Deep Copper Removal from High-Arsenic, Low-Copper Spent Copper Electrolyte by Gas–Liquid Sulfidation

The separation of copper and arsenic from spent copper electrolyte plays a pivotal role in electrolyte recirculation and arsenic-bearing solid hazardous waste minimization. In this study, the deep copper removal process in high arsenic and low copper spent copper electrolyte by gas–liquid sulfidation is studied. Thermodynamic analysis indicates that under strongly acidic conditions, regulating the oxidation-reduction potential enables the selective precipitation of Cu2+ as CuS while inhibiting the formation of As2S3. The influence of hydrogen sulfide excess coefficient and gas–liquid sulfidation temperature on copper and arsenic co-precipitation behavior is investigated. Under the optimal gas–liquid sulfidation conditions with the sulfide excess coefficient of 47 and gas–liquid sulfidation for 60 min at 328.15 K, the copper concentration can be reduced from 0.312 g/L to 1.25 mg/L, while arsenic co-precipitation can be effectively suppressed. The copper gas–liquid sulfidation process is chemical reaction and diffusion mix controlled with an activation energy of 33.47 kJ/mol, while arsenic sulfidation is chemical reaction controlled with an activation energy of 51.22 kJ/mol. The copper–arsenic co-precipitated sludge predominantly consists of As2S3, CuS, and Cu2S. Arsenic precipitation involves a multi-step process: As(V) is first reduced to As(III) and subsequently sulfurized. However, the majority of cupric ions are directly precipitated as sulfides, whereas a minor fraction is firstly reduced by hydrogen sulfide and subsequently precipitated. The present study clarifies the intrinsic mechanism and external regulatory factors for the gas–liquid sulfidation deep copper removal process, providing a theoretical basis for optimizing sulfidation processes to synergistically achieve valuable metal recovery and arsenic pollution control.