Characterization of primary precipitate composition formed during co-removal of Cr(VI) with Cu(II) in synthetic wastewater

BACKGROUND, AIMS AND SCOPE: Hexavalent chromium Cr(VI)] cannot react with either carbonate or hydroxide to form chromium precipitates. However, by using a precipitation technology to treat plating wastewater containing Cr(VI), Cu(II), Ni(II) and Zn(II), approximately 78% of Cr(VI) (initial 60 mg/L) was co-removed with the precipitation of Cu(II), Ni(II) and Zn(II) (each 150 mg/L) by dosing with Na2CO3 (Sun 2003). Direct precipitation by forming Cu(II)-Cr(VI) precipitates followed by adsorption of Cr(VI) onto freshly formed Cu-precipitates was subsequently found to be the main mechanism(s) involved in Cr(VI) co-removal with Cu(II) precipitation by dosing Na2CO3 stepwise to various pH values (Sun et al. 2003). This study was. carried out to further characterize the formation of primary precipitates during the early stages of copper precipitation and simultaneous removal of Cr(VI) with Cu(II). METHODS: Test metal-solutions were prepared with industrial grade chemicals: CuCl2 x 2H2O, Na2SO4 and K2Cr2207. NaCO3 was added drop-wise to synthetic metal-solution to progressively increase pH. For each pH increment, removal of soluble metals was detected by atomic absorption spectrophotometer (AAS) and surface morphology of precipitates was analyzed by scanning electron microscope (SEM). To further characterize the formation of primary precipitates, a series of MINEQL+ thermodynamic calculations/analyses and equilibrium calculations/ analyses were conducted. RESULTS AND DISCUSSION: MINEQL+ thermodynamic calculation indicated that, for a system containing 150 mg/L Cu(II) and 60 mg/L Cr(VI) with gradual Na2CO3 dosing, if any precipitates can be formed at pH 5.0 or lower, it should be in the form of CuCrO4. Comparison tests using systems containing the same equivalent of Cu(II) plus Cr(VI) and Cu(II) plus SO4(2-) showed that the precipitation occurred at a pH of around 5.0 in the Cu(II)-Cr(VI) system and around 6.0 in the Cu(II)-SO4(2-) system. The discrepancy of the precipitation was indeed caused by the formation of Cu-Cr precipitates. The initiation of copper removal at pH around 5.0 for the Cu-Cr co-removal test was not attributable to the formation of Cu-CO3 precipitates, instead, it was most likely through the formation of insoluble Cu-Cr precipitates, such as CuCrO4 and CuCrO4 x 2Cu(OH)2. Experimental tests, equilibrium calculations, MINEQL+ thermodynamic calculations and surface morphologies for systems using higher concentrations of Cu(II) and Cr(VI) further verified the most probable composition of primary precipitates is copper-chromate. CONCLUSION: In the Cu-Cr co-removal test with Na2O3 dosing to increase pH and induce metal precipitation, copper-chromate precipitates are the primary precipitates produced and contribute to the initial simultaneous removal of copper and chromium.