Determination of Rhenium in Sediments of the Volga Shale Basin by the X-ray Method with Preliminary Electrochemical Concentration

Abstract

The shales of the Kotsyubinsky deposit in the Volga basin are promising as an alternative source of a rare and strategically important metal --- rhenium. To assess the feasibility of their processing, data on the quantitative content of rhenium is required, which requires the development of a relatively fast and reliable analysis method. In the article, the determination of rhenium is carried out by the X-ray fluorescence method with preliminary electrochemical concentration of the metal by its deposition on the cathode after preliminary opening of the sample. The use of X-ray fluorescence analysis makes it possible to determine rhenium against the background of a tenfold excess of molybdenum and other metals. The rhenium content in clay shales was found to be 0.68--0.20 g/t, which makes their processing economically justified. Rhenium was not found in black shales. The results of analysis using the X-ray fluorescence method with preliminary electrochemical concentration are comparable to those obtained by the ICP-MS method. At the same time, analysis by the ICP-OES method leads to underestimated results on the rhenium content, which is apparently due to its refractoriness. Comparing two methods that lead to reliable results (ICP-MS and electrochemical concentration + X-ray fluorescence analysis), it can be noted that the proposed method does not require expensive equipment and can be implemented in the field

The work was carried out within the framework of the State Assignment (project no. FSFN-2025-0013 (0705-2025-0013))

Please cite this article in English as:

Shakurov R.I., Kuznetsov V.V., Filatova E.A., et al. Determination of rhenium in sediments of the Volga Shale basin by the X-ray method with preliminary electrochemical concentration. Herald of the Bauman Moscow State Technical University, Series Natural Sciences, 2025, no. 6 (123), pp. 120--132 (in Russ.). EDN: ZEHRKE

References

[1] Sporykhina L.V., Bykhovskiy L.Z., Chernova A.D. The state and usage of Russian mineral resource base of scattered elements. Mineralnye resursy Rossii. Ekonomika i upravlenie [Mineral Recourses of Russia. Economics and Management], 2020, no. 2, pp. 23--34 (in Russ.). EDN: BZCFFX

[2] Bortnikov N.S., Volkov A.V., Galyamov A.L., et al. Mineral resources of high-tech metals in Russia: state of the art and outlook. Geol. Ore Deposits, 2016, vol. 58, no. 2, pp. 83--103. DOI: https://doi.org/10.1134/S1075701516020021

[3] Rahman M., Davey K., Qiao Sh.-Zh. Advent of 2D rhenium disulfide (ReS₂): fundamentals to applications. Adv. Funct. Mater., 2017, vol. 27, no. 10, art. 1606129. DOI: http://dx.doi.org/10.1002/adfm.201606129

[4] Biloen P., Helle J.N., Verbeek H., et al. The role of rhenium and sulfur in platinum-based hydrocarbon-conversion catalysts. J. Catal., 1980, vol. 63, no. 1, pp. 112--118. DOI: https://doi.org/10.1016/0021-9517(80)90064-0

[5] Gothe M.L., Silva K.L.C., Adolfo L., et al. Rhenium --- a tuneable player in tailored hydrogenation catalysis. Eur. J. Inorg. Chem., 2021, vol. 2021, no. 39, pp. 4043--4065. DOI: https://doi.org/10.1002/ejic.202100459

[6] Broadbent H.S., Bartley W.J. Rhenium catalysts. VII. Rhenium (VI) oxide. J. Org. Chem., 1963, vol. 28, no. 9, pp. 2345--2347.

