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9, 2003, pp. 1515!1517. Original Russian Text Copyright + 2003 by Panov, Gyul’khandan’yan, Pakshver.
ENVIRONMENTAL PROBLEMS ÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍ OF CHEMISTRY AND TECHNOLOGY
Regeneration of Exhausted Chrome Tanning Solutions from Leather Production as a Method Preventing Environmental Pollution with Chromium
V. P. Panov, E. M. Gyul’khandan’yan, and A. S. Pakshver
St. Petersburg State University of Technology and Design, St. Petersburg, Russia
Received February 5, 2003
Abstract Photochemical degradation of organic impurities in exhausted chrome tanning solutions is studied. A method for regeneration of these solutions is proposed, allowing reduction of chromium loss with wastewater.
Leather production in the volume of water consumption and, correspondingly, in the volume of water supply ranks first among the branches of light industry. Since tanneries are arranged mostly near water basins used as sources of drinking and industrial water, the problem of preventing pollution of these basins with leather production discharges is very topical. After tanning of hide (skin after removal of the hair side), 22 to 35% of the chrome tanning agent remains in exhausted tanning solutions, which corresponds to a residual chromium concentration of 338 g l31 (recalculated to Cr2O3). According to published data, more than 25 000 t of Cr(III) is discharged to the environment with leather production wastes all over the world, whereas the discharge from metallurgical works is about 1500 t [13 4]. One of the promising ways to reduce the discharge of chrome tanning agents and, correspondingly, the Cr(III) consumption is recycling of chrome tanning solutions. Recovery of chromium(III) from exhausted tanning solutions by precipitation requires large amounts of alkaline reagents and sulfuric acid for dissolution. The resulting Cr(III) hydroxide sludge is poorly settled and filtered, being contaminated with residual proteins. Presently growing efforts are devoted to developing methods of waste treatment without phase transfer, for example, ultrafiltration on various membranes allowing separation of solutes, fats, and protein residues . However, to provide reasonable service life for the membranes, the solutions should be pretreated to thoroughly remove suspended materials prior to ultra-
filtration. Wide application of the method is also limited by high cost and batch process mode. The problem of recycling of tanning solutions may be solved only after solving the problem of removal of organic impurities from them, for example, by degradation. Recent studies demonstrate high efficiency of liquid-phase oxidation of organic impurities under the combined effect of active oxygen, hydroxy radicals formed in UV treatment of the solutions after addition of hydrogen peroxide, and ozone. In this case, degradation of organic acids, particularly, amino acids proceeds more rapidly by two orders of magnitude than with the use of an oxidant only [6, 7]. There is no information in the literature on the effect of UV irradiation on Cr(III) complexes with amino acids. It may be expected that photolysis will break down such complexes, providing mineralization of the amino acids. As a result, the chrome tanning agent will be regenerated. In this work we studied photochemical degradation of organic impurities with simulated and actual exhausted tanning solutions. The process was monitored by the chemical oxygen demand (COD) using the standard procedure. The amino acid concentration was determined by paper partition chromatography using water3acetone3n-propanol3acetic acid (1 : 2 : 1.5 : 0.2) as a mobile phase and polarography. Experiments on determination of COD of solutions containing such amino acids as glycine, b-alanine, DL-proline, and arginine showed that, under the COD determination conditions (boiling in 18 N sulfuric acid for 2 h), the degree of mineralization of organic impurities ranges
1070-4272/03/7609-1476$25.00 C 2003 MAIK