Preparation of high-purity γ-Mn 3 O 4 by decomposing MnCO 3 from low-grade rhodochrosite ore

Abstract

High-purity Mn₃O₄ was prepared from low-grade rhodochrosite ore (LGRO). The Mn recovery efficiency was more than 97% with the blended precipitant of Na₂CO₃ and NH₄HCO₃ (1∶1 mol mol⁻¹). The total Mn content (TMC) of product increased with increase of decomposition time and temperature. The quantitative relationship between TMC and decomposition time as well as decompositions temperature could be fitted by empirical formulae. When decomposing MnCO₃ at 1323 K for 120 min, the TMC of Mn₃O₄ could reach 72·01%, which was larger than that of the premium grade of mangano-manganic oxide for preparing soft magnetic ferrites. The product was investigated by XRD, FTIR and SEM. SEM images revealed that the product consisted of small and uniform particles with smooth surface and good dispersion. Through XRD, FTIR and determination of TMC, the as-prepared product was confirmed to be high-purity γ-Mn₃O₄. The ionic distributions were formulated as [Mn²⁺][Mn²⁺ _0·3024Mn³⁺ _0·2937 Mn⁴⁺ _0·3786 □_0·0254]₂O₄.

Keywords

LGRO Thermal decomposition

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References

Ahmed

KAM

, Hong

, Wu

and Huang

. 2011. Hydrothermal preparation of nanostructured manganese oxides (MnO_x) and their electrochemical and photocatalytic properties, Chem. Eng. J., 172, 531–539.

Anilkumar

and Ravi

. 2005. Synthesis of nanocrystalline Mn₃O₄ at 100°C, Mater. Res. Bull., 40, 605–609.

Apte

, Naik

, Sonawane

, Kale

, Pavaskar

, Mandale

and Das

. 2006. Nanosize Mn₃O₄ (Hausmannite) by microwave irradiation method, Mater. Res. Bull., 41, 647–654.

Dubal

, Dhawale

, Salunkhe

, Fulari

and Lokhande

. 2010. Chemical synthesis and characterization of Mn₃O₄ thin films for supercapacitor application, J. Alloys Compd., 497, 166–170.

Gopalakrishnan

, Bagkar

, Ganguly

and Kulshreshtha

. 2005. Synthesis of superparamagnetic Mn₃O₄ nanocrystallites by ultrasonic irradiation, J. Cryst. Growth, 280, 436–441.

Hare

and Fernald

. 1984. Effect of prime pigment on metal primer performance, Mod. Paint Coat., 74, 40–46.

Hassouna

, Ouassim

, Faouzi

and Fathi

. 2012. Mn₃O₄ nanoparticles: synthesis, characterization, and dielectric properties, ISRN Spectrosc., 10, 1–8.

, Zhou

and Peng

. 2007. A study of the preparation of manganese carbonate with high purity by the use of industry manganese, China Manganese Ind., 25, (2), 14–17.

Huang

, Yi

, Peng

and Jiang

. 2012. Effects of roast temperature on properties of oxide pellets and its gas-based direct reduction, J. Cent. South Univ. (Sci. Technol.), 43, (8), 2889–2895.

10.

Laarj

, Kacim

and Gillot

. 1996. Cationic distribution and oxidation mechanism of trivalent manganese ions in submicrometer Mn_xCoFe_2-xO₄ spinel ferrites, J. Solid State Chem., 125, 67–74.

11.

, Qi

, Peng

, Liu

and Zhou

. 2010. Kinetics of chromite ore in oxidation roasting process, Chin. J. Nonferrous Met., 20, (9), 1821–1828.

12.

, Zhou

, Gao

, Miao

, Zhang

and Xu

. 2009. Synthesis of Mn₃O₄ nanoparticles and their catalytic applications in hydrocarbon oxidation, Powder Technol., 190, 324–326.

13.

Liu

, Jin

and Wang

. 2001. Kinetics of formation reaction of Zn₂SiO₄ during roasting high silica-containing sphalerite concentrate, Chin. J. Nonferrous Met., 11, (3), 514–517.

14.

Peng

, Xu

and Chen

. 2010. Preparation and characterization of high specific surface area Mn₃O₄ from electrolytic manganese residue, Cent. Eur. J. Chem., 8, 1059–1068.

15.

Rohani Bastami

and Entezari

. 2012. A novel approach for the synthesis of superparamagnetic Mn₃O₄ nanocrystals by ultrasonic bath, Ultrason. Sonochem., 19, 560–569.

16.

Shen

, Ji

, Miao

, Yang

and Chen

. 2011. Hydrothermal synthesis of MnCO₃ nanorods and their thermal transformation into Mn₂O₃ and Mn₃O₄ nanorods with single crystalline structure, J. Alloys Compd., 509, 5672–5676.

17.

Silva

, Almeida

, Angela

and Ciminelli

VST

. 2012. Preparation and application of a magnetic composite (Mn₃O₄/Fe₃O₄) for removal of As (III) from aqueous solutions, Mater. Res., 15, (3), 403–408.

18.

, Qu

, Wen

, Tong

and Li

. 2008. Morphology control in preparation process of spherical manganese carbonate particles, Chin. J. Process Eng., 8, (2), 280–284.

19.

Wang

and Ao

. 2008. Synthesis and optical properties of Mn₃O₄ nanowire by decomposing MnCO₃ nanoparticles in flux, Cryst. Growth Des., 8, (1), 358–362.

20.

Xie

, Xu

, Peng

, Chen

and Zhao

. 2013. Leaching process and kinetics of manganese from low-grade manganese ore, Chin. J. Geochem., 32, 222–226.

21.

Xiong

, Huang

and Liu

. 2000. Study on determination of Mn²⁺, Mn³⁺, Mn⁴⁺and their distribution in tetragonal spinel-type Mn₃O₄, Chin. J. Anal. Lab., 19, (5), 68–70.

22.

and Huang

. 2004. Valence state of manganese in mangano-manganic oxide and analytical method for its paste sample, Min. Metall. Eng, 24, (1), 58–6063.

23.

Zhang

, Yang

, Liu

, Tang

, Han

and Chen

. 2004. Controlled synthesis of Mn₃O₄ nanocrystallites, MnOOH nanorods by a solvothermal method, J. Cryst. Growth, 263, 394–399.

24.

Zhang

, Qiao

and Hu

. 2004. Preparation of Mn₃O₄ nanocrystallites by low-temperature solvothermal treatment of γ-MnOOH nanowires, J. Solid State Chem., 177, 4093–4097.

25.

Zhao

, Xu

and Xie

. 2013. Preparation of chemical manganese dioxide from low-grade rhodochrosite ore, Chin. J. Geochem., 32, 380–384.

26.

Zhao

, Nie

, Wang

, Tian

, Ning

and Li

. 2012. Direct synthesis of palladium nanoparticles on Mn₃O₄ modified multi-walled carbon nanotubes: a highly active catalyst for methanol electro-oxidation in alkaline media, J. Power Sources, 218, 320–330.