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Hydrometallurgy 92 (2008) 73 78 www.elsevier.com/locate/hydromet

Technical note

Preparation of chemical manganese dioxide from Moroccan pyrolusite mine waste

Y. Darmane a,, M. Cherkaoui b , S. Kitane a , A. Alaoui a , A. Sebban c , M. Ebn Touhami b
b

Laboratoire Hydromtallurgie et Environnement, ENIM B.P. 753 Rabat, Morocco Laboratoire Electrochimie, Corrosion et Environnement, Facult des Sciences, Knitra, Morocco c Dpartement de Chimie, Facult des Sciences, Ben M'sik Casa, Morocco

Received 1 September 2007; received in revised form 14 January 2008; accepted 15 January 2008 Available online 26 January 2008

Abstract The preparation of manganese(IV) oxide from a Moroccan pyrolusite mine waste was studied. A sample of mine waste containing about 35% Mn was leached with 6.36 M HCl at 70 C for 1 h with 98% leaching efficiency. The resulting solution was conditioned at pH 5 and sodium hypochlorite was added to obtain various oxide phases (Mn2O3, MnO2). Finally the oxides were transmuted by addition of nitric acid to obtain the -MnO2, nH2O phase with 97% purity. 2008 Elsevier B.V. All rights reserved.
Keywords: Pyrolusite; HCl leach; Hypochlorite; Transmutation; MnO2

1. Introduction The IMINI mine, like majority of its counterpart old mines in Morocco, operates with unsophisticated techniques that result in under-exploitation of the deposit. A mineralogical study shows that this mine waste is composed primarily of manganese oxides (pyrolusite, psilomelane, hollandite) with a low content of iron oxide. There are many physical, chemical and physico-chemical techniques that have been developed and used for the enrichment of deposit. The traditional methods of enrichment consist of reducing the pyrolusite (-MnO2) in a first stage under high temperature to manganese(II) oxide followed by leaching with sulphuric acid and then a chemical or electrochemical oxidation (Atlam, 1997; Abou-El-Sherbini, 2002). Many leaching techniques cited in the literature reduce the pyrolusite in sulphuric acid with reducing agents like hydrogen peroxide (Tao Jiang et al.,

Corresponding author. E-mail address: darmaney@yahoo.fr (Y. Darmane). 0304-386X/$ - see front matter 2008 Elsevier B.V. All rights reserved. doi:10.1016/j.hydromet.2008.01.007

2003; Ibrahim et al., 2003), oxalic acid (Sahoo et al., 2001), glucose (Furlani et al., 2006) and iron(II) sulphate (Das et al., 1982). Leaching of manganese(IV) dioxide has also been carried out with hydrochloric acid alone (Abdrashitov `et al., 2001) or in the presence of pyrite (Kanungo, 1999a,b) or with hydrogen peroxide (El Hazek et al., 2006). However, these leaching techniques have high costs of oxidants and reductants. The precipitation of MnO2 from the Mn(II) leach solution can result from either an electrolytic process (Atlam, 1997) or a chemical process involving oxidation by air, H2O2 or KClO3 (Pagnanelli et al., 2007); SO2/O2 gas mixtures (Zhang et al., 2 2001); NaClO3 ( Abdrashitov et al., 2001) or by aqueous S2O8 , O2 and Cl2 (Strobel and Charpenton, 1986). Other studies have considered obtaining MnO2 chemically from permanganate solution (Brenet and Grund, 1956). Our present technique consists of carrying out direct leaching by hydrochloric acid followed by chemical oxidation with the sodium hypochlorite after conditioning the pH with caustic soda (NaOH). Finally, the manganese oxides formed undergo transmutation in nitric acid solution. During the leaching stage, the oxidation of chloride ion produces chlorine. This is then paddled in sodium hydroxide solution (NaOH) and the hypochlorite

