Manganese Metallurgy Part I

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Hydrometallurgy 89 (2007) 137 159 www.elsevier.com/locate/hydromet
Manganese metallurgy review. Part I: Leaching of ores/secondary materials and recovery of electrolytic/chemical manganese dioxide
Wensheng Zhang , Chu Yong Cheng
Parker Centre for Integrated Hydrometallurgy Solutions, CSIRO Minerals, PO Box 7229, Karawara, WA 6152, Australia Received 6 July 2007; received in revised form 24 August 2007; accepted 25 August 2007 Available online 1 September 2007
Abstract The world rapidly growing demand for manganese has made it increasingly important to develop processes for economical recovery of manganese from low grade manganese ores and other secondary sources. Part I of this review outlines metallurgical processes for manganese production from various resources, particularly focusing on recent developments in direct hydrometallurgical leaching and recovery processes to identify potential sources of manganese and products which can be economically produced. High grade manganese ores (N 40%) are typically processed into suitable metallic alloy forms by pyrometallurgical processes. Low grade manganese ores (b 40%) are conventionally processed by pyrometallurgical reductive roasting or melting followed by hydrometallurgical processing for production of chemical manganese dioxide (CMD), electrolytic manganese (EM) or electrolytic manganese dioxide (EMD). Various direct reductive leaching processes have been studied and developed for processing low manganese ores and ocean manganese nodules, including leaching with ferrous iron, sulfur dioxide, cuprous copper, hydrogen peroxide, nitrous acid, organic reductants, and bio- and electro-reductions. Among these processes, the leaching with cheap sulfur dioxide or ferrous ion is most promising and has been operated in a pilot scale. The crucial issue is the purification of leach liquors and the selective recovery of copper, nickel and cobalt is often difficult from solutions containing soluble iron and manganese. For treatment of manganese bearing materials including waste batteries, spent electrodes, sludges, slags and spent catalysts, a leaching or reductive leaching step is generally needed followed by various purification steps, which makes the processes less economically viable. It is concluded that the recovery of manganese from nickel laterite process effluents which contain 15 g/L Mn offers a growing low cost resource of manganese. Part II of this review considers the application of various solvent extraction reagents and precipitation methods for treating such manganese liquors. 2007 Elsevier B.V. All rights reserved.
Keywords: Manganese; Metallurgy; Leaching; Chemical manganese dioxide; Electrolytic manganese dioxide
1. Introduction Manganese is an important metal in human life and industry. In recent years, the world manganese demand has been driven by soaring steel production, particularly
Corresponding author. E-mail address: wensheng.zhang@csiro.au (W. Zhang). 0304-386X/$ - see front matter 2007 Elsevier B.V. All rights reserved. doi:10.1016/j.hydromet.2007.08.010
in China. Steelmaking, including its iron making component, has accounted for most of the world manganese consumption, presently in the range of 85% to 90% of the total demand (Corathers, 2004, 2005). Most of the manganese is consumed in steelmaking in the form of manganese ferro-alloys. In 2004, manganese consumption was 60% higher than that of 2003. World production of manganese ore rose steadily by 9% in 2004
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and 2005 on a contained-weight basis compared with that in 2004. The price of metallurgical-grade ore (N40%) increased by 16% in 2004 and 63% in 2005 internationally. Combined world production of ferromanganese and silicomanganese rose by 8% on a grossweight basis compared with that in previous year (Corathers, 2004, 2005). The rapid growing demand for manganese metal as an alloying element comes primarily from the aluminium industry followed by the steel industry and that for electrolytic manganese dioxide (EMD) and chemical manganese dioxide (CMD) come from the primary and secondary battery industries. Industry EMD usage in alkaline batteries in 2002 exceeded 230,000 t per annum with an annual growth rate in excess of 9.6% between 1996 and 2002 (Anon, 2003). Future growth in the EMD market is expected to exceed current growth rates, as global demand for batteries will increase in areas such as mobile communications. A wide range of new products, such as disposable mobile telephone batteries, could see growth rates of up to 8% a year (Anon, 2003). Electrically powered consumer products, from cameras and watches to sophisticated children's games and toys are also an area of robust growth. Extra growth in the demand for EMD is also expected from the secondary or rechargeable battery market as lithium manganese ion batteries (that use EMD in their manufacture) replace cobalt type batteries as the cheaper and more environmentally friendly alternative. Growth is also likely to come from the use of EMD in hybrid electric vehicles (HEV's). As the environmental impact of traditional cars continues to cause problems in densely populated cities, the increased usage of HEVs to minimize pollution levels seems inevitable. With the rapid growing demand for manganese products, low grade manganese ores (b 40%), manganese ocean nodules and secondary manganese sources, which cannot be economically processed by conventional pyrometallurgical processes or pyro-pre-treatment, become increasingly important sources of manganese. In recent years, various hydrometallurgical processes have been studied and developed for recovery of manganese from these manganese sources. In this part of review, conventional pyrometallurgical processes and pyro-pre-treatments for production of major manganese products are briefly outlined. Recent developments in direct hydrometallurgical processes for leaching and recovery of manganese are reviewed in details. The aims of this part review are to obtain a general knowledge of manganese metallurgy including pyrometallurgy, pyro-hydrometallurgy and hydrometallurgy
and to identify potential sources of manganese and products which can be economically produced. 2. Manganese resources and pyro-processes 2.1. Manganese resources Manganese is the twelfth most abundant element in the earth's crust (0.096%). Its deposits are generally of sedimentary origin, with oxide ore layers inter-bedded with iron-rich formations (Kaneko et al., 1993). The most common mineral is pyrolusite, which is mainly MnO2. Manganese is also found in several minerals, such as pink rhodochrosite (MnCO 3), rhodonite (MnSiO3), black manganite (MnO(OH)), and alabandite (MnS) (Calvert, 2004). The main sources of manganese come from the former U.S.S.R, Brazil, South Africa, Australia, Gabon and India. Russia and South Africa produce about 85% of the world's pyrolusite. Manganese nodules or ferro-manganese concretions, usually containing 3036% Mn, have been found on ocean floors (Calvert, 2004) and could provide another source of manganese. These nodules are found in both the Atlantic and Pacific Oceans, but principally in the Pacific Ocean. Although the primary interests in deepsea nodules are nickel, copper, and cobalt values, the large quantities of manganese could also be of future importance. As a result, much research work has been devoted to recovering not only nickel, copper and cobalt but also manganese as well. Manganese bearing materials such as waste batteries and spent electrodes, spent catalysts, steel scraps, sludge and slag are secondary manganese sources. Manganese minerals are often associated with zinc sphalerite ores and nickel laterite ores, which are leached and rejected to the waste effluents in subsequent processing steps. These manganese-containing industrial waste effluents could be potentially important manganese sources. For instance, in the leach solution of the Murrin Murrin Operation of Minara Resources Ltd., the ratio of nickel/ manganese concentrations is in the order of 2:1. Its current nickel production is 36,000 t per annum. Therefore, the manganese in the waste stream is about 18,000 t per annum (Zhang and Cheng, 2006). 2.2. Manganese pyro-metallurgy Metallurgical grade manganese ores (N 40% Mn) are usually processed into suitable metallic alloy forms by pyrometallurgical processes, which are very similar to iron pyrometallurgical processes. Ferro-manganese is a commonly used alloy. In its production process, a mixture of
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manganese ore, reductant (a form of carbon) and flux (CaO) are smelted at above 1200 C to enable reduction reactions and alloy formation. Standard grade ferromanganese contains more than 76% Mn and about 7% C, and can be produced either in a blast furnace or in an electric furnace (Yucel and Ari, 2001). High carbon ferromanganese can be made by three different practices: blast furnace, discard slag electric furnace, and high manganese slag electric furnace. Medium carbon ferromanganese can be produced by a de-carbonation process or through a redox reaction between silicon in the silicomanganese alloy and manganese ores. Low carbon ferro-manganese is produced by the reaction of manganese ore and low carbon silico-manganese. Silicomanganese is another commonly used alloy, containing 1416% Si, 6568% Mn, and about 2% carbon. Lower carbon levels result when the silicon content is increased. Special grades with up to 30% Si are produced for use in the manufacture of stainless steel. The production of silico-manganese is very similar to that of electric smelting of ferro-manganese. It differs in furnace charge which contains large amount of quartz (SiO2) (Yucel and Ari, 2001). Off-grade silicon bearing materials such as ferrosilicon fines, drosses, or ladle dig-outs provide a relatively cheap source of silicon for the silico-manganese making operation because re-melting these materials uses less energy than smelting silicon. 2.3. Manganese pyro-hydrometallurgy A pyrometallurgical pre-treatment followed by hydrometallurgical processing plays an important role in the treatment of low grade manganese ores and manganese sea nodules containing Ni, Co and Cu values as their oxides. These metal oxides in the nodules often occur in the lattices of iron and manganese minerals. Therefore, breaking up these lattices by pyrometallurgical reduction or hydrometallurgical reductive dissolution is an essential step for the satisfactory recovery of valuable metals. The suggested pyrometallurgical pre-treatments are smelting (Cooper et al., 1959), reduction-roasting (Rolf, 1969), sulphatising (Freitas et al., 1993), and chloridising (Cooper et al., 1959). Compared with pure hydrometallurgical processes, combining pyro-hydrometallurgical treatments yield better results for efficient recovery of Ni, Co, Cu and Mn values from poly-metallic manganese nodules (Kohga et al., 1995), but they require more energy consumption. In sulphation roasting, the manganese ores or Mnbearing materials are roasted in the presence of sulfuric acid or ammonium sulfate to convert the manganese minerals to soluble sulfates. Sulphation of manganese ore with gaseous SO2 has been reported (Freitas et al., 1993).
