Computer simulation of the sorption of heavy metal ions by a sulphur-containing modified zeolite

This paper considers complex-chelating and complex-coordinating mechanisms of sorption of heavy metal ions, which have an affinity for sulphur atoms, by sulphur-containing sorbents. The advantages and disadvantages of sulphur-containing sorbents obtained by modification of natural materials are shown. The STATGRAPHICS Plus environment was used to analyse the applicability of classical linearized Freundlich and Langmuir equations for describing the adsorption isotherms of zinc, copper and nickel ions from aqueous solutions by the Kholinsky zeolite modified with a sulphur-containing polymer. It is shown that the classical Freundlich equation accurately describes the sorption isotherms of Zn²⁺ and Ni²⁺ by the sorbent under study at the aqueous solution temperatures of 20-40 °C and 20 °C, respectively. The use of the Freundlich equation to describe the sorption isotherms of Cu²⁺ is impractical due to its low accuracy. For this purpose, regression models for approximating experimental data or a linearized Langmuir equation are more suitable. It is shown that the Langmuir equation describes 99.35, 98.41 and 92.12% of the experimental values of Cu²⁺ sorption at the aqueous solution temperatures of 20, 40 and 60 °C, respectively. It was established that an increase in the temperature of the model solution leads to an increase in the equilibrium constant and equilibrium adsorption capacity, at the same time as decreasing the accuracy of isotherm description. The sorption isotherms of Zn²⁺ and Ni²⁺ do not obey the Langmuir equation, which can be explained by the Pearson acid-base concept (HSAB). According to this concept, Zn²⁺ and Ni²⁺ ions are acids of intermediate hardness, while Cu²⁺ ions refer to ‘soft’ acids capable of forming the strongest compounds with ‘soft’ bases (polymer sulphur atoms). Zn²⁺ and Ni²⁺ ions bind not only to sulphur atoms, but also to oxygen atoms (‘hard’ base) of the zeolite matrix, thus moving along the sorbent surface in search of sites more convenient for coordination. Therefore, for Zn²⁺ and Ni²⁺ ions, one of the basic principles of the Langmuir theory is violated, i.e. localization of the sorbate on the sorbent surface. Apparently, it is for this reason that the Langmuir equation is not applicable for describing the Zn²⁺ and Ni²⁺ sorption.

1. General toxicology. Kurlyandskii BA, Filov VA (eds.) Moscow: Meditsina; 2002. 606 p. (In Russian)

2. Chekushin VS, Borbat VF. Extraction of noble metals by sulfides and sulfoxides. Moscow: Nauka; 1984. 152 p. (In Russian)

3. Zeynalov RZ, Tatayeva SD, Atayeva NI. Preconcentration and determination of copper, zinc and cadmium chelating modified sorbent. Analitika i kontrol = Analytics and Control. 2013;17(1):89-96. (In Russian)

4. Myasoedova GV, Savvin SB. Chelating sorbents. Moscow: Nauka; 1984. 171 p. (In Russian)

5. Burba P. Anion exchangers functionalized by chelating agents (AnChel) for preconcentration of trace elements: capabilities and limitations. Fresenius Journal of Analytical Chemistry. 1991;341(12):709-715. https://doi.org/10.1007/BF00321572

6. Rafikov SR. Peculiarities of properties of Sulphur containing polymers. Vysokomolekulyarnye soedineniya = Polymer Science. Series A. 1979:21 (11):2518-2528. (In Russian)

7. Tovbin Yu.K. Molecular Theory of Adsorption in Porous Bodies. Moscow: Fizmatlit; 2013. 624 р. (In Russian)

8. Lucke H. Aliphatic Polysulfides. Publisher Huthing & Wepf, Verlag Basel; 1994.

9. Hakimullin YuN, Minkin VS, Polyutin FM, Der-berdeev TR. Sealants based on polysulfide oligomers. Synthesis, properties, application. Moscow: Nauka; 2007. 301 p. (In Russian)

10. Darmanskaya TA, Korchevin NA, Aslamova VS. Recycling of ashy waste products. Ekologia i promyshlennost Rossii = Ecology and Industry of Russia. 2010;1;39—41. (In Russian)

11. Redinova AV, Ignatova ON, Grabel'nykh VA, Levanova EP, Russavskaya NV, Terek SV, et al. Method for producing sulfur sorbents for wastewater treatment of heavy metals. Patent RF, no. 2475299; 2013. (In Russian)

