while in the coal charge for the production of coke on coke oven batteries №№ 5, 6 there is a decrease in the share of highly volatile coals with a simultaneous increase in the content of medium-volatile and low-volatile components. The given values of the quality indicators of the obtained blast-furnace coke indicate that the use of tamping technology makes it possible to obtain blast-furnace coke of a higher quality than by using a traditional technology. In particular, the coke obtained at the oven batteries №№ 5, 6 are characterized by lower values of ash content, total sulfur content and abrasion (M10) with higher values of mechanical strength in terms of M25 and post-reaction strength (CSR). Keywords: coal, inter-basin raw material base, coking, charge tamping, coke quality. Corresponding author N.V. Mukina, е-mail: [email protected]