Electrochemical recovery of nickel from nickel sulfamate plating effluents

Abstract

Nickel sulfamate solutions are widely used for industrial nickel plating, when electrodeposits with low stress are required. Partial decomposition of sulfamate with decreasing pH below ca. 2.5 degrades the properties of nickel electrodeposits, decreases the charge yield and results in spent solutions, from which nickel must be recovered before they could be discharged to sewers. Results are reported of charge yields for nickel recovery from an industrial sulfamate effluent, using an electrochemical reactor operated at constant current in batch-recycle mode and incorporating a nickel mesh cathode, a Ti/Ta2O5–IrO2 mesh anode and a cation-permeable membrane to prevent anodic oxidation of sulfamate. A micro-kinetic model was developed, treating the processes of nickel(II) and proton reduction in sulfamate solutions as two multi-step reactions involving adsorbed intermediates, Ni ads I and Hads, respectively. The unknown kinetic parameters were obtained using gPROMS software by iterative fitting of the model to experimental data obtained over a range of nickel(II) concentrations and bulk solution pH, enabling evaluation of nickel(II) reduction charge yields as a function of nickel(II) concentration, bulk pH and electrode potential. A model combining the micro-kinetic equations with mass and charge balances on the reactor was used to determine the control parameters for electrochemical recovery of elemental metal from nickel(II) in batch-recycle mode. It was determined experimentally that a decrease in catholyte pH to values below ca. 2.5 resulted in a decrease in nickel(II) reduction charge yields to values below 0.9. The decrease in catholyte pH, caused by the flux of protons from the anolyte where they were generated via anodic oxygen evolution, was obviated by continuous addition of NaOH at a rate determined by the model, permitting nickel(II) recovery with an average charge yield of 0.94.