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№ 12 (129)_*** науки_декабрь. 2024 г.
DOI - 10.32743/UniTech.2024.129.12.18997
METHODS FOR SYNTHESIZING SULFATE CATION EXCHANGERS BASED ON PYROLYSIS OIL FOR THE REMOVAL OF TOXIC AND HEAVY METALS FROM WASTEWATER
Yulduzoy Ergasheva
Senior lecturer in pharmacology, Department of General Medicine, Angren University, Uzbekistan, Angren E-mail: [email protected]
Hasan Beknazarov
DSc, Professor,
Head of the Department of "General Medicine" of the Faculty of Medicine, Angren University, Uzbekistan, Angren
Feruz Ismailov
Doctoral student
at the Tashkent Chemical Technology Research Institute,
Uzbekistan, Tashkent
МЕТОДЫ СИНТЕЗА СУЛЬФОКАТИОНИТА НА ОСНОВЕ ПИРОЛИЗНОГО МАСЛА ДЛЯ УДАЛЕНИЯ ТОКСИЧНЫХ И ТЯЖЕЛЫХ МЕТАЛЛОВ ИЗ СТОЧНЫХ ВОД
Эргашева Юлдузой Олимовна
ст. преподаватель кафедры общей медицины, Ангренского университета, Республика Узбекистан, г. Ангрен
Бекназаров Хасан Сойибназарович
д-р техн. наук, профессор, зав. кафедрой Общая лечебная дело, Ангренского университета, Республика Узбекистан, г. Ангрен
Исмаилов Феруз Собирович
докторант
Ташкентского химико-технологического научно-исследовательского института, Республика Узбекистан, г. Ташкент
ABSTRACT
The article synthesizes a new type of sulfocationite ion exchange resin based on pyrolysis oil, an industrial waste. In the work, a product consisting of a naphthalene fraction was sulfonated, and a polymer with a tertiary structure was synthesized from the resulting sulfocompound based on formalin. Factors affecting the reaction were studied. Its composition and structure were determined using IR spectroscopy.
АННОТАЦИЯ
В статье синтезирован новый тип ионообменной смолы сульфокатионита на основе пиролизного масла из промышленного отхода. В работе сульфирован продукт, которое состоит из нафталиновой фракции, и на основе полученного сульфосоединения синтезирован сшитый полимер с формалином. Изучены факторы, влияющие на реакцию. Его состав и структура были определены с помощью ИК-спектроскопии.
Keywords: pyrolysis oil, sulfuric acid, Sulfo cationite, dispersant, wastewater.
Ключевые слова: пиролизное масло, серная кислота, сульфокатионит, диспергатор, сточные воды.
Библиографическое описание: Ergasheva Y., Beknazarov Kh.S., Ismailov F. METHODS FOR SYNTHESIZING SULFATE CATION EXCHANGERS BASED ON PYROLYSIS OIL FOR THE REMOVAL OF TOXIC AND HEAVY METALS FROM WASTEWATER // Universum: технические науки : электрон. научн. журн. 2024. 12(129). URL: https://7universum.com/ru/tech/archive/item/18997
Introduction. Currently, the chemical industry is undergoing a transition from raw materials to finished products through the effective use of local raw materials, including the production of semi-finished products, including organic synthesis and nanotechnologies. At the same time, one of the urgent tasks is to gradually reduce the export of raw materials (natural gas, industrial salts, etc.) and organize their processing in the republic. For this purpose, the Ustyurt gas and chemical complex, owned by Uz-KorGaz Chemical LLC, is engaged in the production of import-substituting products using secondary products by processing "pyrolysis oil", a by-product of which is used in industrial enterprises[1-4].
The chemical industry cannot develop without new synthetic ion exchangers, which are widely used in various fields: the production of purified or desalinated water, the separation of non-ferrous and precious metals in the hydrometallurgical industry, the separation of toxic and heavy metals from wastewater [5-8].