In this case, the gaseous SO2 plays dual roles in the sulphation process: a reductant and a sulphation agent. Sulphation roasting followed by water leaching has been investigated for recycling of zinc-carbon spent batteries with a production of manganese and zinc sulfates (Abbas et al., 1999). The process involves mechanical separation and sulfuric acid leaching, sulphation roasting in the presence of sulfuric acid or ammonium sulfate, followed by water leaching. Maximum manganese recovery efficiency (93.4%) is achieved by using an ammonium sulfate roasting process. In a patented process by Kasimov et al. (1990), the Mn-containing slag, after mixing with (NH4)2SO4, was roasted and then leached with aqueous (NH4)2SO4 to recover manganese compound at low (NH4)2SO4 consumption. The sulfate-containing residue was then pressure-leached at 100150 C with aqueous (NH4)2CO3 at a NH3:CO2 mole ratio of 1:1 1.5 and heated to recover (NH4)2SO4 for recycling. This approach for recycling (NH4)2SO4 appears to be expensive involving NH3 input and high pressure leach step, and thus less practical. Smelting or reduction roasting at about 700900 C followed by sulfuric acid leaching is by far the most commonly employed method in the manganese industry for production of intermediate or final manganous sulfate for further electrowinning process (Paixao et al., 1995). The reduction reaction can be presented as: MnO2 CO=H2 MnO CO2 =H2 O MnO2 CMnO COCO2 1 2
This process converts higher valent manganese oxides to lower ones which are readily soluble in sulfuric acid. 3. Leaching processes The typical leaching processes involve a chemical reductive step, including bio-leaching and electroleaching except for acid leaching of Mn(II) ores. Purification, separation and final recovery processes such as solvent extraction, electrolysis and electrowinning, and other recovery processes are then used. 3.1. Reductive leaching with ferrous iron solution Treatment of manganese ore or manganese bearing slimes with acidified ferrous sulfate or pickle liquors has been reported in several studies (Brantley and Rampacek, 1968; Das et al., 1982; Vu et al., 2005). A rather novel process for recovery of manganese with pickle liquor (weak FeSO4-H2SO4-(NH4)2SO4
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Fig. 1. Flowsheet for the process of Mn recovery using pickle liquor to leach ore (based on Brantley and Rampacek 1968).
solutions) from low grade manganese ores was developed by US Bureau of Mine (Brantley and Rampacek (1968)). The process is schematically shown in Fig. 1. This process features the simultaneous high temperature hydrolysis of Fe(III) and precipitation of manganese as manganese double salt (NH4)2Mn2(SO4)3 which is then separated from coprecipitated Fe2O3 by dissolution of the salt in water. A relative pure manganese pregnant solution for electrolysis is expected to be obtained in this way. The economical concern of this process is its involvement of expensive H2O2 oxidant and a high temperature autoclave process. However, recent developments in pressure oxidation and autoclave technologies may make this approach more attractive. A study by Das et al. (1982) showed that the reaction of MnO2 in the low manganese ore with ferrous sulfate could occur in three ways: with neutral ferrous sulfate solution MnO2 2FeSO4 2H2 O MnSO4 FeOHSO4 FeOH3 3
More than 90% of manganese could be extracted by leaching the low manganese ore with a stoichiometric amount of ferrous sulfate at 90 C for 1 h with solidliquid ratio of 1:10. The leach slurry obtained under the above conditions was gelatinous and difficult to filter. An addition of sulfuric acid made filtration easier and greater Mn extraction, but resulted in 3- 4-fold more iron extraction (Das et al., 1982). Dundua and Agniashvili (1999) used FeSO4 as leaching agent for manganese recovery from residual slimes in the electrochemical production of manganese dioxide. The resulting liquor was purified by removal of Fe(II) ions using manganese carbonate from low-grade ores. The optimised leaching was proposed for manganese recovery from sludge wastes in the closed-cycle electrochemical production of MnO2. 3.2. Reductive leaching with sulfur dioxide or sulfite solutions Reductive leaching of manganese nodules and low grade manganese oxide ores with SO2 dioxide or sulfite salts has well been documented in the literature. It is an effective reductant for higher manganese oxide minerals such as MnO2 and manganese nodules in the hydrometallurgical leaching process. Aqueous SO2 has been investigated for both percolation and agitation leaching. Typical studies on leaching of manganese ores with SO2 or sulfite salts are summarised in Table 1. The reactions which may occur during leaching manganese oxides are (Petrie, 1995): MnO2 SO2 Mn2 SO2 4 6 7 MnO2 2SO2 Mn2 S2 O2 6
with ferrous sulfate solution and small amount of acid MnO2 2FeSO4 H2 SO4 MnSO4 2FeOHSO4 4
and with ferrous sulfate solution and excess amount of acid MnO2 2FeSO4 2H2 SO4 MnSO4 FeSO4 3 2H2 O
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2MnOOH SO2 2H 2Mn2 SO2 2H2 O 4 8 2MnOOH SO2 2H 2Mn2 S2 O2 2H2 O 6 9

2 The SO2 is oxidised to SO4 and a proportion of 2 dithionate S2O6 by-product depending on solution pH, temperature and redox potentials (Das et al., 1998; Ward et al., 2004; Ward, 2005). A radical mechanism was proposed for formation of dithionate, involving the 2 formation of SO3 radicals and dimerisation to S2O6 (Petrie, 1995). In early 1946, a dithionate process was first developed for recovery of manganese from low-grade ores (Ravitz et al., 1946). This is essentially a SO2 reductive process. The advantage of this process is to utilise the dithionate intermediate product of the reductive reaction to stabilise both the reduced Mn(II) and calcium in solution while extra calcium is precipitated as CaSO4 precipitate. This allows lime to be used as a cheap neutralisation agent. In the semi pilot-plant tests, about 40 runs were carried out on ores assaying 1318% Mn. Manganese recovery was more than 90% in most cases. A final product containing more than 60% Mn, meeting ferro-grade specifications, was produced. For each unit of manganese extracted, 1.52.2 unit of SO2 and 1.11.5 CaO were consumed. The quantity of SO2 consumed was 6070% of that introduced. Dithionate was also used for the treatment of low-grade manganese slimes (Maslenitskii et al., 1969) at a laboratory scale. A recovery of 90% Mn was achieved when the carbonate manganese accounted for 50% of the total manganese content. The manganese content in the
produced concentrate was always 5560%, irrespective of the content in the slimes. The concentrates could be used to produce ferromanganese by the fluxless method or to make electrolytic manganese with the dithionate process. However, it is generally undesirable to form dithionate in SO2 leach processes as it requires long residence time to oxidise the dithionate to sulfate and would contaminate the manganese sulfate products by slowly reacting to release sulfur dioxide. A process that minimises the 2 formation of (S2O6 ) to below 1 g/L by addition of SO2 continuously at a controlled rate determined by monitoring the solution potential has been developed and reported (Ward et al., 2004; Ward, 2005, see also Section 5.4). Direct aqueous SO2 leaching was used for rich Greek manganese ores (Grimanelis et al., 1992). The reaction was found fast with N 95% Mn recovery in about 10 min and with low iron impurity. In the studies using low manganese ores (Naik et al., 2000, 2002, 2003), the rate was proposed to be controlled by SO2 diffusion to the reaction surface, evidenced by a low apparent activation energy of 16.6 kJ/mol. Twice the stoichiometric quantity of SO2 was required for dissolution of manganese. The (NH4)2SO3bisulfite mixture at the bisulfite/H2SO4 (w/w) ratio of 1:(0.521.55) was also used as the reductant in leaching the FeMn ore concretions (Sventsitskii et al., 2003; Partenov et al., 2004). The reaction rate was found to be first order with respect to SO2 concentration and controlled by diffusion of SO2 to the reaction surface (Partenov et al., 2004). In processing manganiferrous silver ores where manganese and silver minerals are intimately associated, the reductive leaching by aqueous SO2 extracts manganese into solution, leaving silver minerals in the residue
Table 1 Reductive leaching of Mn ores/slimes by aqueous SO2/sulfite Feed MnO2 minerals Rich Mn ore (N40% Mn) Low Mn ore (b40% Mn) Reagents Aq. SO2 Aq. SO2 Dithionate Aq. SO2 Aq. SO2 Low Mn slimes FeMn concretions Dithionate Conditions Studied leaching chemistry Key results Ref Petrie 1995 Das et al. 1998 Grimanelis et al. 1992 Ravitz et al. 1946 Naik et al. 2000; 2003 Ward et al., 2004; Ward 2005 Maslenitskii et al. 1969 Sventsitskii et al. 2003
(NH4)2SO3 bisulfiteH2SO4 Aq. SO2 Kinetic study
Sulfate/dithionate ratio depends on pH, Eh and Tem. Atm. pressure and room temp. N95% Mn in 10 min Lime for neutralisation N60% Mn, meeting ferro-manganese Atm. pressure and room temp. Rapid leaching rate 95% Mn recovery b60 C controlled Minimised dithionate to 1 g/L Eh for adding SO2 90% Mn recovery 5560% Mn content pH 3.55.5 3070 C 96% Mn recovery
Low Mn ores (Percolation) Aq. SO2
Size 1.32.5 cm 1.5%-sat. [SO2] 1520 days
E = 16,6 kJ/mol SO2 diffusion Partenov et al. 2004 control First order: [SO2] Abbruzzese 1987 Pahlman and Rate depends on [SO2] and pH N90% Mn recovery Khalafalla 1988 Abbruzzese 1990
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which could be recovered by subsequent cyanidation (Pahlman et al., 1987). In percolation (Abbruzzese, 1990), the extent of the extraction depends mainly on the dissolved SO2 concentration and the acidity of the leach solution, which govern the thermodynamic conditions of the system. The pH must be maintained below the pKa and the concentration of SO2 around the saturation value (6%). Ambient temperature and small particle size favour manganese recovery. The maximum extraction was achieved in 1520 days of leaching. Simultaneous dissolution of iron was found to be significant when the ore contained goethite and siderite. Dissolution of calcium could be inhibited by low flow rate of the leach solution. Over 90% Mn recovery could be achieved (Pahlman and Khalafalla, 1988). Pilot percolation plant leaching tests (Abbruzzese 1987) showed that total manganese recovery was 94.4% which was slightly lower than values obtained in the batch tests. The pregnant solution of MnSO4 containing mainly Fe and Zn impurities was purified using 20% DEHPA in kerosene for extraction of Fe(III) at pH 1.51.8 and Zn at pH 4. The main concerns on the application of the aqueous SO2 for leaching of manganese ores in percolation is the control of SO2 and the acidity, which appear difficult and costly. 3.3. Reductive leaching with organic reductants Many studies have focused on reductive leaching of manganiferrous ores containing tetravalent manganese using organic reductants, including sawdust (Sanigok and Bayramoglu 1988), glucose, sucrose (Veglio and Toro 1994a,b), lactose (Ali et al., 2002 Ismail et al., 2004), glycerine (Arsent'ev et al., 1991), oxalic acid,
Table 2 Reductive leaching by organic reductants Reductant Glucose Sawdust (C6H10O5)n Sucrose (C12H24O11) Lactose (C12H22O11) Ore Mn nodules Low Mn Ore Pyrolusite Low Mn Ore MnAg Ores Glycerine Triethanolamine and Thiosulfate Oxalic Acid (OX) Carboxylic Acid (15%) HF (9%) Mn ores MnO2 Low Mn Ore Ferro columbite Conditions
