Recovery of valuable and toxic metals from crystalline-Si modules
Valuable and toxic metals including Ag, Pb, Sn and Cu can be recovered from end-of-life Si solar modules. This study presents the recovery of Ag, Pb, Sn and Cu from a simulated leach solution of crystalline-Si modules. 11.4% HNO3 is used as the leach solution. Ag, Pb, Sn and Cu pellets are dissolved in the solution to simulate the metals from front contacts and soldered wires in Si modules. Sn precipitates in the solution as SnO2, which can be separated by filtration or sedimentation. Voltammetry reveals the reduction potentials for Ag and Cu. It is demonstrated that 3-electrode sequential electrowinning can extract Ag and Cu one by one from the solution. The recovery rates of Ag and Cu are 74% and 83%, respectively. Toxic Pb is deposited on the anode as PbO2 during Cu recovery. The purity of the extracted metals is above 99%.
Leaching and electrochemical recovery of copper, lead and tin from scrap printed circuit boards
The recovery of copper, lead and tin from scrap printed circuit boards (PCBs) has been achieved using a combination of leaching, electrochemical ion exchange and electrodeposition. A simple aqueous nitric acid stripping solution, with the concentration range of 1–6 mol dm−3, has demonstrated the potential for selective extraction of copper and lead from the PCBs. Precipitation of tin as H2SnO3 (metastannic acid) occurred at acid concentrations above 4 mol dm−3. Preliminary galvanostatic electrolysis from simulated leaching solutions has investigated the feasibility of electrodeposition of copper and lead at different concentrations of HNO3. Cathodic lead deposition, particularly at high electrolyte conditions, resulted in poor current efficiency. This was mainly due to dentritic metal formation and subsequent re-dissolution. An alternative method investigated for recovering the metal values was the simultaneous electrodeposition of copper at the cathode and lead dioxide at the anode. Electrohydrolysis for acid and base regeneration from the spent nitric acid electrolyte has also been investigated. 
 
© 2002 Society of Chemical Industry
Autocatalytic dissolution of Pb in HNO3
The reaction between Pb and HNO3 has been investigated using the thermometric technique. Weight-loss measurements on the reaction were also obtained. As the HNO3 concentration is increased from 5×10−2 to 4mol l−1, the corrosion rate increases. This is shown thermometrically by a substantial increase in the maximum temperature attained, Tm, as well as a decrease in the time, t, required for reaching Tm. Dissolution of Pb in HNO3 is proposed to take place according to an autocatalytic mechanism. Passivation sets were detected in solutions ≥11 mol l−1 HNO3. A parallel indication between the thermometric technique and weight-loss measurements was obtained. The rate-determining step of the autocatalytic process involves HNO2 in dissolution of Pb in HNO3. This is supported by the results of addition of hydrazine to the solution. This additive raises the maximum measured temperature, without affecting the corresponding time necessary to reach it. The effect of addition of NaNO2, NaNO3, NaCl, Na2SO4, NaH2PO4 and NaClO4 on the reaction number, RN, of Pb in 4 mol l−1 HNO3 was examined. Only NaNO2 accelerates the dissolution reaction while the other salts show as inhibition effect. It was found that these additives inhibit dissolution due to the displacement of some cathodic depolarizing components, as NO2, from the active sites on the metal surface. The effect of addition of HCl, H2SO4, HClO4 and H3PO4 on the reaction number, RN, of Pb in 4 mol l−1 HNO3 was also investigated. The observed acceleration and retardation of the dissolution of Pb was found to be dependent on both the concentration and nature of anions of the extra acids added.