Processing of ferromanganese fumes into high-purity manganese sulphate monohydrate

J Air Waste Manag Assoc. 2020 Sep;70(9):944-955. doi: 10.1080/10962247.2020.1783027.

Abstract

A novel process for recovering manganese (Mn) values from two types of ferromanganese (FeMn) fumes (wastes from smelters) was developed incorporating several stages of leaching, roasting, and precipitation. Fumes containing high K (as K2O) were first leached in water at ambient conditions to recover K, purified to remove metal impurities, and precipitated as 99.9% pure K2SO4. The residues containing Mn and remaining impurities were then leached in sulfuric acid at 80 °C using oxalic acid as reductant yielding Mn sulphate liquors. The leach liquors were then purified to remove Fe at 95°C as jarosite at pH 2.8 and Fe(III) hydroxides at pH 5.5. Base and transition metal impurities were removed as sulfides. K, Na, Ca, and Mg were separated from Mn in a novel step based on precipitation of Mn hydroxide from the Mn sulphate liquors. Subsequent redissolution of Mn hydroxide in sulfuric acid under reducing conditions using oxalic acid produced a high purity Mn sulphate liquors containing <5 ppm of these impurities. After evaporation by boiling manganese sulphate monohydrate (MSM) was crystallized, achieving purity >99.5%. Another fume containing oil contaminants having low K was subjected to sulfation roasting to produce Mn sulphate. The calcine was water leached to produce Mn sulfate liquors and treated in a similar process to make high purity MSM. Novelty aspects of the proposed process include the recovery of K as a by-product and separation of Mn2+ from other impurities by its selective precipitation to produce a high purity Mn sulphate solution for MSM recovery. Implications: Ferro-manganese smelters discharge wastes (fumes) that are collected by bag filters or electrostatic precipitators and then store them on the ground with coverage to prevent their dispersion into the surrounding atmosphere. The work presented propose a process to reprocess these wastes into high purity manganese sulphate monohydrate (MSM). Processing of wastes containing high potassium as KOH also yields high purity potassium sulfate used as fertilizers. Some smelters spray oil onto the fume dumps to prevent material being blown onto the surrounding area. The oil-contaminated fumes have to be first roasted to burn off the oil, before they can be processed. The process developed therefore converts a hazardous waste into high purity MSM and potassium sulphate used in many applications.

MeSH terms

  • Air Pollutants / chemistry*
  • Industrial Waste
  • Iron / chemistry*
  • Manganese / chemistry*
  • Manganese Compounds / chemistry*
  • Metallurgy
  • Recycling
  • Sulfates / chemistry*

Substances

  • Air Pollutants
  • Industrial Waste
  • Manganese Compounds
  • Sulfates
  • ferro-manganese alloy
  • potassium sulfate
  • Manganese
  • Iron
  • manganese sulfate