citric acid, tartaric acid, formic acid (Sahoo et al., 2001; Rodriguez et al., 2004), and triethanolamine and thiosulfate (Yavorskaya et al., 1992). The conditions and main results are summarised in Table 2. The carbohydrate reductants are considered to be cost effective and non-hazardous, which may be used either in pure form or from industrial wastes (Veglio and Toro 1994a,b). The stoichiometry was proposed as follows. C6 H12 O6 12MnO2 24H 6CO2 12Mn2 18H2 O 10
The reaction products of the glucose were identified using HPLC (Furlani et al., 2006). In sulfuric acid medium, the glucose was oxidized via formation of monocarboxylic polyhydroxyacids and formic acid. Formic acid was identified and quantified as the major component. Poly-hydroxyacids, especially glyceric and glycolic acid, were found in minor quantities together with traces of gluconic acid. Sawdust and oxalic acid are also of interest to industrial applications due to its cheap cost and availability. 3.4. Bio-reductive leaching In addition to the studies on chemical leaching processes, a certain emphasis has been placed on reductive biological treatment that generally uses heterotrophic microorganisms (Abbruzzese et al., 1990; Veglio et al., 1997). The mechanism can be direct and indirect. In direct leaching mechanism, the bacteria are capable of utilizing the MnO2 as a final acceptor of electrons in the
Key Results (%) Cu 100, Ni 90, Co 60 9095% Mn (99.6% pure) 9495% Mn recovery 9092% Mn recovery 97% Mn 98% Ag and Au Increased Mn recovery Maximum Mn recovery 98.4% Mn recovery TR increases %Fe and Mn OX decreases %Mn
References Das et al. 1986 Sanigok and Bayramoglu 1988 Veglio and Toro 1994a; 1994b Ali et al. 2002 Ismail et al. 2004 Ziyadanogullari and Buyuksahin 1995 Arsent'ev et al. 1991 Yavorskaya et al. 1992 Sahoo et al. 2001 Rodriguez et al. 2004
2.5 M NH3, 0.37 M NH4Cl, 0.2 g glucose/g of nodules, 85 C, 4 h Aq. H2SO4 5090 C 20 g/L of sucrose H2SO4: Mineral = 0.98 Sucrose:Mineral = 0.1 100 mesh, 2 h, 90 C H2SO4/ MnO2 = 1.8 lactose/Mn-ore = 0.75 Two stage leach with H2SO4 and then thiourea Aq. H2SO4 glycerine/MnO2 = (12.5) H2SO4:Mn b2.6 Thiosulfate/ MnO2 = (0.250.28) 30.6 g/l OX, 0.5 M H2SO4 85 C, 105 min. HF + tartaric (TR), citric, formic, oxalic (OX) acids
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respiratory chain of their metabolism, instead of oxygen. In the indirect mechanism, the reductive process is associated with the formation of reductive compounds, resulting from their metabolism. In all cases, the biological process occurs in the presence of organic carbon and energy sources. The mechanism of the bioleaching was found to be predominantly indirect through the production of organic acids, mainly oxalic acid and citric acid in the leaching medium which reduced manganese oxides (Acharya et al., 2003). Oxalic acid is potentially of greater interest than citric acid due to its reductive activity for MnO2 according to the following reaction (Abbruzzese et al., 1990): MnO2 2H C2 O4 H2 Mn2 2 CO2 2H2 O 11 The manganese ions (released as manganese oxalate and manganese citrate) formed a product layer on the ore, and the reaction was proposed to be controlled by diffusion of the reactants through the permeable product layer (Acharya et al., 2003). The kinetic equation could be expressed by the shrinking core model [1 (1 )1/3]2 kt (where is the fraction of manganese reacted, k the rate constant and t the reaction time) (Acharya et al., 2003). Acharya et al. (2001) investigated microbial extraction of manganese from the low grade manganese ore which was collected from Joda East manganese mines of Orissa. The microorganism used was an indigenous fungal culture, Penicillium citrinum, isolated from the top soil of the same mines. An extraction of 64% manganese was obtained within 30 days. Research workers in Greece and Italy (Veglio et al. 1997) investigated a batch and semi-continuous process for bioleaching of manganiferrous minerals with heterotrophic mixed microorganisms. 95100% of manganese extraction could be obtained in 3648 h of treatment using a content of pulp containing 20% (w/v) of ore having a Mn grade of 1720%. Final tests in a pilot plant (V = 70 L) were performed under non-sterilised conditions. The experimental results showed a technical feasibility of the process although several problems have to be resolved to allow for a full-scale application, such as the biomass disposal, the purification of the leach liquor before the final manganese recovery, and the high cost of the process. 3.5. Electro- reductive leaching Electro-leaching dissolves the manganese minerals in leach solutions whose potential is controlled potentios-
tatically. This method is based on the principle that manganese dioxide can be used as an electrode because it is a semi-conductor. In the electroslurry process, manganese is cathodically dissolved from oxide slurry by direct electroreduction. Elsherief (2000) has recently applied electro-reductive leaching for upgrading Egyptian low-grade manganese ores in sulfuric acid solutions using a slurry electrolysis cell. It was found that MnO became readily soluble in acid under reductive conditions. Cyclic voltametric studies on carbon paste electrodes of the ore and its mineral constituents showed that maximum reduction of manganese occurred at 0 mV with respect to a mercury/mercurous sulfate reference electrode. The acid concentration, the reaction temperature, and the applied potential affected the reaction rate and level of extraction of manganese from the ore. The rate of reduction increased with increasing acidity. The reactions were proposed as follows: MnO2 4H 2e Mn2 2H2 O MnO2 H e MnOOH MnOOH 3H e Mn2 2H2 O

12 13 14
With sufficient accumulation of MnOOH on the surface of the MnO2, further reduction to Mn(OH)2 could occur: MnOOH H e MnOH2 15
The presence of Fe2+ and Mn2+ ions greatly increased the speed of reaction. This could be due to an involvement of Fe2+ in the chemically reductive reactions as shown in reactions (35). Temperature was found to have a major influence on the leaching process. The main reduction process resulted in Mn2+ release and selectivity could be achieved. At 20 C, very poor recoveries of metals were recorded. Under optimum conditions at 70 C in 50 g/L H2SO4 solutions at 0 mV, manganese was fully extracted whereas 56% iron was extracted in 45 minute electrolysis. The amount of manganese leached by the electrolysis at 0 mV was approximately five times more than that recovered by chemical leaching without applied potential. 3.6. Simultaneous leaching manganese(IV) oxide and sulfide minerals Many studies have been carried out to leach manganese oxides and sulfide minerals simultaneously in an acid medium, H2SO4 or HCl. In this leaching process, the
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Table 3 Simultaneous leaching of Mn oxides and metal sulfide minerals Sulfides Pyrite (FeS2) Mn oxides Low Mn ore Mn ore Mn Conc. (58% MnO2) MnAg ores MnO2 MnAg ores Mn ore Mn nodules Mn nodules Low Mn ore Conditions H2SO4, 175 C (1) with O2 (2) without O2 10% H2SO4 Mn ore:pyrite ore = 1:1 10% H2SO4 8595 C Residue cyanidation H2SO4 sol. H2SO4 sol. Ag by NH3 leach H2SO4 sol. 1.52.0 M HCl 95 C, 80 min HCl solution, 70 C 1.9 M H2SO4 Ore/lignite = 1:1.8 99 C, 3 h Key results (1) MnSO4.H2O product (2) FeSO4 suitable for leaching at room temp milled before leaching increased Mn recovery 99% Mn recovery 93% Mn recovery 92% Ag recovery MnSO4, ZnSO4 suitable for electrowinning 98% Mn recovery 92% Ag (99% pure) Key factor: MnOx:MeS, Temp. N90% Ni and Cu and 80% Co 97% Mn, 92% Co, and 88% Ni N99% Mn recovery Ref Thomas and Whalley 1958 Gaprindashvili et al. 1993 Omarov and Beisembaev 1996 Lu and Zou 2001 Li 2000 Yaozhong 2004 Kholmogorov et al. 1998 Chen et al. 1992 Kuh et al. 2001 Naik et al. 2002
ZnS FeS2/ZnS/PbS Ni matte Zn matte Pyriti-ferrous lignite
sulfide minerals function as reductants while the manganese oxides as oxidants. The sulfide minerals include galena (PbS) (Kholmogorov et al., 1998), sphalerite (ZnS) (Kholmogorov et al., 1998; Li, 2000; Yaozhong, 2004) or zinc matt (Li, 2000), pyrite (FeS2) (Thomas and Whalley, 1958; Gaprindashvili et al., 1993; Omarov and Beisembaev, 1996; Kholmogorov et al., 1998; Lu and Zou, 2001), nickel matte (Li, 2000), pyriti-ferrous lignite (Naik et al., 2002). The key operation parameters were found to be the MnOx:MeS ratio, acid concentration, temperature and leach time (Kholmogorov et al., 1998). The leach conditions and major results are summarised in Table 3. Among the sulfides, pyrite concentrate offers some advantages: 1. The iron introduced can be easily removed as iron oxides or hydroxides in the presence of oxygen. 2. In the absence of oxygen, Fe(II) can be used as a reductant in subsequent leaching process. Other valuable metal sulfides such as nickel and zinc can only be justified for special cases, e.g. a comprehensive recovery of these metal values from polymetallic manganese nodules. 3.7. Leaching with hydrogen peroxide Jiang et al. (2003) investigated a simultaneous leaching process for extraction of manganese and silver by one-step leaching in sulfuric acid solution in the presence of hydrogen peroxide. Thermodynamics of the MnH2O and AgH2O systems show that there is a predominance region where Mn2+ and Ag+ coexist in solution. Hydrogen peroxide plays dual roles in the
process: as an oxidizing agent for native silver and a reducing agent for manganese dioxide based on the following reactions: MnO2 H2 O2 2H Mn2 2H2 O O2 E 0:549 V 2Ag H2 O2 2H 2Ag 2H2 O E 0:971 V 16 17
A recovery of 98% for manganese and 85% for silver was attained for an ore analysing 12.2% Mn and 1850 g/t Ag under the conditions of 0.8 mol/L H2O2, 0.8 mol/L H2SO4, 25 C, and 2 h of residence time. 3.8. Leaching with hydrochloric acid solution A hydrochloric acid leaching process for manganese recovery from manganese ores has been proposed and patented by Abdrashitov et al. (2001). In this process, the Mn-ore feed was leached with aqueous 520% HCl solution, which resulted in the associated evolution of Cl2 and the formation of MnCl2. The leach solution together with MnCl2 and Cl2 was treated in the subsequent stage by addition of Na2CO3 to precipitate purified MnO2 product in the presence of aqueous NaCl and evolved CO2. The typical manganese recovery into solution by the acidic leaching was 97.0% at 101.6 g/L Mn, and the MnO2 precipitate in the second stage was 98.0% pure compared with 1750% Mn and 50% SiO2 in the ore feed. The novelty of the invented process utilises the chloride ions as the reductant at high acidity and the Cl2 product as the oxidant to precipitate the reduced manganese as MnO2 in alkaline conditions. However, this process is expected to be rather expensive
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and inefficient because a very high acidic condition is needed for the chloride ions to function as a reductant. In addition, the corrosive Cl2 gas has to be collected and to be used in the subsequent precipitation step. 3.9. Leaching with nitrogen dioxide and nitric acid solutions A nitrous-nitric process was developed for recovery of manganese from manganese ores by Dean et al. (1942) at U. S. Bureau of Mines. The process involved leaching the ore with NO2 and decomposing the resulting Mn(NO3)2 solution. Five hours of nitration of Cuyuna Merritt ore ( 65 mesh) gave at least 95% extraction of manganese in a solution low in iron and phosphate. HNO3 formation could be maintained as low as 0.3 g per gram of manganese by controlling the NO2 flow and eliminating air pressure. Manganese concentrations of 300 g/L could be obtained. Evaporation of the pregnant liquor resulted in quantitative precipitation of Fe and P. Electrolytic decomposition of the filtered solution, heated by alternative current, proved to be the best method to decompose the salt and gave a highpurity MnO2. Magnesium nitrates could be removed by bleeding and re-crystallisation. In a recent development by Drinkard and Woerner (1997), HNO3 has been used in leaching for recovery of metal values from metallurgical dust wastes. Although
