Coupling of resorcinols in retorted kukersite semi-coke; pp. 75–85Full article in PDF format
| doi: 10.3176/proc.2014.1.10
Coupling products of three major phenols appearing in the waste streams of shale oil production from kukersite oil shale were isolated and analysed using high-resolution mass spectrometry (HRMS). The pattern of water-soluble phenols in retorted kukersite semi-coke leachate changes quickly during weathering. The amount of phenols decreases, but the rate of disappearance is dissimilar for different constituents. Oxidation experiments with three major phenols (resorcinol, 5-methyl resorcinol, and 2,5-dimethylresorcinol) and their mixtures in pairs were performed in a reaction medium similar to semi-coke leachate. Reaction products were detected using silica gel thin layer chromatography (TLC) and isolated for further analysis by silica gel dry-column chromatography. The composition of primary reaction products was confirmed by nuclear magnetic resonance (NMR) spectroscopy. The primary coupling products of the studied resorcinols included the corresponding dimeric mono- and diquinones. Further coupling brought about the formation of water-insoluble products, which is the reason for the disappearance of resorcinols from the leachate.
1. Tiikma, L., Mölder, L., and Tamvelius, H. Resources of water-soluble alkylresorcinols in the oil fractions and retort water formed by processing oil shale in generators of high unit capacity. Oil Shale, 1991, 8, 350–354.
2. Koel, M. and Bunger, J. Overview of program on US–Estonian science and technology cooperation on oil shale research and utilization (strategic importance of oil shale studies for Estonia and USA). Oil Shale, 2005, 22, 65–79.
3. Kahru, A., Maloverjan, A., Sillak, H., and Põllumaa, L. The toxicity and fate of phenolic pollutants in the contaminated soils associated with the oil shale industry. Environ. Sci. Pollut. Res., 2002, 9, 27–33.
4. Habicht, J. and Mäeorg, U. Retorted oil shale – a true synthesis laboratory. In 30th Estonian Chemistry Days, Abstracts of Scientific Conference. Tartu, 2007, 29.
5. Yamamura, S. Oxidation of phenols. In The Chemistry of Phenols (Rappoport, Z., ed.). John Wiley & Sons Ltd., 2003, 1153–1346.
6. Kirso, U., Gubergrits, M., and Kuiv, K. Oxidizability of phenols contained in tar waters from tunnel kilns and a unit with a solid heat carrier. Slantsevaya Khimiya, 1966, 4, 19–22 (in Russian).
7. Kirso, U., Kuiv, K., and Gubergrits, M. Kinetics of phenol and m-cresol oxidation by molecular oxygen in an aqueous medium. Zhurnal Prikladnoj Khimii, 1967, 40, 1583–1589 (in Russian).
8. Kirso, U., Gubergrits, M., and Kuiv, K. Kinetics of the oxidation of substituted monohydric phenols by molecular oxygen in an aqueous medium. Zhurnal Prikladnoj Khimii, 1968, 41, 1257–1261 (in Russian).
9. Trapido, M. and Gubergrits, M. Oxidation of resorcinols in water. ENSV TA Toim. Keemia, 1980, 29, 103–108.
10. Mamedov, A., Aslanova, T., Alekperov, A., and Alieva, N. Features and products of oxidation of 1,3-benzendiol by oxygen in an alkaline medium. Azerbajdzhanskii Khimicheskii Zhurnal, 2004, 59–63 (in Russian).
11. Preis, S., Terentyeva, Y., and Rozkov, A. Photocatalytic oxidation of phenolic compounds in wastewater from oil shale treatment. Water Sci. Technol., 1997, 35, 165–174.
12. Kamenev, I., Munter, R., Pikkov, L., and Kekisheva, L. Wastewater treatment in oil shale chemical industry. Oil Shale, 2003, 20, 443–457.
13. Christjanson, P., Köösel, A., and Suurpere, A. Evaluation of condensation rate of methylolphenols. Oil Shale, 1998, 15, 374–383.
14. Christjanson, P., Köösel, A., and Suurpere, A. Condensation of methylolphenols. Oil Shale, 1999, 16, 369–376.
15. Chrisjanson, P., Pehk, T., Siimer, K., and Paju, J. Structure of polycondensates from hydroxymethylphenols. J. Appl. Polymer Sci., 2008, 107, 1226–1234.
16. Musso, H. and Rathjen, C. Die Autoxydationsprodukte des 2.5-Dimethyl-resorcins in Ammoniak und Kalilauge. Chem. Ber., 1963, 96, 1593–1609.
17. Musso, H., Gizycki, U., Krämer, H., and Döpp, H. Über den Autoxydations-mechanismus bei Resorcinderivaten. Chem. Ber., 1965, 98, 3952–3963.
18. Musso, H. Über Phenol-Oxidationen. Angew. Chem., 1963, 75, 965–977.
19. Eesti Standard EVS-EN 12457-1:2002. Characterisation of waste – Leaching – Compliance test for leaching of granular waste materials and sludges – Part 1: One stage batch test at a liquid to solid ratio of 2 l/kg for materials with particle size below 4 mm (without or with size reduction). Eesti Standardikeskus, 2002.
20. Harvey, T., Matheson, T., and Pratt, C. Chemical class separation of organics in shale oil by thin-layer chromatography. Anal. Chem., 1984, 56, 1277–1281.
21. Fisher, W., Bund, O., and Hauck, H. Thin-layer chromatographic analysis of phenols on TLC aluminium sheets RP-18 F254s
. Frensius J. Anal. Chem.
, 1996, 354
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