74 Table 1 Chemical composition of the raw product Composed Content % MnO2 54.62 SiO2 20.53

Y. Darmane et al. / Hydrometallurgy 92 (2008) 7378

BaO 3.80

CaO 2.72

MgO 1.75

K2O 1.18

Fe2O3 1.05

Na2O 0.16

P2O5 0.04

Pb 1.98

formed can be used for the oxidation of Mn(II) in the leach solution. The efficiency of leaching, as well as that of oxidation, is controlled by several parameters; the most important being the acid concentration, temperature and the amount of oxidant. 2. Experimental 2.1. Ore material The mining tailings, which are the object of this study, result from half a century of mining and exploitation. After treatment, generally based on physical separation, thousands of tonnes of mineral waste have been deposited near the mine site with an average composition described in Table 1. 2.2. Analysis and equipment The X-ray diffraction (XRD) determination of the structures present in the product was carried out by an X'Pert Pro powder diffractometer with a vertical configuration using a power of 45 kV and a current of 40 mA. The solid products were dried at

105 C for 24 h before each analysis. The XRD analysis of the raw product is shown on Fig. 1. Complete elemental analysis was determined by an XRF spectrometer AXIOS (PAN analytical) operating at 60 kV, with a tube current up to 125 mA and a power of 3 kW. Elemental analysis of the manganese through the three stages of preparation was carried out using a colorimeter (Jenway PCO 10). This technique uses potassium periodate as an oxidant in sulphuric acid to oxidize Mn(II) to Mn(VII). 2.3. Procedure The chosen acid leach solution was mixed and equilibrated in a flask with the solids of particular size and solid/liquid ratio at a controlled temperature for 1 h. The solution was filtered to separate silica and then diluted 5/2 times. A small volume (100 mL) was agitated with a few mL of sulphuric acid to eliminate lead and barium in the form of insoluble salts (PbSO4, BaSO4), then the filtrate was conditioned at pH = 5 with caustic soda solution (NaOH, 2.5 M). The resulting solution was then oxidized by hypochlorite ion (ClO) and the brown precipitate was sampled and dried at 105 C for analysis. Finally, nitric acid

Fig. 1. Diffraction analysis of the raw product.

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was added at a definite concentration and temperature; and again the solid product was washed with distilled water and dried at 105 C.
3. Results and discussion Stage 1: Acid leaching The leaching of pyrolusite (MnO2) by hydrochloric acid results in the evolution of chlorine. MnO2 4HClMnCl2 Cl2 2H2 O 1

The parameters which govern this Reaction (1) are the acid concentration, the temperature, grain size, the solid/liquid ratio and the time of contact. These parameters were studied separately.
Fig. 3. Effect of reaction time on Mn leaching efficiency.

3.1. Effect of grain size Four samples of different sizes were prepared and successively leached with 5.7 M HCl at 70 C with a solid/liquid ratio of 90 g/L for 1 h. Results show that the rate of reduction of the Mn(IV) minerals was inversely proportional to the grain size, indicating a surface diffusion controlled reaction rate. The highest extraction (86%) was recorded starting from grain size of 125 m. 3.2. Effect of HCl concentration Various acid concentrations were prepared (4.4 to 7.7 M) in order to study the effect of the acid concentration on the leaching efficiency. The results presented in Fig. 2 show an increase in the dissolution of Mn(II) which is proportional to the HCl concentration. The extraction of Mn(II) rises from 66% (in 4.4 M HCl) to 98% (in 6.4 M HCl) which was taken as the optimal condition for leaching. This is a common phenomenon due to the oxidizing power of Mn(IV) towards hydrochloric acid. Under these optimum conditions, the initial amount of HCl in 0.1 L was 0.636 moles; but after leaching, the volume of 2.5 M NaOH necessary to neutralize the leach solution was 0.065 L. Then the amount of HCl consumed during the leaching of 90 g of solid product was 0.474 moles. 3.3. Effect of temperature To determine the required temperature, several experiments were carried out at different temperatures. The extraction of reduced Mn(II) rises from 80% at 50 C to 99.5% at 90 C. At higher temperatures, losses due to evaporation of HCl vapours were noted which obstruct the recovery of chlorine gas. The optimum temperature for leaching was therefore fixed at 70 C. 3.4. Effect of the liquid/solid ratio Under the above optimum condition, various solid/liquid ratios were examined in a constant volume of acid. With 85 g/L, the 6.4 M acid solution completely dissolved the manganese oxide contained in the sample. However, for economic reasons, the optimum ratio was fixed at 90 g/L which gave 98% recovery efficiency. 3.5. Kinetics of leaching The reaction kinetics was also investigated over different intervals of time as shown in Fig. 3. The extraction of Mn(II) rises from 88% in the first 15 min to 98% in 1 h and then starts to fall. The experimental error was determined to be approximately 1%, therefore this decrease is attributed to the precipitation of an insoluble Mn salt which was confirmed by analysis of the leaching residue. Therefore, the optimum time necessary for the reaction was fixed at 1 h. Stage 2: Oxidation in aqueous medium The suspension obtained from leaching was filtered and diluted 5/2 times before adding sulphuric acid to eliminate barium and lead present in the sample. Sodium hypochlorite (bleach) was the preferred oxidant as it is cheap. The principal parameters which governed the oxidation stage were: pH, Mn/ClO ratio and the temperature whilst time and stirring were kept unchanged during these experiments. 3.6. Effect of the pH The present experiment proceeded after conditioning the solution at different pH (ranging from pH 1 to 12.5). The principal objective was to attain maximum oxidation of Mn(II) with the minimum coprecipitation. The other parameters: Mn/ClO ratio (0.81 mol/mol) and temperature (25 C) were held constant. It was found that at pH = 5 this objective was achieved with a recovery efficiency of 75% and 34% Mn in the solid. In more acid medium (pH b 5), the hypochlorite ions (ClO) were reduced to chlorine (Cl2) gas. Furthermore, part of Cl2 was lost with stirring to the gas phase, hence the oxidation efficiency of the Mn decreased. In alkaline medium (pH 9), we observed the appearance of purple permanganate ion (MnO) accompanied by a decrease in the amount 4