12. Redinova AV, Grabel'nykh VA, Levanova EP, Korchevin NA. Extraction of heavy metal ions from water solutions by sulfur-containing polymer sorbents. Vestnik Irkutskogo gosudarstvennogo tekhnicheskogo universiteta = Proceedings of Irkutsk State Technical University. 2013;1:113-116. (In Russian)

13. Chernysheva EA, Grabel'nyh VA, Levanova EP, Russavskaja NV, Rozencvejg IB, Korchevin NA. New Approach to the Realisation of Adsorption Properties of Lignin: Preparation of Sulphur-Containing Sorbents for Heavy Metal Ions. Khimiya v interesah ustoichivogo razvitiya = Chemistry for Sustainable Development. 2017;25(3):327-332. (In Russian) https://doi.org/10.15372/KhUR20170312

14. Chernysheva EA, Grabel'nykh VA, Levanova EP, Ignatova ON, Rozentsvejg IB, Russavskaja NV, et al. Method of producing sorbent for removing heavy metals from waste water. Patent RF, no. 2558896. (In Russian)

15. Chelishchev NF, Berenshtein BG, Volodin VF. Zeolites are a new type of mineral raw materials . Moscow: Nedra; 1987. 82 p. (In Russian)

16. Deryagina EN, Levanova EP, Grabel'-nykh VA, Sukhomazova EN, Russavskaya NV, Korchevin NA. Thiylation of polyelectrophiles with sulfur in hydrazine - hydrate - amine systems. Russian Journal of General Chemistry. 2005;75(2):194-199. https://doi.org/10.1007/s11176-005-0197-y

17. Obuzdina MV, Rush EA, Dneprovskaya AV, Shalunts LV, Ignatova ON, Levanova EP, et al. Method of obtaining a sorbent to extract heavy metals from wastewater. Patent RF, no. 2624319; 2016. (In Russian)

18. Aslamova VS, Shalunc LV, Obuzdina MV, Grabel'nykh VA. Modelling the process of adsorption in the liquid-solid system: Regression analysis of copper extraction from aqueous solutions by zeolite from the Kholinskoye deposit modified by a sulphur-containing polymer. Izvestiya Vuzov. Prikladnaya Khimiya i Biotekhnologiya = Proceedings of Universities. Applied Chemistry and Biotechnology. 2019;9(2):351-359. (In Russian). https://doi.org/10.21285/2227-2925-2019-9-2-351-359

19. Karnaukhov AP. Adsorption. Texture of dispersed and porous materials. Novosibirsk: Nauka; 1999. 470 p. (In Russian)

20. Marchenko Z. Photometric determination of elements. Moscow: Mir; 1971. 376 p.

21. Aslamova VS, Shalunc LV, Obuzdina MV, Rush EA. Regression models for the extraction of nickel ions from aqueous solutions by modified zeolite. In: Matematicheskie metody v tekhnike i tekhnologiyah: sbornik trudov XXXI mezhdunarodnoi nauchnoi konferentsii = Mathematical methods in engineering and technology: Proceedings of XXXI International Scientific Conference. 10-14 September, 2018. St. Petersburg: Polytechnical University; 2018, vol. 10, p. 37-40. (In Russian)

22. Aslamova VS, Shalunc LV, Grabel'nykh VA, Aslamov AA. Regression models of zinc ion adsorption from aqueous solutions on zeolite from Kholinski deposit, modified with a sulphur-containing polymer. Izvestiya Vuzov. Prikladnaya Khimiya i Bio-tekhnologiya = Proceedings of Universities. Applied Chemistry and Biotechnology. 2020;10(1):29-38. (In Russian) https://doi.org/10.21285/2227-2925-2020-10-1-29-38

23. Aslamova VS, Chernysheva EA, Grabel'-nykh VA, Levanova EP, Russavskaya NV. Regression analysis of the regularities of extraction of zinc and cadmium ions from aqueous solutions with a sulfur-based sorbent based on lignin. Izvestiya Vuzov. Prikladnaya Khimiya i Biotekhnologiya = Proceedings of Universities. Applied Chemistry and Biotechnology. . 2018;8(4):174-183. https://doi.org/10.21285/2227-2925-2018-8-4-174-183

24. Mamonova MV, Prudnikov VV, Prudnikova IA. Surface physics. Theoretical models and experimental methods. Moscow: Fizmatlit; 2011.400 p. (In Russian)

25. Kukushkin VYu, Kukushkin YuN. Theory and practice of synthesis of coordination compounds. Leningrad: Nauka; 1990. 259 p. (In Russian)