Physico-chemical and sorption properties of original and modified clay from the Levashinskoye deposit of the Republic of Dagestan
Abstract
The high sorption, ion exchange, and catalytic properties of natural clay minerals determine their widespread use in various technological processes. More than 30 deposits of various clays have been identified and explored within the territory of the Republic of Dagestan, one of which is the Levashinskoye deposit. Available data on the adsorption of ions of rare alkali (Rb+ and Cs+) and alkaline earth (Sr2+) metals on clay minerals make the task of study of the possibility of using clay from this deposit as a sorbent for extracting these ions from aqueous solutions even more relevant. This, in turn, is due to the need for effective sorbents for concentrating and extracting ions of alkali and alkaline earth metals when solving problems of complex processing of hydromineral raw materials. The purpose of this study was the investigation of the physicochemical and sorption properties of Rb+, Cs+, Sr2+ native and hydrochloric acid-modified clay from the Levashinskoye deposit of the Republic of Dagestan. Based on a comprehensive study, the mineralogical composition of native clay was established, the main clay minerals of which were: illite, nontronite, and montmorillonite. In addition, the sample contained calcite and quartz.
In order to increase the content of clay minerals, with which the sorption activity of clay is mainly associated, the original clay was treated with a 1 M hydrochloric acid solution, which led to an increase in the content of clay minerals from 62% in the original clay to 75% in the clay treated with HCl.
Sorption experiments for Rb+, Cs+, Sr2+ were carried out in model solutions, the concentration of the studied ions in solutions varied in the range of 20-700 mg/dm3. It was shown that the equilibrium of adsorption of these ions on the studied clay can be satisfactorily described both by equations for a non-uniform surface (Freundlich, Temkin, Dubinin-Radushkevich) and by the Langmuir isotherm for a homogeneous surface. It was found that the modification of the original clay with a solution of hydrochloric acid increases the sorption capacity of the clay for the studied ions. It has been established that the main mechanism of sorption of these ions on both the original and modified clay of the Levashinskoye deposit was ion exchange, while other mechanisms cannot be excluded. The study of the kinetics of Rb+, Cs+, Sr2+ sorption on modified clay showed that the sorption process of these ions can be described by a mixed-diffusion model and a pseudo-second-order model.
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Prirodnye resursy i poleznye iskopaemye Respubliki Dagestan https://geologdgu.blogspot.com/p/blog-page_9.html (data obrashcheniya 31.03.2023)
Temerdashev Z., Abakumov A., Bolshov M.,Khalafyan A., Ageeva N., Vasilyev A., Ramazanov A. Instrumental assesmentof the formation of the elemental composition of wines with various bentonite clays. Microchem. J. 2022; 175: 107145. https://doi.org/10.1016/j.microc.2021.107145
Vezencev A.I., Korol'kova S.V., Volovicheva N.A. Fiziko-himicheskie harakteristiki prirodnoj i modificirovannoj gliny mestorozhdeniya polyana Belgorodskoj oblasti. Sorbtsionnye i khromatograficheskie protsessy. 2008; 8(5): 790-795. (In Russ.)
Shcherbakov A.A., Solodkij N.F., Viktorov V.V., Zhestkov V.M., Serikov A.S., Klepikov M.S. Fiziko-himicheskie issledovaniya glin Nizhneuvel'skogo mestorozhdeniya. Vestnik YuUrGU. 2011;33: 86-89. (In Russ.)
Ramazanov A.Sh., Kasparova M.A., Saraeva I.V., Mirzaeva H.A., Ramazanova G.R., Ataev D.R. Sorbcionnye svojstva prirodnyh glinistyh materialov Respubliki Dagestan. Vestnik Dagestanskogo gosudarstvennogo universiteta. 2013; 13(1): 212-217. (In Russ.)
Ramazanov A.Sh., Esmail G.K., Sveshnikova D.A. Kinetika i termodinamika sorbcii ionov tyazhelyh metallov na montmorillonit soderzhashchih glinah. Sorbtsionnye i khromatograficheskie protsessy. 2015; 15(5): 672-682. (In Russ.)
