Co-removal of hexavalent chromium during copper precipitation

In our recent study using the nucleated precipitation technology to treat plating wastewater, it was found that about one half of hexavalent chromium was co-removed with copper, nickel and zinc. Since hexavalent chromium could not react with either hydroxide or carbonate to from precipitates, this study was undertaken to evaluate the mechanism(s) involved in the chromium co-removal. Batch tests were conducted with synthetic solutions containing either only copper or both copper and hexavalent chromium. Metal precipitation was induced by adding Na2CO3 to different pH, and the quantitative removal of copper and chromium was determined. Besides, the [Cr]/[Cu] molar ratio of produced precipitates were also assessed in conjunction with the EDAX analysis to determine their compositions. Experimental results indicate that for pure copper solution, precipitation begins at pH 6.0, and completes at pH 7.0. The chemical forms of the precipitates are copper carbonates [CuCO3.Cu(OH)2 and CuCO3.2Cu(OH)2]. On the other hand, in a bi-metal solution of copper plus chromium, precipitation of copper begins at about pH 5.0, and copper precipitation is always accompanied by some chromium removal. From the removal stoichiometry of the two metals, it is found that at low pH, the co-removal is a result of “co-precipitation” which results in the formation of CuCrO4 crystallites. Once such crystallites are formed, they provide a heterogeneous environment which enhances an early formation of copper carbonate at a lower pH (below 5.5). It is further found that once copper carbonate precipitates are produced, the remaining soluble will precipitate in such form, and at this stage further removal of copper is no longer accompanied by additional chromium removal. The test data also reflect that the produced copper carbonates are positively charged, as verified by zeta potential measurement, at pH below 7.5. Thus they are able to adsorb some anionic chromium (existing as chromate) through electrostatic attraction and/or inorganic ligand exchange. At pH of 6 to 10, the extent of adsorption decreases with increasing pH, and the adsorption capacity seems to coincide with the progressive reduction of positive zeta potentials of the precipitated particles.