Fig. 2. Effect of HCl concentration on Mn leaching efficiency.

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Fig. 4. Effect of Mn/ClO stoichiometric ratio on the oxidation efficiency. Fig. 5. Effect of the HNO3 concentration on the Mn% content.

of Mn(II) in the solid product as well as the precipitation of other elements. 3.7. Effect of Mn/ClO stoichiometric ratio A series of oxidation experiments were carried out on the conditioned solution at pH 5 and 25 C with different quantities of oxidant to determine the minimum quantity required to maximise the oxidation of Mn(II). The results given in Fig. 4 show that the oxidation of Mn(II) rises from 34% (with 2.66 mol/mol Mn/ClO) to 99% with 0.69 mol/ mol Mn/ClO. In the presence of strong oxidants such as ClO, oxidation produces either the -MnO2 or -MnO2 phases (Pourbaix, 1963). These conditions provide a friable and porous blackish-brown product which is a mixture of manganese oxides (MnO2 and Mn2O3) whose content is 34% Mn. The principal reaction is given below: 3Mn2 4ClO H2 OMn2 O3 MnO2 2H 2Cl2 2

manganous ion (Mn2+) (Brenet and Grund, 1956). The stability of Mn2O3 exists only for slightly acidic, neutral or alkaline solutions (Pourbaix, 1963). The acid which was chosen for this transmutation was nitric acid; taking into consideration its higher oxidizing power. The parameters studied in this stage were acid concentration, temperature, solid/liquid ratio and the time of reaction. 3.9. Effect of the acid concentration The aim of this third phase is to reach a maximum amount of MnO2 in the solid obtained after filtration. The colour change (brownish-black to the black) of the solid product is an additional indication of the end of the reaction. Depending on the acid concentration, the cubic form of chemically pure Mn2O3 can be used to form either -MnO2 or of MnO2 (Brenet and Grund, 1956). Also, Fe3+, Cr3+ and K+ have a tendency to prevent or to favour the formation of -MnO2 or -MnO2 (Brenet, 1956). The action of the acid on Mn2O3 can be attributed to its hydrolyzing and oxidizing capacity. Six nitric acid solutions (ranging from 1 M to 7 M) were prepared in order to determine the adequate concentration for this reaction. This experiment proceeded at a temperature of 60 C, a solid/liquid ratio (S/L) of 100 g/L for 1 h and the results are presented in Fig. 5. The hydrolysis of manganese oxides is not desirable but it is inevitable in this experiment. With a concentration of 5 M HNO3, the
Table 3 The optimum leaching, oxidation and transmutation conditions Conditions Leaching Grain size (m) HCl concentration (M) Temperature (C) Solid/liquid ratio (g/L) Time (min) Oxidation pH Mn/ClO stoichiometric ratio (mol/mol) ClO concentration (mol/L) Temperature (C) Transmutation HNO3 concentration (M) Temperature (C) Pulp density (g/L) Time (min) Value b125 6.36 70 90 60

