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缩合单宁凝胶中氧化还原作用对六价铬的吸附机制

Adsorption mechanism of hexavalent chromium by redox within condensed-tannin gel.

作者信息

Nakano Y, Takeshita K, Tsutsumi T

机构信息

Interdisciplinary Graduate School of Science and Engineering, Tokyo Institute of Technology, Nagatsuta, Midori-ku, Yokohama 226-8502, Japan.

出版信息

Water Res. 2001 Feb;35(2):496-500. doi: 10.1016/s0043-1354(00)00279-7.

DOI:10.1016/s0043-1354(00)00279-7
PMID:11229004
Abstract

We have proposed a new recovery system of hexavalent chromium Cr(VI) that is of great toxicity utilizing condensed-tannin gels derived from a natural polymer with many polyhydroxyphenyl groups. The adsorption mechanism of Cr(VI) to the tannin molecules was clarified. The adsorption mechanism consists of four reaction steps; the esterification of chromate with tannin molecules, the reduction of Cr(VI) to trivalent chromium Cr(III), the formation of carboxyl group by the oxidation of tannin molecules and the ion exchange of the reduced Cr(III) with the carboxyl and hydroxyl groups. It was found in this recovery system that a large amount of proton was consumed accompanied with the reduction of Cr(VI) so that the acidic solution containing Cr(VI) was transferred automatically to neutral one by choosing an appropriate initial pH. The carboxyl group which was created by the oxidation of tannin molecules parallel to the reduction of Cr(VI) to Cr(III) contributed to an increase in the ion-exchange sites of the reduced Cr(III). The maximum adsorption capacity of Cr(VI) reached 287 mg Cr/g dry tannin gel under the conditions of 0.77 water content of tannin gel and the initial pH = 2. This adsorption capacity was five to ten times higher than that obtained by the ion exchange between ordinary Cr(III) and tannin molecules for the tannin gels prepared under similar conditions. The system proposed here will provide an important information on a zero-emission-oriented process because it has such advantages as higher adsorption capacity of chromium and lower volume of secondary wastes compared with conventional process.

摘要

我们提出了一种新的六价铬(Cr(VI))回收系统,Cr(VI)具有高毒性,该系统利用了源自具有多个多羟基苯基的天然聚合物的缩合单宁凝胶。阐明了Cr(VI)对单宁分子的吸附机制。该吸附机制包括四个反应步骤:铬酸盐与单宁分子的酯化反应、Cr(VI)还原为三价铬(Cr(III))、单宁分子氧化形成羧基以及还原后的Cr(III)与羧基和羟基的离子交换。在该回收系统中发现,伴随着Cr(VI)的还原会消耗大量质子,因此通过选择合适的初始pH值,含Cr(VI)的酸性溶液会自动转变为中性溶液。与Cr(VI)还原为Cr(III)同时发生的单宁分子氧化所产生的羧基,有助于增加还原后的Cr(III)的离子交换位点。在单宁凝胶含水量为0.77且初始pH = 2的条件下,Cr(VI)的最大吸附容量达到287 mg Cr/g干单宁凝胶。该吸附容量比在类似条件下制备的单宁凝胶通过普通Cr(III)与单宁分子之间的离子交换所获得的吸附容量高五到十倍。这里提出的系统将为零排放导向的工艺提供重要信息,因为与传统工艺相比,它具有铬吸附容量更高和二次废物量更低等优点。

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