Characteristics of Products from the Acid Ammonium Oxalate Treatment of Manganese Minerals

Abstract

AbstractTo determine the parameters that control the attack of Mn minerals by acid ammonium oxalate in darkness (AAOD), rhodochrosite, pyrolusite, manganosite, hausmannite, and bixbyite were shaken with AAOD for 2 hr. These treatments were followed systematically by X-ray powder diffraction (XRD) and AAOD-extractable Mn analyses. About 5% of original hausmannite (surface area = 6 m2/g) remained in the solid residue of the AAOD treatment; however, if the hausmannite surface area was increased to 8 m2/g, by grinding, it completely dissolved in oxalate. Synthetic hausmannite of high surface area (37 m2/g) and rhodochrosite were completely dissolved by oxalate. Manganosite (1.5 m2/g) and especially pyrolusite (~ 1 m2/g) were more resistant to AAOD attack. Ground manganosite (4.2 m2/g) dissolved completely, but ground pyrolusite (7.2 m2/g) was only partially attacked by AAOD, inasmuch as about 25% of pyrolusite was found in the residue. An increase of the extraction time to 4 hr did not completely dissolve the ground pyrolusite.As a result of the AAOD treatment, MnC2O4 · 3H2O and MnC2O4 · 2H2O precipitated from the oxalate solutions with all starting minerals, except pyrolusite (~ 1 m2/g), which only slightly dissolved. The seldom reported MnC2O4 · 3H2O phase was identified in residues of freshly extracted samples by its strong characteristic peak at 6.5.-6.6 Å, the intensity of which gradually decreased and disappeared over several days when the sample was exposed to ambient conditions (22°C and 70% relative humidity). The trihydrate phase also collapsed after heating AAOD-treated rhodochrosite at 50°C; α-MnC2O4 · 2H2O was identified as the main crystalline product. Heating the α-MnC2O4 · 2H2O product at 115°C overnight transformed most of it to MnC2O4. The color of the oxalate-treated samples ranged from pinkish-gray to black (7.5 YR); their surface area ranged from about 20 to 30 m2/g. The degree of transformation of Mn minerals by oxalate depended on the surface area and structural characteristics of the starting materials.