nitrous-nitric process is effective, HNO3 is an expensive reagent and the resulting effluent is difficult to treat. 3.10. Acid leaching of Mn(II) carbonate and silicate ores and slags Manganese carbonate and silicate minerals are soluble in acids, e.g., in sulfuric and hydrochloric acids. Several acid leaching processes have been developed to recover manganese from these kinds of manganese minerals. Arsent'ev et al. (1992) investigated hydrometallurgical methods for processing of Vorkutinsk manganese ores. The ores containing 41.1% Mn consisting of 5355% carbonates and 4043% silicates were ground and leached with H2SO4 (0.8 kg/kg ore) for 1.5 h at above 90% Mn recovery. The leach solution was then neutralized, and a carbonate concentrate was produced, containing 3545 Mn and 0.2% SiO2 at 98% removal. Das et al. (1978, 1979) investigated the recovery of manganese from ferro-manganese slag by acid leaching. The slag from ferro-manganese manufacture contained 1230% Mn(II) with the main impurities being CaO, SiO2, and Al2O3. The slag was leached with HCl or H2SO4. Manganese recovery was over 90% under optimum conditions. Comba et al. (1991) developed a calcium fluorideenhanced hydrochloric acid leaching procedure for
Table 4 Reductive leaching of manganese nodules by aqueous SO2/sulfite Reagents (NH4)2SO3 (S1) (NH4)2CO3 (S2) SO2H2SO4 SO2 SO2NH3 SO2NH3 (Pressure leach) (NH4)2SO3 SO2(a)H2SO4 (b)(NH4)2SO4(c) Na2SO3(NH4)Cl Conditions 100 mesh 80 C, 120 min 50 g/L (S1) 120 g/L (S2) Control the ratio of mole of SO2 to nodule weight Key results S1 enhanced recovery (%) Ni 93, Co 98, Cu 97 Mn and Fe b 1 Selective for Ni, Co, and Mn over Fe and Cu SO2 alone non-selective SO2NH3 selective for Ni, Co, and Cu (%) 85 Cu, 90 Ni, 80 Co 55% Mn in Mn cake Ea = 62 kJ/mol R = k[S(IV)][MnO2]0.5 Fit 1 (1 a)1/3 = kt (%) 88.5 Cu, 99.8 Ni, 91.8 Co, 97.8 Zn, 99.6 Mn and 2.4 Fe R depends on [S1] and [S1] R(Mn, Ni, and Cu) pore diffusion R(Fe) surface chemical Rate (Co) jointly controlled (1) leach Ni and Cu (2) leach Co and Mn N90% Ni, Cu and Mn N85% Co (1) monitor Eh for Co recovery (2) selective for Ni and Cu 5157% Mn recovery Selective (%) 93 Ni, 92 Cu, 65 Co Ref Maslenitskii et al. 1969 Pahlman and Khalafalla 1979; Kanungo and Das 1988 Kawahara et al. 1991 Mittal and Sen 2003 Das et al. 1998 Demirbas 1999 Acharya et al. 1999 Choi et al. 1996 Li et al. 1997 Sventsitskii et al. 2003 Kane and Cardwell 1976 Vu et al. 2005 Jana et al. 1999 Javorek 1988 Saha et al. 1993
Pilot plant pH 89 80110 C 60 g/L (a), 3% (b), 100 g/L (c) 20% solid, 3 h 1080 C 0.52.5 h
(1) spent electrolyte (2) 100 g/L FeSO4 FeSO4H2SO4 Roasting NH3/Air leach Roasting NH3CO2 leach Roasting aq. NH3(NH4)2CO3
(1) 4080 C (2) 50 C, pH 34 90 C, 30 min Roasted at 750 C Two stage leaching 190200 NH3 85110 g/L CO2 Leachate aeration Leach with air
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recovery of manganese from manganese-bearing silicate ores. The proposed process is an alternative to hightemperature and energy-intensive extractive techniques. Single-stage leaching with a stoichiometric amount of HCl and F-Mn mole ratio of 0.2 extracted 96% Mn when the leaching conditions were 50 C, 3 h, and 35% solids. Manganese at 98% recovery was achieved during a countercurrent leaching under similar conditions and 99% CaF2 was reclaimed. 4. Processing of manganese nodules, heterogenite and secondary materials 4.1. Processing of manganese nodules
4.1.1. Leaching with sulfur dioxide The higher oxides of Mn Ni and Co in manganese nodules, if present, would require reductant to convert the higher oxides to soluble forms. Goethite may give ferric sulfate or is reduced to give ferrous sulfate in solution. The various reactions in the presence of aqueous SO2 have been reported by Acharya et al. (1999): MnO2 H2 SO3 MnSO4 H2 O Co2 O3 2H2 SO3 2CoSO4 2H2 O Ni2 O3 2H2 SO3 2NiSO4 2H2 O 2FeOOH 3H2 SO4 Fe2 SO4 3 4H2 O 18 19 20 21 22
Manganese nodules have been recognized as a potential source of various metals such as Cu, Ni, Co and Mn. It is well known that the manganese nodules contain these metals as higher oxides or hydroxides and usually amorphous in nature. Therefore, it is essential to roast or leach the manganese nodules in the presence of a reductant. In pre-roasting, non-coking coal can be used as reductant followed by leaching (Javorek, 1988; Saha et al 1993). In direct reductive leaching, various reductants were investigated including sulfur (Mohanty et al., 1994), SO2 or sulfurous acid (Pahlman and Khalafalla, 1979; Kanungo and Das, 1988), manganous ion (Acharya and Das, 1987), glucose (Das et al., 1986), Charcoal (Das et al., 1989) and ferrous iron (Anand et al., 1988). Among these reductants, SO2 and FeSO4 are two of the effective reductants for MnO2 leaching. However, SO2 is preferred for its rapid rate of reaction, low temperature operation, ease of purifying leach liquor and elimination of barren solution disposal problem. Importantly, SO2 is cheap to make and can be easily extracted from spent gas of smelters. In comparison to manganese ores, the leaching of manganese nodules is more complex and difficult due to their matrix structures and polymetallic value recoveries. These metals are present in nodules as oxides or hydroxides. The major matrices for Mn and Fe are todorokite (buserite), MnO2, goethite, maghemite or Mn-hematite, where nickel and copper are mainly associated with manganese oxide phases and cobalt mostly with the iron phase, but possibly also with the manganese oxides. The most stable species of these elements in the ocean environment are MnO2, Fe2O3, CuO, Ni3O4 and Co2O3 (Vu et al., 2005). The recent developments in processing ocean manganese nodules have been reviewed by Mukherjee et al. (2004). Table 4 summarises typical studies on reductive leaching of manganese nodules.
2FeOOH H2 SO4 H2 SO3 2FeSO4 3H2 O
The selectivity of Ni, Co and Mn over Cu, Fe and Al was found to depend on the ratio of the mole of actually dissolved SO2 in the solution (MSO2) to the weight of ground nodules (Wsn) (Pahlman and Khalafalla, 1979). Optimum ratio of MnSO2/Msn would vary with specific composition and amount of nodules. For the Indian Ocean nodules which are low in copper, such selective leaching may not be economically viable (Kanungo and Das, 1988). Depending on the reaction conditions, formation of manganese dithionate or soluble metal bisulfites may take place. The Fe(III) present in the solution may precipitate as jarosite in the presence of ammonium sulfate as shown below: 3Fe2 SO4 3 12H2 O NH4 2 SO4 2NH4 Fe2 SO4 3 OH6 23
The rate of leaching with aqueous SO2 was found to increase with dissolved SO2 concentration up to 80 C (Demirbas, 1999). In the temperature range of 80100 C, the activation energy was determined to be 6265 kJ/mol, indicating a chemically controlled process (Das et al., 1998; Demirbas, 1999). In sodium sulfite and NH4Cl solution, the dissolution rates of manganese, nickel and copper were found to be controlled by pore diffusion, whereas iron by surface chemical reactions and cobalt limited by both surface chemical reactions and pore diffusion (Choi et al., 1996). With an increase in temperature from 80 to 100 C, the ratio of Mn2+/Mn3+ increased by about five times indicating favourable formation of lower valency states of manganese ions at higher temperatures (Das et al., 1998). Similar to the leaching of manganese ores, the reaction product of SO2 was mainly sulfate with a

2 proportion of dithionate (S2O6 ), depending on specific leach conditions (Popov et al., 1981). The ratio of dithionate to sulfate was found to increase with increasing SO2 concentration and higher solution pH in the leach solution. For processing polymetallic values such as Ni, Co, Cu, Mn, and Fe, the leaching with aqueous SO2 alone was found to be non-selective (Kawahara et al., 1991; Li et al., 1997). A selective extraction of Ni, Co, and Cu from Mn nodules can be achieved by using ammonia/carbonate solution in the presence of sulfur dioxide as the reductant. Strategies in the presence and absence of O2 (air) can be used to selectively complex metal values in the solution or to precipitate basic manganese carbonate via heating and recovery of ammonia (Rokukawa 1990). Pre-treatment of the ores with dilute acetic solution was found to be effective to remove a substantial quantity of calcareous and carbonaceous material from the nodules (Pahlman and Khalafalla, 1988). An increase in temperature suppressed the dissolution of iron into the leach solution. The leaching residue was mainly composed of manganese ammonium sulfite hydroxide ((NH4)2Mn2(SO3)3) in an ammonia solution while manganese carbonate was detected in the leaching with ammonium carbonate solution. Most of Cu, Ni, and Co was extracted into solutions, leaving most manganese in the residue at 80 C for 120 min. A polymetallic manganese nodules pilot plant of 500 kg per day processing capacity was designed and set up at Hindustan Zinc Limited, Udaipur (India) (Mittal and Sen, 2003). The process was based on the reductive alkaline pressure leaching of nodules using sulfur dioxide as reducing agent in the presence of ammonia at pH 89. The overall process scheme is shown in Fig. 2.
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In this process, the partially dissolved manganese during leaching along with copper, nickel and cobalt was precipitated and separated out as manganese dioxide in a demanganisation autoclave by sparging oxygen. Free ammonia present in the leach liquor was recovered in an ammonia stripper and recycled back to leach autoclave as recycled ammonia. Ammonia free leach liquor was subjected to single stage copper extraction with LIX 84I at controlled pH for selective removal of copper. The copper ranate containing dissolved nickel and cobalt was subjected to sulfide precipitation using sodium sulfide. The nickel and cobalt were precipitated as sulfides along with minor impurities like copper, zinc, iron etc. The cake was dissolved in a dilute sulfuric acid solution in the presence of oxygen under medium temperature and pressure conditions. The cobalt and nickel in the purified leach solution were extracted with PC88A and D2EHPA respectively and produced as pure metal through electro-winning. The experiments conducted in the pilot plant showed an average recovery for copper, nickel and cobalt as 85%, 90% and 80%, respectively. The process has several advantages and compares well with other alternative hydrometallurgical processes for extraction of metals from poly-metallic nodules. First, the major reagent is sulfur dioxide, which is comparatively cheap and can also be economically extracted from smelter off-gases. Second, the high recoveries for nickel, copper and cobalt values can be achieved, which not only covers the mining cost but gain additional profits. Last, the manganese cake containing 55% manganese can directly be used for the production of highgrade ferro-manganese.
