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SYNTHESIS AND ANALYSIS OF SULFOCATIONITE BASED ON SECONDARY PRODUCTS
Maxliyo Ganibekova
Lecturer in chemistry, Department of General Medicine, Angren University, Uzbekistan, Angren E-mail: oybek [email protected]
Hasan Beknazarov
DSc, Professor, Head of the Department of General Medicin, Angren University, Uzbekistan, Angren
Feruz Ismailov
Doctoral student
at the Tashkent Chemical Technology Research Institute,
Uzbekistan, Tashkent
СИНТЕЗ И АНАЛИЗ СУЛЬФОКАТИОНИТА НА ОСНОВЕ ВТОРИЧНЫХ ПРОДУКТОВ
Ганибекова Махлиё Фархадовна
преподаватель, кафедры общей медицины, Ангренского университета, Узбекистан, г. Ангрен
Бекназаров Хасан Сойибназарович
д-р техн. наук, профессор, заведующий кафедрой Общее лечебное дело Ангренского университета, Узбекистан, г. Ангрен
Исмаилов Феруз Сабирович
докторант
Ташкентского химико-технологического научно-исследовательского института,
Узбекистан, г. Ташкент
ABSTRACT
Based on scientific experiments, sulfonation of pyrolysis oil with 96% sulfuric acid. The secondary product "pyroly-sis oil" of the Ustyurt Gas Chemical Complex, owned by Uz-KorGaz Chemical LLC, was sulfonated with sulfuric acid. Production of import-substituting products using secondary products of processing "pyrolysis oil", cationites were synthesized and used in industrial enterprises. This is a synthetic polymer consisting of a network of cross-linked functional groups of sulfonic acid, which, as has been studied, has a high charge and high selectivity. Optimum conditions for the ratio of substances and temperature during the reaction were determined. IR spectral analysis of the obtained product was carried out. The separation of toxic and heavy metals from wastewater was studied analytically based on literature data.
АННОТАЦИЯ
На основе научных экспериментов сульфирование пиролизного масла 96% серной кислотой. Вторичный продукт «пиролизная нефть» Устюртского газохимического комплекса, принадлежащего ООО «Uz-KorGaz Chemical», сульфонировали серной кислотой. Производство импортозамещающей продукции с использованием вторичных продуктов переработки «пиролизного масла», синтезированы катиониты и применяются на промышленных предприятиях. Это синтетический полимер, состоящий из сети сшитых функциональных групп сульфо-новой кислоты, который, как было изучено, имеет высокий заряд и высокую селективность. Определены оптимальные условия по соотношению веществ и температуре в ходе реакции. Проведен ИК-спектральный анализ полученного продукта. Разделение токсичных и тяжелых металлов из сточных вод было изучено аналитически на основе литературных данных.
Keywords: pyrolysis oil, sulfonation, sulfuric acid, formalin, naphthalene sulfonic formaldehyde resin
Библиографическое описание: Ganibekova M.F., Beknazorov H., Ismailov F. SYNTHESIS AND ANALYSIS OF SULFOCATIONITE BASED ON SECONDARY PRODUCTS // Universum: технические науки : электрон. научн. журн. 2025. 1(130). URL: https://7universum.com/ru/tech/archive/item/19181
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Ключевые слова: пиролизное масло, сульфирование, серная кислота, формалин, нафталинсульфоформаль-дегидная смола
Introduction. The chemical industry is implementing transition processes from raw materials to finished products through organic synthesis, using local raw materials effectively. At the same time, the organization of raw materials and their processing in the republic is an urgent task. For this purpose, the Ustyurt gas-chemical complex, owned by Uz-KorGaz Chemical LLC, is used in industrial enterprises for the production of import-substituting products using secondary products by processing "pyrolysis oil", naphthalene sulfonic acid formaldehyde. The joint venture of JV LLC "Uz-Kor Gas Chemical" is one of the largest manufacturers of polymer products in Central Asia based on the processing of natural gas in the Ustyurt region. The plant's annual production capacity is 387 thousand tons of polyethylene and 83 thousand tons of polypropylene. At the same time, more than 102 thousand tons of pyrolysis distillate, 8 thousand tons of pyrolysis oil (TPS - heavy pyrolysis pitch) and more than 10 thousand tons of tar products are produced. Pyrolysis distillate, pyrolysis oil and tar products are not processed in the republic [1]. Highly sulfonated polymers used as acid catalysts are of increasing interest in many chemical industries [2-5]. Several solid acids with sulfonated polymers are