From Ferrous Sulfate Waste to Fertilizer and Metal Powder: Thermodynamics, Process Integration, and Circular Economy Opportunities for Dual-Product Recovery

Ferrous sulfate is produced in large quantities by hydrometallurgical operations, steel pickling, titanium dioxide manufacturing, acid regeneration circuits, and several wastewater treatment processes. Despite numerous utilization routes, significant quantities remain underutilized or require costly disposal and stabilization. This review critically evaluates an integrated process concept for converting ferrous sulfate solutions into two commercially valuable products: ammonium sulfate fertilizer and powder-metallurgy iron. The first stage involves urea-assisted conversion of dissolved ferrous sulfate into ammonium sulfate and ferrous carbonate. Thermodynamic assessments indicate strongly favorable reaction equilibria across typical process temperatures, and the low solubility of ferrous carbonate promotes efficient iron recovery from solution. The second stage involves thermal decomposition and hydrogen reduction of ferrous carbonate to produce metallic iron powder. Available thermodynamic and kinetic studies indicate that hydrogen reduction becomes increasingly favorable at moderate temperatures and may provide a low-carbon alternative to conventional iron powder production routes. The review compares existing ferrous sulfate management strategies, discusses the chemistry of urea hydrolysis and siderite precipitation, evaluates thermodynamic and process limitations, and examines industrial opportunities associated with fertilizer and powder metallurgy markets. Particular attention is given to reaction feasibility, process integration, product quality requirements, and scale-up challenges. The analysis suggests that the proposed dual-product pathway is a promising circular economy strategy that can reduce environmental liabilities while generating two independent revenue streams from a widely available industrial residue.