Kushnareva O.P., Kanygina O.I. Ionoobmennye svojstva prirodnoj montmorillonit soderzhashchej gliny Orenburgskoj oblasti. Vestnik Orenburgskogo gosudarstvennogo universiteta. 2017; 9: 23-26.
Vezencev A.I., Peristaya L.F., Nguen Fuk Kao, Peristyj V.A., Kopylova E.V. Issledovanie sorbcionnyh svojstv prirodnyh montmorillonitovyh glin raznyh mestorozhdenij dlya ochistki vody ot ionov svinca (II). Sorbtsionnye i khromatograficheskie protsessy. 2018; 18(1): 43-51. (In Russ.)
Novacović T., Rožić L., Petrović S., Rosić A. Synthesis and characterization of acid-activated Serbian smectite clays obtained by statistically designed experiments. Chem. Eng. J. 2008; 137: 436-442. https://doi.org/10.1016/j.cej.2007.06.003
Ilker Kipçak, Emel Kurtaran Ersal, Mine Őzdemir Adsorptive removal of Ni2+ ions from aqueous solutions by nodular sepiolite (Meerschaum) and industrial sepiolite samples from Erkișehir, Turkey. Clay Clay Miner. 2020; 68: 220-236. https://doi.org/10.1007/s42860-020-00077-7
Smičiklas I., Dimović S., Plećaš I. Removal of Cs+, Sr2+ and Co2+ from aqueous solutions by adsorption on natural clinoptilolite. Appl. Clay Sci. 2007; 35: 139-144. https://doi.org/10.1016/j.clay.2006.08.00
Ramazanov A.Sh., Ataev M.B., Kasparova M.A., Saraeva I.V., Dzhamueva R.A. Adsorbciya ionov ceziya i stronciya iz vodnyh rastvorov prirodnym alyumosilikatom. Vestnik Dagestanskogo nauchnogo centra. 2011; 43: 33-37. (In Russ.)
Yildiz D., Erten H.N., Kiş M. The sorption behavior of Cs+ ion on clay minerals and zeolite in radioactive waste management: sorption kinetics and thermodynamics. J. Radioanal. Nucl. Chem. 2011; 288: 475-483. https://doi.org/10.1007/s10967-011-0990-5
Milyutin V.V., Vezencev A.I., Sokolovskij P.V., Nekrasov N.A. Sorbciya radionuklidov ceziya iz vodnyh rastvorov na prirodnyh i modificirovannyh glinah. Sorbtsionnye i khromatograficheskie protsessy. 2014; 14(5): 879-883. (In Russ.)
Zaunbrecher L.K., Cygan R T., Elliott C. Molecular models of cesium and rubidium adsorption on weathered micaceous minerals. J. Phys. Chem. A. 2015; 119: 5691-5700. https://doi.org/10.1021/jp512824k
Konopleva I.V. Selektivnaya sorbciya radioceziya sorbentami na osnove prirodnyh glin. Sorbtsionnye i khromatograficheskie protsessy. 2016; 16(4): 448-456. (In Russ.)
Zabulonov Y. , Kadoshnikov V., Zadvernyuk H., Melnichenko T.,Molochko V. Effect of the surface hydration of cesium and strontium from dilute solution. Adsorption. 2021; 27: 41-48. https://doi.org/10.1007/s10450-020-00263-y
Baklaj A.A., Makovskaya N.A., Leont'eva T.G.,Kuz'muk D.A. Izuchenie mineral'nogo sostava prirodnyh glin Respubliki Belarus' i ih sorbcionnyh svojstv po otnosheniyu k radionuklidam ceziya i stronciya. Sorbcionnye i hromatograficheskie processy. 2021; 21(2): 246-255. https://doi.org/10.17308/sorpchrom.2021.21/3358 (In Russ.)
Goldovskaya-Peristaya L.F., Volovicheva N.A., Vezencev A.I., Peristyj V.A. Izoterma sorbcii ionov stronciya montmorillonit-gidroslyudistymi glinami. Sorbtsionnye i khromatograficheskie protsessy. 2011; 11(2): 165-171. (In Russ.)