[7] Kessler V.G., Seisenbaeva G.A. Rhenium nanochemistry for catalyst preparation. Minerals, 2012, vol. 2, iss. 3, pp. 244--257. DOI: https://doi.org/10.3390/min2030244

[8] Korzhinsky M., Tkachenko S., Shmulovich K., et al. Native AI and Si formation. Nature, 1995, vol. 375, art. 544. DOI: https://doi.org/10.1038/375544a0

[9] Balikhin A.V., Barkovskaya O.E. Perspectives of rhenium recovery from volcanic gases. review. Kompleksnoe ispolzovanie mineralnogo syrya [Complex Use of Mineral Resources], 2017, no. 3, pp. 16--23 (in Russ.). EDN: YYAEKT

[10] Shakurov R.I., Kuznetsov V.V., Filatova E.A., et al. Determination of rhenium in igneous rock by Х-ray fluorescence spectrometry with prior electrochemical concentration. Tsvetnye metally, 2021, no. 10, pp. 43--49 (in Russ.). DOI: https://doi.org/110.17580/tsm.2021.10.06

[11] Samoylov A.G., Engalychev S.Yu., Zozyryaev N.Yu., et al. Rhenium potential of the Upper Jurassic oil shale in the central part of the Volga Shale basin. Regionalnaya geologiya i metallogeniya [Regional Geology and Metallogeny], 2018, no. 75, pp. 67--77 (in Russ.).

[12] Samoylov A.G., Zozyrev N.Yu., Engalychev S.Yu., et al. Rhenium in the Volzhsky stage deposits of the Volga Shale basin central part. Izvestiya Saratovskogo universiteta. Novaya seriya. Ser. Nauki o Zemle [Izvestiya of Saratov University. Earth Sciences], 2017, vol. 17, no. 1, pp. 58--61 (in Russ.). DOI: https://doi.org/10.18500/1819-7663-2017-17-1-58-61

[13] Malinovsky D., Rodushkin I., Axelsson M.D., et al. Determination of rhenium and osmium concentrations in molybdenite using laser ablation double focusing sector field ICP-MS. J. Geochem. Explor., 2004, vol. 81, iss. 1-3, pp. 71--79. DOI: https://doi.org/10.1016/j.gexplo.2003.08.003

[14] Mank A.J.G., Mason P.R.D. A critical assessment of laser ablation ICP-MS as an analytical tool for depth analysis in silica-based glass samples. J. Anal. At. Spectrom., 1999, vol. 14, iss. 8, pp. 1143--1153. DOI: https://doi.org/10.1039/A903304A

[15] Solt M.W., Wahlberg J.S., Myers A.T. Determination of rhenium in molybdenite by X-ray fluorescence: a combined chemical-spectrometric technique. Talanta, 1969, vol. 16, iss. 1, pp. 37--43. DOI: https://doi.org/10.1016/0039-9140(69)80238-9

[16] Peddy R.V.C., Gopalakrishnan K., Koshy V.J., et al. Determination of the platinum, rhenium and chlorine contents of alumina-based catalysts by X-ray fluorescence spectrometry. Analyst, 1991, vol. 116, iss. 8, pp. 847--850. DOI: https://doi.org/10.1039/AN9911600847

[17] Kolpakova N.A., Buinovskii A.S., Mel’nikova I.A. Determination of rhenium in gold-containing ores by X-ray fluorescence spectrometry. J. Anal. Chem., 2009, vol. 64, no. 2, pp. 144--148. DOI: https://doi.org/10.1134/S1061934809020099

[18] Zawisza B., Sitko R. Determination of Te, Bi, Ni, Sb and Au by X-ray fluorescence spectrometry following electroenrichment on a copper cathode. Spectrochimica Acta B, 2007, vol. 62, iss. 10, pp. 1147--1152. DOI: https://doi.org/10.1016/j.sab.2007.07.004

[19] Kuznetsov V.V., Gamburg Yu.D., Zhulikov V.V., et al. Electrodeposited NiMo, CoMo, ReNi, and electroless NiReP alloys as cathode materials for hydrogen evolution reaction. Electrochimica Acta, 2020, vol. 354, art. 136610. DOI: https://doi.org/10.1016/j.electacta.2020.136610

[20] Eliseeva E.A., Berezina S.L., Boldyrev V.S., et al. Influence of the morphology of Co₂O₃ particles on the dissolution kinetics in electrolytes. Tsvetnye metally, 2020, no. 11, pp. 14--18 (in Russ.). DOI: https://doi.org/10.17580/tsm.2020.11.02