considered suitable for reactions involving water as a reagent, such as hydrolysis, in terms of activity, stability and insolubility [6-7]. Many environmentally important synthetic aromatic compounds (e.g. aromatic carboxylic acids, naphthalene and benzenesulfonic acids) and quaternary benzyl ammonium compounds exist as ions in the aqueous phase over a wide pH range. They are often called hydrophobic ionizable organic compounds [8-9]. Previous studies have shown the effective sorption of sulfocations on polymer anion exchangers [10]. Unfortunately, due to the high sorption affinity between cation exchangers and strongly basic anion exchangers, the regeneration of spent anion exchangers becomes a particularly difficult and expensive. The plant regeneration process for these heat exchangers requires large volumes of concentrated saline or alkaline solutions or even organic solvents [11]. Naphthalene can be sulfonated under various conditions. Different naphthalene sulfonic acids are obtained depending on the temperature and the sulfonating agent used. The most important from an industrial point of view is sulfonation with 96% sulfuric acid at high temperatures (above 400 K). Under such conditions, sulfonation primarily produces naph-thalene-2-sulfonic acid, which is used as a starting material for the very important intermediate 2-naphthol. Pyrolysis oil (secondary raw material of the UzKorGaz chemical complex, containing up to 85-90% naphthalene), Heavy oils separated from naphthalene are usually divided into three fractions: the first small phenolic fraction; the second main fraction, which contains methylnaphthalenes and acenaphthene, crystallizes upon cooling and is a residue added
to anthracene oil. Acenaphthene crystallizes easily from fluorine-containing temperature cuts, but is contaminated with fluorine. Purification is achieved by recrystallization from solvents such as alcohol or naphtha. Indole and a- and p-methylnaphthalenes can be obtained from the 240-255°C fraction. Seven out of ten possible dimethylnaphthalenes are isolated from the 260-270°C fraction. When the 280-290°C fraction is cooled, a large amount of mixed crystals are separated, mainly containing acenaphthene, diphenyl oxide and fluorene. 2-, 3-, 6- and 1-, 3-, 7-trimethylnaphthalenes were isolated from the residual oil. Skatole occurs together with the 2-, 5- and 7-isomers, and its isolation is based on the fact that all four compounds do not form carboxylic acids when the sodium derivative is treated with carbon dioxide. Physical properties Density 1.14 g/cm3, melting point 80.26°C, boiling point 217.7°C, water solubility 30 mg/l, flammability 79-87 °C, molar mass 128.17052 g/mol, vapor pressure (at 80 °C) 1040 Pa.
Methodology. This reaction was first described by Faraday in 1826 and has been the subject of various studies in the following years. A comprehensive kinetic analysis of this reaction was initiated by Ioffe. Its simple model was developed by Küchler and Langbeir, Zarzycki and Starzak, separately, and Passet et al. An analysis of the usefulness of all these models for the sulfonation of naphthalene with 96% sulfuric acid showed that none of them gave a sufficiently accurate description of the process.
Experimental part. The main objective of this work was to experimentally study the sulfonation reaction of naphthalene under a wide range of operating conditions and determine the kinetic model. Sulfonation experiments were carried out by heating the pyrolysis oil dropwise with an aqueous solution of sulfuric acid. A 250 ml standard 3-necked glass flask and a 25 mm diameter impeller with a controlled rotation speed were used as a reactor. The reactor was heated in an oil bath at a constant temperature. The operating procedure is as follows. A measured amount of pyrolysis oil is placed in the reactor and heated to 70 °C. After reaching the required temperature, the required amount of sulfuric acid is added at a constant rate for 15-20 seconds. The use of sulfuric acid prevents excessive temperature increase of the reaction mixture, and the reaction temperature is raised to 160 °C and held for 3 hours. The temperature changes during the reaction are measured and recorded. The reaction is immediately cooled to 110 °C and slowly added with 36% formalin solution. The resulting product is neutralized. The concentration of sulfuric acid and the naphthalene sulfonic acid based on pyrolysis oil are analyzed.