Zhao Y., Shao Zh., Chen Ch., Hu J.,Chen H. Effect of environmental conditions on adsorption behavior of Sr(II) by Na-rectorite. Appl. Clay Sci. 2014; 87: 1-6. https://doi.org/10.1016/j.clay.2013.11.021
Yurchenko V.V., Sviridov A.V., Sviridov V.V., Nikiforov A.F., Pryanichnikov S.V. Adsorbciya stronciya na modificirovannyh sloistyh alyumosilikatah. Sorbtsionnye i khromatograficheskie protsessy. 2017; 17(1): 506-512. https://doi.org/10.17308/sorpchrom.2017.17/407 (In Russ.)
Nikashina V.A., Serova T.B., Kusmina T.G., Lihareva N.L. Kinetics of Sr2+ sorption on clinoptilolite-containing tuffs of different deposits from the surface drinking water. Sorbtsionnye i khromatograficheskie protsessy. 2017; 17(6): 886-892. https://doi.org/10.17308/sorpchrom.2017.17/449 (In Russ.)
Alhasov A.B., Alhasova D.A., Alishaev M.G., Ramazanov A.Sh., Ramazanov M.M. Osvoenie geotermal'noj energii / Pod.red. V.E. Fortova. M.: Fizmatlit, 2022. 320 p. (In Russ.)
Lygina T.Z., Mihajlova O.A., Haprinov A.N., Konyuhova T.P. Tekhnologiya himicheskoj aktivacii neorganicheskih prirodnyh mineral'nyh sorbentov. – Kazan': Izd-vo Kazan. gos. tekhnol. un-ta. 2009. 120 p. (In Russ.)
Jablońska B., Bush M., Kityk A.V., Huber P. Natural and chemically modified post-mining clays – structural and surface properties and preliminary tests on copper sorption. Minerals. 2019; 9: 1-20. http://doi.org/10.3390/min9110704
Mostalygina L.V., Chernova E.A., Buhtoyarov O.I. Kislotnaya aktivaciya bentonitovoj gliny. Vestnik YuUrGU. 2012; 24: 57-61. (In Russ.)
Maslova M.D., Belopuhov S. L., Timohina E.S. i dr. Termohimicheskie harakteristiki glinistyh mineralov i slyud. Vestnik Kazanskogo tekhnologicheskogo universiteta. 2014; 17: 121-127. (In Russ.)
Vezencev A.I., Korol'kova S.V., Volovicheva N.A. Ustanovlenie kineticheskih zakonomernostej sorbcii ionov Cu2+ nativnymi i magnij-zameshchennymi formami montmorillonitovyh glin. Sorbtsionnye i khromatograficheskie protsessy. 2010; 10(1): 115-120. (In Russ.)
Permyakov E.N., Ejrish Z.N. Kristallohimicheskie i strukturnye osobennosti montmorillonita i ih vliyanie na svojstva bentonitovyh glin. Bentonity. M., Nauka, 1980. 117-125 p. (In Russ.)
Kirovskaya I.A. Adsorbcionnye processy. Irkutsk, Izd-vo Irkutskogo un-ta, 1995. 304 p. (In Russ.)
Filatova E.G., Matienko O.I. Issledovanie adsorbcii ionov nikelya (II) prirodnymi sorbentami. Sorbtsionnye i khromatograficheskie protsessy. 2023; 23(1): 116-128. http://doi.org/10.17308/sorpchrom.2023.23/10999 (In Russ.)
Venicianov E.V., Rubinshtejn R.N. Dinamika sorbcii iz zhidkih sred. M. Nauka, 1983. 237 p. (In Russ.)
Alosmanov R.M. Issledovanie kinetiki sorbcii ionov svinca i cinka fosforsoderzhashchim kationitom. Vestn. Mosk. Un-ta. Ser.2. Himiya. 2011; 52: 145-148. (In Russ.)
Ho Y. Second-order kinetic model for the sorption of cadmium onto tree fern: a comparison of linear and non-linear methods. Water Res. 2006; 40: 119-125. https://doi.org/10.1016/j.watres.2005.10.040
Khamizov R.H., Sveshnikova D.A., Kucherova A.E., Sinyaeva L.A. Modeli kinetiki sorbcionnyh processov v ogranichennom ob"eme. Zhurn. Fiz. Himii. 2018; 92: 1451-1460. https://doi.org/10.1134/S0044453718090121 (In Russ.)