Stepwise recycling of Fe, Cu, Zn and Ni from real electroplating sludge via coupled acidic leaching and hydrothermal and extraction routes.

Fe/S-bearing erdite flocculant has been proven to be effective in the precipitation of heavy metals from real electroplating wastewater, with the only drawback being the huge production of sludge. This sludge was rich in Fe/S/Zn/Cu/Ni and refractory to be recycled due to the extractant pollution by free Fe and the dissolution of sulphide. Herein, a multistep separation method was developed to dissolve sulphide and separate Fe prior to Zn/Cu/Ni. Results showed that more than 92% sludge was dissolved as Fe/Zn/Cu/Ni-rich leachate after the sludge was leached by nitric acid, with the rest of the remaining undissolved elemental sulphurs. When the leachate was directly extracted by using commercially extractant Acorga M5640 and Di-(2-ethylhexyl) phosphoric acid (P204), Fe was complexed by the phosphate group of the extractant. The Fe was effectively removed prior to Zn/Cu/Ni to avoid the extractant pollution. The Fe removal efficiency was only 38.34% without sucrose, but it rose to 99.94% with the addition of 0.5 g sucrose. The added sucrose reacted with nitrate to consume H+, which showed a similar rate to the H+ release from Fe hydrolysis. Thereafter, the Fe hydrolysis was continued to remove, the Fe at a high level. The removed Fe was in the form of high-purified hematite nanorod with a diameter and length of 300-600 nm and 0.5-2.5 µm, respectively. After Fe removal, Cu/Zn/Ni was extracted by using Acorga M5640 and P204 to form three halite, including a mixture of copper sulphate hydrate and bonattite (96.8% CuSO4·H2O/CuSO4·3H2O), gunningite (97.5% ZnSO4·H2O) and dwornikite (97.9% NiSO4·H2O). The rest of the solution was neutralised by lime water to remove sulphate as gypsum (95.9% CaSO4) to meet the discharge standard of the electroplating industry. In summary, the recycling efficiency of Fe/Cu/Zn/Ni from the sludge reached 94.4%, 92.6%, 94.7% and 95.3%, which provided an alternative strategy to resource utilise Fe/S-bearing solid waste.

Resource utilization of hazardous Cr/Fe-rich sludge: synthesis of erdite flocculant to treat real electroplating wastewater.

Cr/Fe-bearing sludge is a hazardous solid waste, produced at mass production in smelting, plating and surface finishing industries. Such waste is commonly treated by chemical detoxification and safety landfill, whereas only a few Cr-rich sludge is recycled as a tanning reagent. In this study, a novel route was developed to recycle Cr/Fe-bearing sludge as erdite-bearing flocculant for wastewater treatment. Results showed that two sludges were irregular aggregates, one of which contained 1.6 wt.% Cr (short for LS) and the other contained 4.2 wt.% Cr (HS). After hydrothermal treatment, stable Cr(III)/S-bearing product was formed from the Cr(VI) reduction in the sludges. Conversely, erdite was generated in nanorod form with diameter and length of 200 nm and 0.5-1 µm from LS, respectively, whereas grew radially to 1.5-2.5 µm for HS. The two erdite-bearing products were spontaneously hydrolysed to Fe/S-bearing flocs and showed similar performance in the treatment of real electroplating effluent with 91.55, 1.94 and 0.25 mg/L of Zn, Ni and Cr, respectively. For instance, by adding 1 g/L product of LS, the release of Cr from the products did not occur, and the residual Zn, Ni and Cr in the effluent was 0.25, 0.65 and 0.17 mg/L, respectively, which met the discharge standard of the electroplating industry. With the two converted products, the residual Zn/Ni/Cr concentrations were apparently lower than those of the raw sludges and other common reagents (e.g. polymeric ferric sulphate, activated carbon and diatomite). Thus, such erdite-bearing products could serve as a flocculant and then be applied in electroplating wastewater treatment.