Fig. 2. Schematic flowsheet of manganese nodule pilot operation using SO2 reductant in Indian (based on Mittal and Sen 2003).
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The National Metallurgical Laboratory (NML) of India developed a two stage ammoniacal leaching scheme with a prior pre-conditioning step (Jana et al., 1999). The necessity of monitoring redox potential in the first stage leaching to control cobalt recovery has been emphasized. Based on the two stage leaching scheme, recycle leaching has been carried out to generate leach liquor having suitable composition for the subsequent solvent extraction-electrowinning operation. The average recovery of metals in 16 cycles of leaching has been found to be 92% Cu, 90% Ni and 56% Co. 4.1.2. Leaching with FeSO4 A two-stage leaching process for selectively extracting metal values from manganese nodule was developed by Kane and Cardwell (1976). In the first stage leaching, spent electrolytes containing about 4% free acid were used to leach the nodule for 14 h at 4080 C for preferentially extracting nickel and copper values. In the second stage, the filtered solids were reductively leached with solutions containing approximately 100 g/L FeSO4 at about 50 C and pH 34 to extract cobalt and manganese. Air was bubbled through the leach solution in the second stage to remove iron as oxides/ hydroxides to the residue. Copper was extracted at pH 2 from the first stage leach solution using a -hydroxy oxime or 8-hydroxyquinoline. The copper strip solution was electrolysed to give the cathodic copper product, and the raffinate from the solvent extraction was similarly treated in a nickel cell for the recovery of cathodic nickel. After iron was removed from the second leach solution, cobalt was extracted by the organic solution at pH 3.54.5, and the raffinate was electrolysed for the recovery of manganese. Leaching of manganese nodule in ammoniacal medium using FeSO4 as the reductant was investigated by Anand et al. (1988). Ferrous iron in ammonia-ammonium solution can form a sable ferrous ammine complex in the pH range of 9.5 to 9.8. It is oxidised and precipitated as ferric hydroxide by simultaneous reduction of MnO2, Ni3O4, Co2O3 minerals to lower-valence metal ions which can be stabilised in the solution as metal ammines. While maintaining the total molarity of ammonia and ammonium sulfate at 5.85 M, most of the copper, nickel and cobalt, and about 32% of manganese could be leached within 10 min. An extension of leach time resulted in partial precipitation of manganous ammine as MnO or Mn2O3 and the loss of nickel and cobalt due to coprecipitation or adsorption. This process could eliminate iron in the solution in the ppm level. However, it was difficult to optimise the selectivity of Ni, Co and Cu over manganese by varying the total concentration of
ammonia and ammonium sulfate in the range of 1.96 to 5.85 M. Other variable affecting the extent of extraction of Ni, Co, Cu and Mn included the amount of ferrous sulfate, leaching temperature and initial pH. More recently, the leaching of manganese nodule with FeSO4H2SO4H2O solutions has been reported (Vu et al., 2005). The manganese deep ocean nodules originated from the IOM area, located in the Clarion Clipperton ore field. The optimum conditions established were as follows: stoichiometric amount of FeSO4, 1.6-fold excess over stoichiometric amount of H2SO4, 90 C, l/s of 7:1, grain size 1000 m. Under these conditions, more than 85% of Co and 90% of Ni, Cu and Mn could be extracted within 30 min. The leach liquors contained approximately 146 mg/L Co, 1.63 g Ni/L, 1.69 g Cu/L and 30 g/L Mn. Compared with a non-selective leaching process, the two-stage leach process enable nickel to be separated from cobalt at early leaching stages and make the subsequent separation process simple and easy, but the energy consumption is expected to be high in the leaching stages. The applicability of the process would largely depend on the valuable metal grades in the nodules and the availability of cheap spent industrial pickle liquors. 4.1.3. Leaching with nitrogen dioxide and nitric acid Nitrous-nitric method was tested for processing ocean nodules to recover the manganese value selectively (Welsh and Sochol, 1978). The nodules comprised primarily oxides of manganese and iron with lesser amounts of Cu, Ni, Co, alkali metal and alkaline earth metal compounds. The process was comprised of leaching the nodules at 80 C with an aqueous solution of nitrous and nitric acids; removing insoluble iron oxide and gangue at pH b 2.5 by filtration, adding Mn (OH)2 to the filtrate to selectively precipitate Cu, Ni and Co metals as hydroxides and adding to the filtrate H2S to precipitate metal traces as sulfides to obtain purified manganese sulfate solution. 4.1.4. Leaching with cuprous copper solution Szabo (1976) developed an ammoniacal cuprous leach process for recovery of metal values from manganese deep sea nodules. This process has been tried at a pilot plant. The process consisted of ore preparation, reduction-leach, oxidation and wash-leach, LIX separation of the metals, and electrowinning. The nodules were leached with an ammoniacal solution containing Cu(I) ions to reduce the manganese oxides and extract Cu, Ni, Co and Mo into solution. The cuprous ions used for the leaching were regenerated by reduction of the Cu (II) with a reducing gas such as a mixture of CO 95%
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and H2 5%. The nodule residue was washed with an ammoniacal-(NH4)2CO3 solution to remove entrained metal values and the wash effluent contained Cu, Ni, Co, and Mo values. Rappas (1985) reported a process for the extraction of metals from laterite ores and ocean manganese nodules with a stabilised acidic cuprous ion solution (Cu+L) in a suitable reactor at a temperature up to 90 C and pH in the range of 1.52.5, wherein L is a stabilising ligand selected from the group consisting of CO, XRCN and Cl, X being H or OH and R being aliphatic compound having 14 carbon atoms. The cuprous copper process is considered less suitable for practical applications due to the unstable nature of the cuprous ions in the leach solutions. Sufficient ligands or complexing agents are needed to present in the leach solution and also in the relatively expensive regeneration process. 4.2. Treatment of heterogenite In recent years a new manganese bearing ore has drawn attention. It is heterogenite from Africa, containing cobalt, cupper and significant quantities of manganese. A frowsheet was developed and piloted at Mintek during 1998 for recovering Cu and Co from the Kakanda (Democratic Republic of Congo) tailings (Dry et al., 1998; Sole et al., 2005). This was an acid/SO2 reductive leaching process. Copper in the leach solution was recovered by SX-EW. A bleed of the raffinate went through Fe and Al removal by neutralisation, manganese (about 1 g/L) recovery or removal by solvent extraction using D2EHPA, and cobalt recovery by solvent extraction using Cyanex 272 followed by electrowinning. Recently, processing of African Heterogenite at Rubamin Ltd, India has been reported by Das (2006). A similar reductive acid leaching with SO2 as reductant is used under controlled pH. The leach liquor containing Mn, Zn, Cu, Ni, and Fe along with Co is first neutralised with lime to precipitate most of the Fe and Cu, followed by extraction of Mn and Zn from the leach liquor by D2EHPA, and then extraction of cobalt by phosphonic acid (P507, produced in China). Nickel in the raffinate is recovered as nickel carbonate. The electrolytic cobalt produced at Rubamin has a purity of 99.9%. The overall recovery of cobalt from heterogenite is more than 90% together with production of a wide range of salts of cobalt, copper, nickel, and manganese. 4.3. Treatment of waste batteries Lindermann et al. (1994) described the Batenus process for recycling battery waste. The crushed batteries
were leached in sulfuric acid. Several techniques were employed for the separation of metals. 1. The insoluble manganese dioxide and carbon residue were sold to the ferro-manganese industry and the metal salt solution was treated by ion exchange to recover copper, nickel, cadmium, and mercury. The zinc was recovered by solvent extraction. 2. The manganese from the leach solution was precipitated as carbonate from the raffinate. 3. The remaining alkaline metal sulfate and chloride solution were separated into acid and base by electrodialysis with bipolar membranes. The Batenus process was reported to be free of any emission, and produce raw materials with remarkably high purity. The zinc, nickel, cadmium, copper, and mercury were separated out of the used zinc-carbon, alkaline manganese, and nickel-cadmium batteries. Moreover, the manganese carbonate, obtained as raw material, could be used for the production of manganese dioxide for new batteries. A hydrometallurgical process for the recovery of zinc and manganese from spent batteries was developed by Bartolozzi et al. (1994). In this process, the spent batteries was leached with 32% sulfuric acid, and after liquid and solid separation, the dissolved iron was removed by precipitation by NaOH at pH 3.7 and then by 32% ammonia at pH 5 and 60 C with addition of small amount of H2O2. The subsequent solution was first electrolysed to remove Hg, Ni, and Cd, and then at pH 3.7 was electrolysed to recover cathodic zinc and anodic MnO2. The Mn(IV) in the leach residue was solubilised in acidic hydrogen peroxide (35%) and re-precipitated with NaOH at 40 C. This process appears feasible technically, but hardly likely to be applied economically with so strong conditions and the use of expensive reagents such as H2O2 and NaOH to recover manganese dioxide. For treatment of waste lithium battery, Shibata and Baba (1995) investigated a process in which lithium and manganese were selectively leached from the battery by using diluted mineral acids HCl and HNO3. Lithium and manganese were precipitated as their carbonates from the individual leached solution with sodium carbonate solution. A process for recovery of metal values from chemical by-products of spent MnZn batteries was reported by Ptitsyn et al. (2001b). The by-products from spent MnZn batteries were processed by grinding, magnetic separation of iron scraps, firing the powders, acidic leaching, and electrowinning of zinc on the cathode and MnO2 on the anode.
