| ArticleName |
Closed-loop graphite intercalation technology |
| ArticleAuthorData |
Siberian Federal University (Krasnoyarsk, Russia)
Gilmanshina T. R., Head of Chair, Candidate of Engineering Sciences, Associate Professor, gtr1977@mail.ru Dubova I. V., Associate Professor, Candidate of Engineering Sciences, Associate Professor, idubova@mail.ru Dorovskaya A. A., Student
LLC «LKM-ANTIKOR SIBERIA» (Krasnoyarsk, Russia).
Olshevsky M. Yu., Сhemical Technologist |
| Abstract |
The industrial intercalation of graphite using aqueous oxidizing mixtures, followed by intercalate hydrolysis, results in the generation of significant volumes of wastewater. However, the composition of these effluents and viable methods for their treatment or reuse remain largely undocumented in the open literature. This study investigates the volume, chemical characteristics, and potential for cyclic reuse of wastewater generated during graphite intercalation processes. Graphite of grade GO-1, sourced from the Taiginskoye deposit, was used as the base material. The effectiveness of the intercalation process was assessed by the graphite expansion ratio at 500 °C. Sulfate ion concentrations were determined via titrimetric analysis according to GOST 31940–2012, and total chromium content was measured using the iodometric method per GOST 26473.10–85. It was established that production of 1 kg of intercalated graphite generates up to 200 liters of wastewater, classified by acidity into three categories: highly acidic (pH 0–1), moderately acidic (pH 2–4), and weakly acidic to near-neutral (pH 5–6). Sulfate concentrations ranged from 12.10 to 3.80 g/L, and total chromium content from 2.49 to 0.30 g/L—substantially exceeding regulatory limits. Experimental results confirm the feasibility of cyclically reusing highly acidic wastewater (pH 0–1) in the oxidizing mixture. This approach allows for a 1.7-fold reduction in sulfuric acid and potassium dichromate consumption, without compromising the degree of graphite expansion, which remained stable in the range of 39–43 at 500 °C. |
| References |
1. Tarannum F., Danayat S., Nayal A., Muthaiah R. Large enhancement in thermal conductivity of solvent-cast expanded graphite/polyetherimide composites. Nanomaterials. 2022. Vol. 12, Iss. 11. DOI: 10.3390/ nano12111877 2. Lu A., Wang F., Liu Z., et al. Metal chloride-graphite intercalation compounds for rechargeable metal-ion batteries. Carbon Energy. 2024. Vol. 6, Iss. 10. DOI: 10.1002/cey2.600 3. Zhou G., Li Sh., Zhang X., et al. Synthesis and properties of a fire-retardant coating based on intercalated expandable graphite-modified cellulose for steel structures. Journal of Building Engineering. 2022. Vol. 51. DOI: 10.1016/j.jobe.2022.104270 4. Kassov V., Berezhnaya E., Malykhin N., Antonenko Ya., Zubenko K. Development of the protection coat for metallic structures based on the intercalated graphite compounds. Materials Science Forum. 2021. Vol. 1045. pp. 9–16. 5. Zaritovskii A. N., Kotenko E. N., Grishchuk S. V., Glazunova V. A., Volkova G. K. Graphites and graphite-like materials as microwave acceptors in the synthesis of carbon nanostructures. Izvestiya Vuzov. Khimiya i Khimicheskaya Tekhnologiya. 2025. Vol. 68, Iss. 3. pp. 64–75. 6. Chizhevsky V. B., Fadeeva N. V., Gmyzina N. V. Study of the properties and floatability of oxidized graphite. Obogashchenie Rud. 2019. No. 4. pp. 20–25. 7. Tereshchenko M. D., Yaburov M. I., Lukoyanov V. Yu., Himenko L. L. Review of the existing methods for intercaling graphite. Vestnik Permskogo Natsionalnogo Issledovatelskogo Politekhnicheskogo Universiteta. Aerokosmicheskaya Tekhnika. 2022. No. 71. pp. 174–181. 8. Gilmanshina T. R. Development of technologies for producing activated oxidized and expanded graphite. Zhurnal Sibirskogo Federalnogo Universiteta. Seriya: Tekhnika i Tekhnologii. 2012. Vol. 5, No. 6. pp. 647–657. 9. Antonova K. S., Gyrdymova A. A., Nozdryukhin A. D., Kobeleva A. R. Methods for producing intercalated graphite. Khimiya. Ekologiya. Urbanistika. 2021. Vol. 2021. pp. 172–176. 10. Sujith S. Nair, Tuhin Saha, Pranab Dey, Sambhu Bhadra. Efficiency of different methods of oxidation of graphite: a key route of graphene preparation. Graphene and 2D Materials Technologies. 2021. Vol. 6. pp. 1–11. 11. Zhang X., Sun F., Xiong G., Xu W., Ding M. A review of research progress of graphite oxidation in high temperature gas-cooled reactors. Nuclear Engineering and Design. 2024. Vol. 428. DOI: 10.1016/j.nucengdes.2024.113486 12. Murugan P., Nagarajan R. D., Shetty B. H., Govindasamy M., Sundramoorthy A. K. Recent trends in the applications of thermally expanded graphite for energy storage and sensors — a review. Nanoscale Advances. 2021. Vol. 3, Iss. 22. pp. 6294–6309. 13. Chen X., Qu Z., Liu Z., Ren G. Mechanism of oxidization of graphite to graphene oxide by the hummers method. ACS Omega. 2022. Vol. 7, Iss. 27. pp. 23503–23510. 14. Shulyak V. A., Morozov N. S., Makhina V. S., et al. Intercalation of large flake graphite with fuming nitric acid. Journal of Carbon Research. 2024. Vol. 10, Iss. 4. DOI: 10.3390/c10040108 15. Hrebelna Yu. V., Demianenko E. M., Terets M. I., et al. Synthesis and physico-chemical properties of high-quality expanded graphite. Khimiya, Fizyka ta Tekhnologiya Poverkhni. 2024. Vol. 15, No. 3. pp. 378–389. 16. Wang X., Wang G., Zhang L. Green and simple production of graphite intercalation compound used sodium bicarbonate as intercalation agent. BMC Chemistry. 2022. Vol. 16, Iss. 1. DOI: 10.1186/s13065-022-00808-y 17. Gilmanshina T. R., Dubova I. V., Koroleva G. A., Vasilyev G. V. Conditions for obtaining oxidized graphite with high thermal expansion capacity. Obogashchenie Rud. 2023. No. 5. pp. 13–17. 18. Dorovskaya A. A., Gilmanshina T. R., Dubova I. V., et al. Assessment of wastewater composition during intercalation of graphite used in metallurgy. Metallurgy: Technologies, innovations, quality. Proc. of the XXIV International scientific and practical conference. Novokuznetsk, October 15–17, 2024. pp. 260–262. |