With the 0.6 mol/mol ratio, a purple colour characteristic of MnO 4 ions was observed. This can be explained by the peroxidation of Mn(II) to Mn(VII) in the presence of large quantity of ClO; hence the decrease in the amount of Mn(II) in the solid product. It was also observed that the presence of high amounts of NaCl precipitate as impurity with the Mn oxide and other impurities adsorb on the solid's surface along with water of hydration. The chemical analysis of the product at pH = 5 is described in Table 2. 3.8. Effect of the temperature Tests were carried out at various temperatures in order to improve the oxidation efficiency of this reaction. The objective was to improve the selectivity of the hypochlorite ion (ClO) and obtain a higher Mn (II) content. A maximum efficiency (99%) was obtained with a solution of pH 5 at 25 C and a Mn/ClO ratio of 0.69 mol/mol. However, the results obtained showed that an increase in temperature does not allow selective oxidation of the Mn(II); hence the temperature was kept at 25 C. Stage 3: Transmutation in acid medium It is well-known that manganese sesqui-oxide (Mn2O3) can transmutate in acid medium to manganese dioxide (MnO2) and to
Table 2 Chemical composition of the product at pH 5 Composed Content % O 51.99 Mn 34.16 Cl 8.43 Na 4.31 Mg 0.14 Ca 0.12 K 0.08 Fe 0.07 P 0.07

5 0.69 0.49 25

5 60 120 60

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Fig. 6. Diffraction analysis of the finished product.

solid product becomes black with a light metallic lustre and contains 54% Mn. Beyond this acid concentration, the Mn content remains constant, hence 5 M was fixed as optimal for this experiment. The analysis of the manganese oxide precipitated in the second stage showed significant amounts of NaCl that co-precipitated. Furthermore, incorporation of H2O molecules into the crystal lattice of manganese(II)/(III) oxide prevents a high % Mn content being obtained. During transmutation, nitric acid at moderate temperature oxidizes Mn(II) and Mn(III) to Mn(IV) and dissolves other compounds. 3.10. Effect of the temperature Several tests were carried out at various temperatures since this factor plays an important part during the transmutation reaction. The maximum content of Mn was obtained at 60 C, hence this value was chosen for further experiments.

3.11. Effect of the solid/liquid ratio Several experiments were carried out to determine the best solid/ liquid concentration for optimal transmutation. An increase in the solid/ liquid ratio led to a slight increase in the Mn content which reached 54.4 0.7%. (i.e. 85.9% MnO2) with a ratio of 120 g/L. This value is taken as the optimal ratio of this experiment. 3.12. Effect of the reaction time on transmutation The transmutation was stopped at different times to determine the minimum duration necessary for the reaction. It was found that complete transmutation was reached in the first hour giving a black product containing 54.4% Mn. In general, the variation of Mn content was 53.4 1% in 30120 min. The optimum leaching, oxidation and transmutation conditions as well as the results obtained are summarised in Table 3. The structural analysis of the solid product (MnO2) highlighted the presence of -MnO2, nH2O (n b 1) (Fig. 6) and the composition of the product is given in Table 4.

Table 4 Chemical analysis of the finished product Element MnO2, nH2O (n b 1) Mn Na2O K2O PbO MgO Fe2O3 CaO P2O5 BaO Content % 96.900 54.350 1.080 0.780 0.360 0.110 0.084 0.035 0.010 0.007

4. Conclusions The enrichment of Moroccan pyrolusite tailings made it possible to obtain a product containing hydrated manganese dioxide (97% MnO2.nH2O). This was carried out by using a new process which is composed of three essential stages (a) Direct leaching with 6.4 M HCl at 70 C and a solid/liquid ratio of 90 g/L for 1 h. (b) Oxidation of the Mn(II) filtrate with hypochlorite ions at pH 5, 25 C and Mn/ClO molar ratio of 0.69. (c) Transmutation in 5 M HNO3 at 60 C with a solid/liquid ratio of 120 g/L for 1 h. The liquid waste is composed mainly of NaCl salt which can be treated

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Fig. 7. Flow sheet proposed for enrichment of the pyrolusite mine waste (Morocco).

and crystallised. The proposed process flow sheet is given in Fig. 7. References
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