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4.4. Treatment of Mn-bearing sludges and slags Kukula and Sikora (1977) reported a hydrometallurgical process for the recovery of manganese from slag leaching solutions. The solution contained (g/L) SiO2 1520, Mn 25 and (NH4)2SO4 197, and (mg/L) Cr 1.5, Ni 2.76, Co 7.78, Cu 5.4, Mo 0.95 and Fe 800. The purification was accomplished by the following procedure: 1. SiO2 was removed by precipitation with lime. 2. Fe2+ was precipitated as Fe(OH)3 after oxidation with KMnO4. 3. Nickel and cobalt were removed partly by co-precipitation with iron, partly by reduction with manganese dust added. 4. The excess of cobalt was extracted by solvent extraction, and the organic impurities were removed by adsorption on active carbon. 5. From the pure solution, manganese was recovered electrolytically on aluminium cathode at current density 300400 A/m2 in a membrane system. The feasibility of this process would depend on the initial concentrations of manganese and other valuable metals such as cobalt and nickel in the solution. For this particular case, the initial cobalt content is considered too low to be feasible. A process for the recovery of manganese from electrolytic zinc anodic slime and from scrap dry cells described by Yoon and Kim (1986) involved the following steps: (a) manganese was extracted from anodic slimes of electrolytic zinc anodic slime and scrap dry cells by leaching with HCl. (b) The impurities (Zn, Fe, Pb) were removed from the leach solution prior to electrolysis by neutralization with NH4OH and cemen-
tation with manganese powder. (c) The manganese was electrodeposited from the purified chloride solution with added Na2SeO4. However, evolution of Cl2 during leaching and electrowinning are likely to be issues and consumption of ammonia is expected to be high. A process for recovery of Zn and Mn from a water treatment plant sludge was developed (Pesic et al., 1996; Binsfield et al., 1996). The process features leaching of the sludge with H2SO4 in the presence of SO2 reductant at pH 2 and 60 C for 15 min, three-stage purification, and simultaneous electrowinning of zinc and MnO2. 5. Process for recovery of manganese from solution 5.1. Manganese electrowinning-production of electrolytic manganese Electrowinning of manganese is a major process for production of high purity electrolytic manganese (EM). The electrowinning systems can be classified based on the media such as sulfate and chloride because all the parameters differ substantially in different media. Electrowinning of manganese in sulfate solutions has been conventionally employed for production of most manganese metal required mainly for steel alloys, particularly in special steels such as low carbon stainless steel grades. The overall process for production of electrolytic manganese from ores consists of a series of steps as presented in Fig. 3. Iron(III) is typically removed by hydroxide precipitation at pH 34 and other impurities such as Ni, Co, Cu, Zn are removed by sulfide precipitation. The resultant MnSO4 solution can be used for production of electrolytic manganese. This process was first developed by Fuller et al. (1964) and was implemented
Fig. 3. Conventional process for production of electrolytic manganese (EM) and electrolytic manganese dioxide (EMD).
W. Zhang, C.Y. Cheng / Hydrometallurgy 89 (2007) 137159 Table 5 Electrolysis of manganese from sulfate solution (Pisarczyk 1995) Condition Feed solution, catholyte MnSO4 (NH4)2SO4 SO2 Anolyte MnSO4, g/L H2SO4, g/L (NH4)2SO4, g/L Current density, mA/cm2 Catholyte pH Anode composition Cathode composition Cell voltage Temperature Diaphragm Current efficiency Value 3040, g/L 125150, g/L 0.30.5, g/L 1020, g/L 2540, g/L 125150, g/L 4365 67.2 Pb + 1% Ag Hastelloy, type 316 5.1 V 20 C Acrylic 6070%
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2. Evolution of chlorine at the anode which has to be removed or destroyed. These disadvantages have limited the application of manganese electrowinning in chloride medium. 5.1.1. Effect of additives An addition of 0.155.0 mg/l of Zn2+ to the catholyte in the manganese deposition cell has been reported to increase the cathode current efficiency (Mantell and Ferment, 1969; Ilea et al., 1997) and decrease the minimum current density necessary for manganese deposition on the cathodes. This occurred in both pure solutions and solutions containing trace amounts of impurities in manganese ores, e.g., Co, Ni, Mo, and Cu. This effect was observed for the catholyte containing (g/L) Mn2+ 35, (NH4)2SO4 120, and SO2 0.1 at 30 C and pH 7.2, with the anolyte containing (g/L) MnSO4 15, H2SO4 30, and (NH4)2SO4 130. However, in the presence of Zn2+ greater than 5.0 mg/L, the purity of the deposited manganese was decreased to below 99.9%. The presence of selenium and tellurium ions in the electrolyte was also found to be beneficial for the cathodic current efficiency and specific energy consumption (Louis and Martin, 1976; Ilea et al., 1997). For an industrial electrolyte containing 105 g/L MnSO4 and 1 M (NH4)2SO4 in the presence of 1 mM H2SeO3, the current efficiency reached 82% and specific energy consumption was 6.8 kWh/kg for a conversion of about 44%, at 500 A/m2, pH 78 and 20 C (Ilea et al., 1997). Using Pt or Al cathode and a PbAg anode, selenium was found in the anode mud, as higher valent manganese selenites (Suliakas et al., 1973). Minimum amount of the anodic mud was produced at pH 2 and 40 C at 100 g/l H2SeO3. When selenium was present as SeO4, an insoluble selenium compound appeared only at temperature greater than 70 C and was independent of the electrolyte pH. A natural or synthetic organic H2O-soluble polymer, e.g., a H2O-soluble polyacrylamide or natural guar gum in combination, led to less mechanical work in removing the deposited manganese from the cathodes and an increase in both the quantity and quality of the deposit (Coleman and Griffin, 1984). An addition of thiourea in the range 0.0150.03 g/L was found to promote current efficiencies up to 6068% (Hammerquist, 1951). 5.1.2. Impurity control Since manganese has a high negative value in the electromotive series, the levels of metals with higher reduction potentials have to be controlled to a low level.
by Harris et al. (1977) in South Africa. The plant operated at its rated capacity of 16,500 t/year at current efficiencies of approximately 68%. The typical conditions required for the electrolysis process are summarised in Table 5 (Pisarczyk, 1995). The concentration of MnSO4 was found to be one of the key parameters required for achieving a high current efficiency (Jakuszewski et al., 1972). In electrolysis, both anodic and cathodic yields were improved with an increased MnSO4 concentration. An increased (NH4)2SO4 concentration gave a higher yield of cathodic manganese with an improved quality, while an increased H2SO4 concentration gave a smaller yield of relatively pure MnO2 at anodes (Jakuszewski et al., 1972). A number of studies on electrowinning of manganese in chloride electrolytes have been reported in the literature (Jacobs and Churchward, 1948). Compared with the sulfate system, the electrolytic process in chloride medium offers some potential advantages and disadvantages (Agladze and Muchaidze, 1957a): 1. Lower cell potential can be used, resulting in up to 25% less power consumption. Generally, the efficiencies are higher than the sulfate systems by 510%. 2. 23 times higher current density can be achieved (Parissis and Winand, 1992), thereby decreasing the size of the electrolysis plant. However, it has potential disadvantages: 1. Large amounts of ammonia in the electrolyte may decompose at the anode at approximately 0.3 t per ton of manganese.
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Table 6 The maximum admissible impurity content in industrial manganese electrolytes Elements Maximum admissible (mg/L) References Al Co Fe Cu Ni Zn Mo 1000 0.5 10 5 0.11 20 N5 affect Mn quality 1.5 Ilea et al. 1997
2. After digestion, the pH was adjusted to 5.56.0 to precipitate Fe and some of Mo as sludge. 3. The pH was then adjusted to 7.07.5 and (NH4)2S added to precipitate the Mo, Co, and Ni. The presence of silica is detrimental to the formation of a satisfactory cathodic deposition in manganese diaphragm electrowinning. A coagulation method with Al2 (SO4)3 as the coagulant was developed (Hammerquist, 1948). The process required the solution pH in the range of 5.57.5 and the ratio of 2025 kg of Al2(SO4)3 to about 100,000 kg of electrolyte. The precipitate, Al (OH)3, could then be filtered off. 5.1.3. Effect of anode types The type of anode plays an important part in manganese electrowinning. In addition to the physical properties such as resisting breaking and bending, the electrochemical properties in terms of resistance to corrosion and allowance for low potential for O2 evolution are major concerns. Lead or lead alloy anodes are conventionally used in manganese electrowinning in sulfate medium while in chloride medium, C or graphite is usually employed. Various new types of anodes containing composite elements have been developed. The novel anode types include an alloy of Pb, Sn, Sb and Co (Fink and Kolodney, 1939), a composite anode containing 0.55% Ni and 110% Mn, and balance Ti alloy (Debrodt et al., 1986), a composite anode consisting of 0.502.4% Ag, 0.252.5% As, and the balance Pb (Godsey, 1955), an anode of Ti, Zr, or Ta coated with a layer of MnO2 (Osawa, 1973), and Ti anodes (Ptitsyn et al., 2001a). These composite alloys generally improve the life of the anode and lower the cell energy consumption. However, the composite anodes are costly and the application of these novel types of anodes largely depend on the balance of cost and benefits offered. 5.2. Production of electrolytic manganese dioxide (EMD) EMD can be made by the anodic oxidation of MnSO4 solution with inert electrodes. The cell reactions are: Anode : Mn2 2H2 OMnO2 4H 2e Cathode : 2H 2e H2 Overall : Mn2 2H2 OMnO2 2H H2 24 25 26
O'Keefe 1984 Ilea et al. 1997 Mantell and Ferment 1969 Anon. 1949
Typical impurity contents in the industrial electrolyte and their admissible concentrations are given in Table 6 (Ilea et al., 1997). Not all the metals in the range affect the polarization (Mantell, 1944). Ni, Co, Ag, Cu, Zn and Mo had some effects while Cd, Mg, and Na was found to have no effect. In a patented method (Mantell and Hammerquist, 1944), the level of magnesium in the anolyte was controlled by fluoride precipitation. For the anolyte solution containing MnSO4 115 g/L and (NH4)2SO4 15075 g/L, magnesium in the anolyte was precipitated as MgF2 by addition of a soluble fluoride, e.g., NH4HF2 in a controlled pH range of 1.52.75. The precipitate was then removed by filtration. The concentration of magnesium left in the solution was below 2 g/L. The filtrate was passed to the leaching tank and used for leaching of manganese ores. Nickel, cobalt, and copper are the common impurities in the electrowinning of manganese. The electroplated manganese can couple the electroplated Ni, Co, and Cu to cause redox reactions resulting in hydrogen evolution. A study on the corrosion rate in a solution containing 25 g/L Mn and 150 g/L (NH4)2SO4 at pH 7 and 20 C showed that the MnCo and MnNi couples had slightly greater corrosion rates than manganese alone with relative influence in the order Co N Ni N Cu (Agladze and Gofman, 1957). The presence of molybdenum seriously affects the efficiency of production of high-quality EMD. The upper critical maximum concentration of molybdenum was established to be 1.5 mg/L (Anon, 1949). A procedure was developed for the control of Fe, Mo, Ni and Co in the electrolyte (Wanamaker and Morgan, 1943; Anon, 1949; Wanamaker et al., 1951). It consisted of three major steps: 1. The spent electrolyte was oxidised with the cell sludge as well as additional manganese ore in which manganese must be present in a valence greater than 2.