Dispersant NF is a product obtained by sulfonating naphthalene with sulfuric acid, followed by condensation with formaldehyde and neutralization with sodium hydroxide. Dispersant NF is produced in grades "A" and "B". Dispersant NF is produced in the form of a 35-36% solution or a dry powder with a mass fraction of moisture not exceeding 10% [9-11].
Pyrolysis oil (A 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; and the second main fraction, which contains methylnaphthalenes and acenaphthene, crystallizes upon cooling and is a residue added to anthracene oil. Acenaphthene easily crystallizes from high-temperature cuttings 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 fractions
240-255. Seven out of ten possible dimethylnaphthalenes are separated from fractions 260-270. When fractions 280-290 are cooled, many mixed crystals are separated, mainly containing acenaphthene, diphenyl oxide and fluorine. 2 3 6 - and 1 3 7-trimethylnaphthalenes were isolated from the residual oil. Skatole occurs together with the 2-, 5- and 7-isomers. Its separation 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, vapour pressure (at 80 °C) 1040 Pa.
Experimental part
The following processes are carried out to synthesize the sulfonated ion exchange resin:
The pyrolysis oil was sulfonated with concentrated sulfuric acid (mass ratio 1:1) at 160-165oC for 3-4 hours, resulting in a dark black sulfonates; the sulfonates, placed in a pressure vessel, were diluted with distilled water and polycondensed with 38% formaldehyde (initial mass ratio of naphthalene and formaldehyde 1:2) at 110-120 oC and a pressure of 2-4 MPa; the water-insoluble solid polycondensate was mechanically crushed and heated at 90-95 oC for 12 hours to complete the pol-ycondensation. The pyrolysis oil was suffocated with concentrated H2SO4 to p-naphthalenesulfonic acid. The pyrolysis oil was mixed with sulfuric acid at 70°C and boiled for 1 hour. To achieve complete conversion according to equation 1, the water of the reaction formed during the sulfonation process is distilled azeotropically. During the reaction, along with p-naphthalenesulfonic acid, naphthalene-p-sulfonic acids or p-naphthylsulfones with a naphthalene double ring are formed. The structure of the synthesized products was determined by IR spec-trometry [9].
+ H2SO4
140-160oC
SO3H
Figure 1. Naphthalene fractions Figure 2. p-naphthalene sulfonic acid
The graph showing the effect of various factors on the yield of sulfocationite formation based on pyrolysis oil: time and molar ratios of the initial substances obtained is presented in Figure 2.3.
Figure 3. Time dependence of the yield of sulfocationite obtained from pyrolysis oil The molar ratio of pyrolysis oil and Sulfuric acid: 1- (1:1,5); 2-(1:0.5).
The time dependence of the yield of sulfocationite obtained from pyrolysis oil is
shown in Figure 1. As can be seen from Figure 1, the highest yield compared to others is obtained when the ratio of pyrolysis oil to sulfuric acid is 1:1.5. The synthesis process was carried out for 3 hours. In the experiment conducted for 3.5 hours, the yield of sulfocationite formation remains almost unchanged, that is, the yield in the reaction yield does not increase. We can cite the fact that the substances obtained for the raw material are in different aggregate states during the 3-hour and longer time intervals. Because the presence of interacting substances in two different aggregate states reduces their interaction. We can see the temperature dependence of the yield of the synthesized sulfocationite in Figure 2.
As can be seen from Figure 2, the optimal ratio of components in the synthesis of sulfocationite is 1:1.5,
under such conditions, the yield of sulfocationite is 92.8%. The highest dry residue is obtained with a ratio of starting products of 1:0.5, but the ion exchange capacity of the obtained sulfocationites is low. Based on this, the optimal temperature for obtaining sulfocationite was chosen as 160oC. The reaction time also plays an important role in the synthesis of sulfocationites. Three ratios of the initial products were also chosen to select the optimal reaction temperature. The figure below shows the dependence of the sulfocationite yield on the reaction time at a temperature of 160oC. As can be seen from the figure, as a result of carrying out the reaction for 180 minutes under optimal conditions, a yield of sulfocationite of 92.8% is obtained. Further continuation of the reaction under such conditions leads to a decrease in the reaction yield.