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Figure 1. Sulfuric acid conversion at different mixing speeds
Table 1.
Experimental conditions for sulfonation of pyrolysis oil
№ T 0C Ms Mn s
1 155 119,6 100,0 1,5
2 160 90,8 128,0 0,8
3 165 119,5 100,0 1,5
4 165 195,5 100,0 1,5
5 165 119,0 100,0 1,5
Five sulfonation experiments were conducted with initial molar ratios of sulfuric acid to pyrolysis oil ranging from 1% to 1.5% and temperatures ranging from 160 to 165°C. All experiments were conducted in 96% sulfuric acid and the total reaction time was 4 hours. The experimental conditions are listed in Table 1. When pyrolysis oil was treated with 96% sulfuric acid, high yields of naphthalene monosulfonic acids were obtained. Analyses showed that a maximum of 1.4% by weight of naphthalene reacted to form sulfones, while tars accounted for only 0.1% of the reaction mixture.
Results and Discussion
IR spectroscopy. The IR spectrum of the synthesized naphthalene sulfonic acid formaldehyde,
a plasticizer, was recorded on a spectrometer "IR Tracer-100" (SHIMADZU CORP., Japan, 2017). The high sensitivity of the spectrometer (noise ratio 60,000:1) allows analyzing the wavenumbers of various samples, despite the low intensity of the spectral bands, with a wavenumber scale of 305L39^619.15cm-1. The system for optimizing the operation of the interferometer, together with the built-in self-diagnosis and the built-in automatic drying device, significantly increases the ease of use and also ensures long-term stability of the device. The presence of a high-speed scanning mode (20 spectra per second) allows for monitoring reactions lasting several seconds.
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Figure 2. IR spectrum of pyrolysis oil
With an increase in the number of aromatic rings, the number of absorption bands in the lower frequency part of the IR spectrum increases. You can see this in the IR spectra of pyrolysis oil. The line around 3051.39 cm-1 in the spectrum is due to the valence vibrations of the C-H bonds in the naphthalene molecule. The intense band at 783.10 cm-1 is due to the
vibrations of the naphthalene ring in a plane other than the ring plane. The absorption bands of the benzene ring are absorbed in the following regions: 1456.26 and 1506.41 cm-1, and the presence of -C-C-in the region at 738.74 cm-1 is determined [12; p. 110].
As can be seen from Figure 3, after processing the raw material, it can be said that the obtained superplas-ticizer mainly has the following functional groups based on IR spectroscopy. The new absorption bands in the region of 1161.15 cm-1 indicate that the functional group SO2-OH has changed its structure to the R-SO2-OH chemical bond. In the IR spectrum, there are absorption lines for asymmetric valence vibrations in the region of -1022.27 cm-1, and there are characteristic absorption lines for symmetric valence vibrations
in the region of 748.38-673.16 cm-1. This indicates that the synthesized superplasticizer has a functional group.
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Table 1.
Sulfocationite quality and test results
№ Indicator name Samples
prototip 1 2 3 4 5 6
Brown liquid Dark Dark Dark Dark Dark Dark
1 Appearance brown brown brown brown brown brown
liquid liquid liquid liquid liquid liquid
2 Mass fraction of active ingredients relative to dry product, % not less than 71 70 69 70 71 72 67
3 Mass fraction of water, %, not more than 66,5 68 67 67 66,5 66 67
4 The hydrogen ion activity (pH) of an aqueous solution with a concentration of 2.5 mass percent. % 7,6 7,0 7 8,4 7,6 7.5 7,3
Conclusion. The obtained naphthalene sulfonic formaldehyde resin based on pyrolysis oil was prepared and the physicochemical properties were studied. Pyrolysis oil reacts with concentrated sulfuric acid to form р-naphthalene sulfonic acid at high temperature. The reaction temperature was controlled. Possible formation of polysulfones and sulfones, which affect the
References:
purity of the product. When р-naphthalene sulfonic acid is condensed with formaldehyde, the acidity of the system greatly affects the degree of condensation. A large amount of acid easily leads to polymerization. Naphthalene sulfonic formaldehyde resin was synthesized based on pyrolysis oil.
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