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The mechanism of deposition of MnO2 on anode was proposed to form initial Mn3+ which disproportions according to: Mn3 2H2 OMnO2 Mn2 4H 27
A typical process for production of EMD from MnO2 or MnCO3 ore includes reductive roasting if MnO2 ore is used followed by sulfuric leaching and purification steps (Taylor, 1993) which are similar to those for preparation of EM solutions (see Section 5.1). The removal of potassium is required for production of electrolytic manganese dioxide because the presence of potassium during electrolysis promotes the formation of the -MnO2 which is non-battery active. This is usually achieved by jarosite or alunite precipitation in the leaching process in which ferric sulfate is normally added (Paixao et al., 1995). A jarosite precipitation reaction can be represented by: K 3Fe3 2SO2 6H2 O 4 KFe3 SO4 2 OH6 6H 28
unroasted manganese carbonate and sodium and potassium salts followed by washing and drying to yield the CMD product with 90% as MnO2. A fully hydrometallurgical process for production of CMD was proposed by Raghavan and Upadhyay (1999), which used Na2SO3 reductive leaching instead of conventional reductive roasting. A commercial process for recovery of manganese dioxide is based on thermal decomposition of manganese nitrate solution to produce a substantially pure CMD (N 99.5%) (Welsh, 1973, 1978). The process involved heating a crude Mn(NO3)2 solution from leaching Mn-bearing ores at 90100 C and adjusting pH to 4.55.0 with addition of MnO obtained by the reduction of MnO2-containing ores. The solution was filtered and continuously added to a stirred reactor held at 135146 C, where the Mn(NO3)2 decomposed to MnO2 and NO2 according to the reaction: MnNO3 2 MnO2 2NO2 30
BHP Minerals International built and commercialised an EMD plant comprising conventional reductive roasting, leaching, purification steps in Newcaslte, Australia using a high manganese ore in 1991 (Taylor, 1993). 5.3. Production of chemical manganese dioxide (CMD) Chemical manganese dioxide (CMD) can be prepared by various methods including thermal decomposition of manganese salts such as MnCO3 or Mn(NO3)2 under oxidising conditions. CMD can also result from the reduction of higher valent manganese compounds, eg, those containing the MnO4 ions. The conventional process for production of CMD is via a carbonate route (Raghavan and Upadhyay, 1999). In this process, manganese dioxide ore was treated by reductive roasting followed by sulfuric leaching. After removal of impurities by neutralisation to the pH range of 46 and filtration, manganese in the solution could be sent to electrolysis to produce electrolytic manganese dioxide (EMD) or recovered as MnCO3 by addition of (NH4)2CO3. MnO2 (CMD) was obtained by heating the MnCO3 in the presence of oxygen or air at about 500 C based on the reaction: MnCO3 1=2O2 MnO2 CO2 29
The NO2 generated could be recycled by reaction with water: NO2 H2 OHNO2 HNO3 31
The acid formed then reacted with low grade manganese dioxide ore forming slurry of the crude manganese nitrate to feed the process. Recently, Pagnanelli et al. (2007) investigated three chemical procedures for preparation of chemical manganese dioxide (CMD) for possible applications in dry cell batteries instead of electrolytic manganese dioxide (EMD). The three preparation procedures were: (a) precipitationoxidation by air plus acid activation (two-step-air) (b) precipitationoxidation by H2O2 plus acid activation (two-step-H2O2), and (c) precipitationoxidation by KClO3 (single-stepClO3) The two-step procedures gave larger throughputs of activated manganese dioxide (8086%) compared with single-step preparation. The effect of operating conditions on the chemical, structural and electrochemical properties of CMDs produced under optimised conditions was investigated and compared with those of a commercial EMD sample. The two CMD samples prepared using the two-step procedures demonstrated, by potentiometric titrations, the same acidbase properties
The manganese dioxide and manganese carbonate mixture was further leached with sulfuric acid to removed
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Fig. 4. A schematic diagram for low-dithionate acid leach process (based on Ward et al., 2004; Ward, 2005).
which had the structure and proton insertion properties similar to the commercial EMD, but different structural defects. X-ray and IR spectra showed highly disordered systems of the CMD samples and the presence of Mn2O3 in first step products and of MnO2 in second step product. Voltammetric cycles denoted that CMD samples obtained after acid digestion present similar peaks to the commercial EMD but with a higher current intensity. These are encouraging results for further investigations of CMD and its characterisations in comparison to EMD for applications in battery industry. 5.4. Recent hydrometallurgical processes for production of CMD and EMD Chemical manganese dioxide is conventionally manufactured by a roastingleaching process as shown earlier. However, this is economically justified only for the manganese ores containing N 40% Mn. Some pure hydrometallurgical processes for production of CMD have been developed in recent years. One of the processes has been proposed by Raghavan and
Upadhyay (1999) for recovery of manganese as CMD or EMD from manganese ores and other manganese bearing materials such as anode mud. It involves aqueous SO2 and H2SO4 leach at pH 2.5 and 90 C, purification with limestone to remove the iron present, crystallisation at 4 C to control the build up of sodium sulfate, precipitation of manganese with addition of sodium carbonate at 70 C and calcination at 500 C. The purification of the calcine to remove unroasted manganese carbonate could be achieved by leaching with 5 10 g/L H2SO4 to produce quality MnO2. In processing of manganese nodule ores with SO2 as reductant, one of the problems is the generation of a proportion of dithionate along with sulfate product during the reduction. The presence of dithionate would result in a slow release of SO2 from the MnSO4 product. A low-dithionate acid leach process for the treatment of low-grade manganese ores and Mn-waste sources for manufacture of high-quality EMD for the alkaline battery market has been developed by HiTech Energy Ltd. (Ward et al., 2004; Ward, 2005). The process features leaching with acidic solution at b60 C and controlled
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potential (Eh) for addition of SO2 gas and manganese ore feed to minimise generation of dithionate ion. The manganese in the leach solution was extracted using a carboxylic acid, e.g. Versatic 10, at pH 5.56.5 followed by stripping with spent aqueous H2SO4 electrolyte to obtain MnSO4 feed solution for electrowinning to produce EMD (MnO2). A schematic diagram of the improved Process II vs conventional Process I is shown in Fig. 4. 6. Conclusions The major and potential manganese sources, routes and products are graphically summarised in Fig. 5. Rich manganese ores (N40% Mn) are dominantly processed by pyrometallurgical processes to produce ferro-Mn and silico-Mn alloys, which are mainly used in iron and steel industry. Production of CMD, EM and EMD are mainly accomplished by reductive roasting followed by hydrometallurgical processing. Low manganese ores (b 40% Mn) and polymetallic manganese nodules currently cannot be economically processed by pyro-processes because too much energy is required. A number of hydrometallurgical processes have been developed, both in acidic and basic media. Among the various methods developed, the reductive leaching of Mn(IV) to Mn(II) has been extensively investigated, including the reductants of aqueous SO2, ferrous salts,
reducing organics, H2O2, sulfide minerals, bio- and electro-reduction. Among these processes, the sulfur dioxide reductive leaching process has been developed to a pilot scale for processing of manganese ores and manganese nodules. One problem to use SO2 as the reductant is the formation of dithionate by-product. It can be minimised by controlled the addition of SO2 to achieve a desired solution Eh as developed by HiTech Energy Ltd. However, the crucial issue is the purification of leaching liquors due to the extraction of iron and manganese in the course of leaching operations. Selective recovery of Cu, Ni and Co is often difficult from solutions containing soluble iron and manganese as contaminants. The leaching processes of ocean manganese nodules can be conducted in near ambient conditions, using cheap and readily available chemicals. Selective recovery of Cu, Zn, Ni and Co components is possible over manganese with ammoniacal sulfite alkaline leach. In this strategy, Cu, Zn, Ni and Co metals are extracted into solution as ammines whilst iron and manganese is stabilised in residue as hydroxide, oxides and carbonate. The main methods for recovering manganese from the leach solution include electrolysis for EMD production, electrowinning for EM production and chemical process for CMD production. Purification steps are needed, depending on what product is produced. Generally, iron and aluminium impurities are removed by hydroxide
Fig. 5. A schematic diagram of major and potential manganese sources, process routes and products.
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W. Zhang, C.Y. Cheng / Hydrometallurgy 89 (2007) 137159 Agladze, R.I., Muchaidze, N.N., 1957a. The recovery of metallic manganese by the electrolysis of chloride solutions. Elektrokhim. Margantsa, Akad. Nauk Gruzin. S.S.R. 1, 341353. Ali, E.A., Shahin, M.A., Ahmed, M.S., Ibrahim, I.A., 2002. Leaching of low-grade Sinai manganese ore using lactose as a reductant. Egyptian Journal of Chemistry 45 (2), 359374. Anon., 1949. Electrolyte purification in manganese electrowinning. GB Patent No. 627208. Anon., 2003. Date accessed: 15/6/2006 The Electrolytic Manganese Dioxide Market. http://www.hitec-energy.com.au. Anand, S., Das, S.C., Das, R.P., Jena, P.K., 1988. Leaching of manganese nodule in ammoniacal medium using ferrous sulfate as the reductant. Metallurgical Transactions B 19B, 331335. Arsent'ev, V.A., Kiselev, K.A., Ryl'kov, S.A., Sokolova, V.P., 1992. Experimental processing of Vorkutinsk manganese ores by hydrometallurgical methods. Obogashchenie Rud (Sankt-Peterburg, Russian Federation) (6), 1718. Arsent'ev, V.A., Yavorskaya, G.M., Kovaleva, O.V., 1991. Manganese recovery from oxide ores by leaching with acid. SU Patent No. 1624038. Bartolozzi, M., Braccini, G., Marconi, P.F., Bonvini, S., 1994. Recovery of zinc and manganese from spent batteries. Journal of Power Sources 48 (3), 389392. Binsfield, M.C., Pesic, B., Storhok, V.C., 1996. Recovery of zinc and manganese from Bunker Hill Water Treatment Plant sludge: part II electrowinning process development. In: Ramachandran, V., Nesbitt, C.C. (Eds.), Proceedings of the 2nd International Symposium on Extraction and Processing for the Treatment and Minimisation of Wastes, Minerals. Metals & Materials Society, pp. 719729. Brantley, F.E., Rampacek, C., 1968. Manganese and iron recovery from leach solutions. US Patent No. 3397130. Calvert, J.B., 2004. Date accessed: 29/9/2005 Chromium and Manganese. http://www.du.edu/~jcalvert/phys/chromang.htm. Chen, H., Fu, C., Zheng, D., 1992. Reduction leaching of manganese nodules by nickel matte in hydrochloric acid solution. Hydrometallurgy 28 (2), 269275. Choi, K.S., Han, O.H., Shin, B.S., 1996. Reduction leaching of manganese nodules with sodium sulfite in ammonium chloride solution. Shigen to Sozai 112 (2), 117121. Coleman, T.W., Griffin, R.A., 1984. Electrodepositing metallic manganese. US Patent No. 4478697. Comba, P., Lei, K.P.V., Carnahan, T.G., 1991. Calcium fluorideenhanced hydrochloric acid leaching of a manganese-bearing silicate ore. U.S. Bureau of Mines Report of Investigations. Cooper, H.S., Schaefer, J.C., Schmidt, E.C., 1959. Recovery of manganese from metallurgical by-products by chlorination. US Patent No. 2877110. Corathers, L.A., 2004. Date accessed: 21/6/2007. U.S. Geological Survey (USGS) Minerals Yearbook: Manganese -2004, http://minerals.usgs. gov. Corathers, L.A., 2005. Date accessed: 21/6/2007. U.S. Geological Survey (USGS) Minerals Yearbook: Manganese -2005, http://minerals.usgs. gov. Das, R.P., 2006. Processing of African Heterogenite at Rubamin Limited, India. Paper presented at Mineral Processing 2006, Cape Town, 34 August. South African Institute of Mining and Metallurgy. Das, P.K., Anand, S., Das, R.P., 1998. Studies on reduction of manganese dioxide by (NH4)2SO3 in ammoniacal medium. Hydrometallurgy 50 (1), 3949. Das, R.P., Anand, S., Das, S.C., Jena, P.K., 1986. Leaching of manganese nodules in ammoniacal medium using glucose as reductant. Hydrometallurgy 16, 335344.