Figure 2. Dependence of the yield of sulfonic acid obtained from pyrolysis oil on the molar ratio ofpyrolysis oil
and sulfuric acid
Pyrolysis oil, sulfuric acid molar ratio 1-(1:1,5); 2-(1:0,5);
In our research, the effect of temperature, time, and molar ratios of substances on the yield of the product when producing sulfocationite using pyrolysis oil and sulfuric
acid was studied. The results obtained are presented in Table 1 below.
Table 1.
The effect of molar ratios and time on product yield
№ Mole ratios Time, clock Yiled, % № Mole ratios Time, hour Yiled, %
1 1:0,5 26,2 11 1 0,5 49,4
2 1:0,8 37,3 12 1 0,8 65,8
3 1:1,2 1 47,4 13 1 1,2 3 72,5
4 1:1,3 54,3 14 1 1,3 78,7
5 1:1,5 56,5 15 1 1,5 79.8
6 1:0,5 35,5 16 1 0,5 49,5
7 1:0,8 60,5 17 1 0,8 65,9
8 1:1,2 2 70,5 18 1 1,2 4 72,6
9 1:1,3 72,4 19 1 1,3 78,7
10 1:1,5 75,5 20 1 1,5 78,9
Table 1 shows the effect of various factors on the yield of sulfocationite based on the results presented: time and molar ratios of the initial substances. As can be seen from Figure 2, compared to others, pyrolysis oil is obtained when the highest ratio of sulfuric acid is 1: 1.5, but the resulting product contains a derivative of P-naphthylsulfones. Therefore, derivatives of polyhydric alcohols are of particular importance in studying the effect of mono-, di- and other low-molecular compounds. As can be seen from the results obtained, it was found that the highest yield of sulfocationite was obtained when the molar ratio of pyrolysis oil, sulfuric acid and formaldehyde was 1: 1.5 and the process lasted 3 hours.
Results and Discussion
The IR spectrum of the synthesized sulfocationite 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 3049.39^698.23 cm-1. The system of 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 the 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.
As the number of aromatic rings increases, 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 3049.46 cm-1 in the spectrum is due to the valence vibrations of the C-H bonds in the naphthalene molecule. The intense region at 783.10 cm-1 is due to the vibrations of the naphthalene ring in a plane other than the ring plane. The absorption regions of the benzene ring are absorbed in the following regions at 1456.26 and 1508.33 cm-1, and the region at 738.74 cm-1 is determined to contain -C-C-.
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Figure 4. IR spectrum of pyrolysis oil
From the obtained IR spectroscopy data, it can be concluded that the introduction of groups during the reaction produces stretching and bending vibrations characteristic of these groups[4].
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Figure 5. IR spectrum of the synthesized sulfocationite
As can be seen from Figure 4, the new absorption bands in the region of 2879.72 cm-1 indicate that the functional group -CH has changed its structure to the R-SO2-R chemical bond. In IR spectroscopy, the asymmetric stretching vibrations of the C=C groups in the ring in the region of 1699.29 cm-1 are present, and the characteristic absorption lines of the symmetric stretching vibrations in the region of 746.45 - 669.30 cm-1 are present. This indicates that the synthesized sulfocationite has a functional group.
Conclusion
In summary, sulfocationite ion exchange resin is a versatile and highly selective ion exchange resin that
plays an important role in various industrial processes. Sulfocationite was obtained as a by-product of the technological process of hydrocarbon pyrolysis by rational use of pyrolysis oil. Its production process includes polymer matrix synthesis, crosslinking, sulfonation and washing, resulting in a highly charged and highly selective ion exchange resin with a wide range of applications. Regardless of its use for water treatment, sulfonated cation resin is an important industrial material that helps to ensure the quality and purity of drinking water and other industrial processes.
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