precipitation and other base metals removed by sulfide precipitation. Jarosite precipitation is required for removal of potassium ions for the production of EMD. In recent development by HiTech, solvent extraction has been used to recover manganese from the leach solution and enable early rejection of the majority of impurities. One of the potential sources of manganese, which has not received much attention, is the recovery of manganese from industrial waste solutions, particularly from Ni-Co laterite high pressure acid leach effluents which contains about 15 g/L Mn together with other impurities. This is the focus of Part II of this review which considers the application of various solvent extraction reagents and precipitation methods. Acknowledgments The authors would like to thank CSIRO Minerals library staff for collecting some reference papers, and Dr David Muir for reviewing this paper and providing valuable comments. References
Abbas, H., Askar, M.A., Abd-Elaziz, E.M., 1999. Recycling of zinc carbon spent batteries: I. Production of manganese and zinc as sulfates. Egyptian Journal of Chemistry 42 (4), 361373. Abbruzzese, C., 1987. Aqueous SO2 processing of manganese ores. In: Davies, G.A. (Ed.), Separation Processes in Hydrometallurgy, Society of Chemical Industry. Ellis Horwood Limited, London, pp. 7787. Abbruzzese, C., 1990. Percolation leaching of manganese ore by aqueous sulfur dioxide. Hydrometallurgy 25 (1), 8597. Abbruzzese, C., Duarte, M.Y., Paponetti, B., Toro, L., 1990. Biological and chemical processing of low-grade manganese ores. Minerals Engineering 3 (34), 307318. Abdrashitov, Y.M., Dmitriev, Y.K., Zakharova, N.V., Lakeev, S.N., Lapin, V.V., Loginov, O.N., Pavlov, A.I., Silishchev, N.N., Sorokin, I.A., Shapovalov, V.D., 2001. Acidic leaching for Mn recovery from manganese ores with oxide product precipitation. RU Patent No. 2176679. Acharya, C., Kar, R.N., Sukla, L.B., 2001. Microbial extraction of manganese from low grade manganese ore. Transactions of the Indian Institute of Metals 54 (3), 99103. Acharya, C., Kar, R.N., Sukla, L.B., 2003. Studies on reaction mechanism of bioleaching of manganese ore. Minerals Engineering 16 (10), 10271030. Acharya, R., Ghosh, M.K., Anand, S., Das, R.P., 1999. Leaching of metals from Indian Ocean nodules in SO2H2OH2SO4(NH4)2SO4 medium. Hydrometallurg 53 (2), 169175. Acharya, S., Das, R.P., 1987. Kinetics and mechanism of reductive ammonia leaching of ocean nodules by manganous ion. Hydrometallurgy 19, 169186. Agladze, R.I., Gofman, N.T., 1957. The corrosion of manganese containing the impurities nickel, cobalt, and copper in the metal. Elektrokhim. Margantsa, Akad. Nauk Gruzin. S.S.R. 1, 1524.
W. Zhang, C.Y. Cheng / Hydrometallurgy 89 (2007) 137159 Das, S.C., Anand, S., Das, R.P., Jena, P.K., 1989. Sulfuric acid leaching of manganese nodules in the presence of charcoal. The AusIMM Bulletin and Proceedings 294 (1), 7376. Das, S.C., Sahoo, P.K., Rao, P.K., 1982. Extraction of manganese from low-grade manganese ores by ferrous sulfate leaching. Hydrometallurgy 8 (1), 3547. Das, S.C., Sahoo, P.K., Rao, P.K., Jena, P.K., 1978. Recovery of manganese value from ferromanganese slag through acid leaching. Transactions of the Indian Institute of Metals 31 (4), 265267. Das, S.C., Sahoo, P.K., Rao, P.K., 1979. Technical note on recovery of manganese from low manganese content ferromanganese slag. Proceedings - Australasian Institute of Mining and Metallurgy, 272, 2527. Dean, R.S., Fox, A.L., Beck, A.E., 1942. Nitrogen dioxide process for recovery of manganese from ores. U.S. Bureau of Mines Report of Investigations, vol. 3626. 30 pp. Debrodt, H., Kluger, P., Lieberoth, D., 1986. Anode for electrochemical processes. ZA Patent No. 8602688. Demirbas, A., 1999. Non-isothermal leaching kinetics of braunite in water saturated with sulfur dioxide. Resources Conservation and Recycling 26 (1), 3542. Drinkard, Jr., W.F., Woerner, H.J., 1997. Leaching of metallurgical dust wastes in nitric acid for recovery of metal values. WO Patent No. 9716230. Dry, M.J., Irio, G., Jacobs, D.F., Cole, P.M., Feather, A.M., Sole, K.C., Engelbrecht, J., Matchett, K.C., Cilliers, P.J., O'Kane, P.T., Dreisinger, D.B., 1998. Cu/Co tailings treatment project, Democratic Republic of Congo. Proceedings of ALTA Nickel/ Cobalt Pressure Leaching and Hydrometallurgy Forum. ALTA Metallurgical Services, Melbourne, Australia. 36 pp. Dundua, R., Agniashvili, G., 1999. Manganese recovery from residual slimes in the electrochemical manufacture of manganese dioxide. Izvestiya Akademii Nauk Gruzii, Seriya Khimicheskaya 25 (12), 151154. Elsherief, A.E., 2000. A study of the electroleaching of manganese ore. Hydrometallurgy 55 (3), 311326. Fink, C.G., Kolodney, M., 1939. Anodes for the electrowinning of manganese, vol. 76. Transactions of the Electrochemical Society. 25 pp. Freitas, L.R., Amaral, J.C., Mendonca, C.F., 1993. Sulfation of carajas manganese ore with gaseous SO2. Transactions of the Institution of Mining and Metallurgy Section C - Mineral Processing and Extractive Metallurgy 102, C130C131. Fuller, H.C., Edlund, V.E., Sterner, J.W., McDermaid, J.F., 1964. Metallurgical studies of rhodonite ores, Silverton district, Colorado. III. Melting, quenching, and acid leaching of concentrates and electrolytic recovery of manganese from solution. U.S. Bureau of Mines Report of Investigations RI 6442 (5) 31 pp. Furlani, G., Pagnanelli, F., Toro, L., 2006. Reductive acid leaching of manganese dioxide with glucose: Identification of oxidation derivatives of glucose. Hydrometallurgy 81 (34), 234240. Gaprindashvili, V.N., Bagaturiya, L.V., Bardavelidze, M.V., Tsveniashvili, V.S., Dzhanimanov, T.B., Gogichadze, L.D., 1993. Leaching of oxidized manganese ores in mixtures with pyrite. SU Patent No. 1792995. Godsey, A.R. Jr., 1955. Anode for electrowinning manganese. US Patent No. 2723230. Grimanelis, D., Neousyngouna, P., Vazarlis, H., 1992. Leaching of a rich Greek manganese ore by aqueous-solutions of sulfur-dioxide. Hydrometallurgy 31 (12), 139146. Hammerquist, W.L., 1948. Electrolyte purification in manganese electrowinning. US Patent No. 2445826.
157
Hammerquist, W.L., 1951. Manganese electrowinning process. US Patent No. 2559874. Harris, M., Meyer, D.M., Auerswald, K., 1977. The production of electrolytic manganese in South Africa. Journal of the South African Institute of Mining & Metallurgy 77 (7), 137142. Ilea, P., Popescu, I.-C., Urda, M., Oniciu, L., 1997. The electrodeposition of manganese from aqueous solutions of MnSO4. IV: electrowinning by galvanostatic electrolysis. Hydrometallurgy 46 (12), 149156. Ismail, A.A., Ali, E.A., Ibrahim, Ibrahim, A., Ahmed, M.S., 2004. A comparative study on acid leaching of low grade manganese ore using some industrial wastes as reductants. Canadian Journal of Chemical Engineering 82 (6), 12961300. Jacobs, J.H., Churchward, P.E., 1948. Electrowinning of manganese from chloride electrolytes. Journal of the Electrochemical Society 94, 108121. Jakuszewski, B., Ignaczak, M., Dziegiec, J., Grzejdziak, A., 1972. Electrochemical oxidation and reduction on manganous sulfate in aqueous solutions. Societatis Scientiarum Lodziensis, Acta Chimica 17, 8390. Jana, R.K., Pandey, B.D., Premchand, 1999. Ammoniacal leaching of roast reduced deep-sea manganese nodules. Hydrometallurgy 53 (1), 4556. Javorek, P., 1988. Ammonium carbonate leaching of nodules in manganese recovery. CS Patent No. 256130. Jiang, T., Yang, Y.B., Huang, Z.C., Qiu, G.Z., 2003. Simultaneous leaching of manganese and silver from manganese-silver ores at room temperature. Hydrometallurgy 69 (13), 177186. Kane, W.S., Cardwell, P.H., 1976. Two-stage selective leaching of metal values from ocean floor nodules. US Patent No. 3930974. Kaneko, T., Matsuzaki, T., Kugimiya, T., Ide, K., Kumakura, M., Kasama, A., 1993. Improvement of Mn yield in less slag blowing at Bof by use of sintered manganese ore. Tetsu to Hagane-Journal of the Iron and Steel Institute of Japan 79 (8), 941947. Kanungo, S.B., Das, R.P., 1988. Extraction of metals from manganese nodules of the Indian ocean by leaching in aqueous solution of sulfur dioxide. Hydrometallurgy 20, 135146. Kasimov, A.M., Slotvinskii-Sidak, N.P., Mailyan, N.A., Potapov, V.I., 1990. Roasting and leaching of manganese-containing slag. SU Patent No. 1581762. Kawahara, M., Mitsuo, T., Katayama, K.I., 1991. Leaching of manganese nodules using sulfur dioxide as a reductant. Journal of the Mining and Materials Processing Institute of Japan 107 (12), 871876. Kholmogorov, A.G., Patrushev, V.V., Pashkov, G.L., Kononov, Y.S., Mikhlina, E.V., 1998. Reductive leaching of manganese and sulfide concentrates in sulfuric acid solutions. Zhurnal Prikladnoi Khimii (Sankt-Peterburg) 71 (11), 18901892. Kohga, T., Imamura, M., Takahashi, J., Tanaka, N., Nishizawa, T., 1995. Recovering iron, manganese, copper, cobalt, and high-purity nickel from sea nodules. JOM (USA) 47 (12), 4043. Kuh, S.E., Kim, J.W., Kim, D.S., Choi, K.S., 2001. Extraction of metal values from manganese nodules in the ocean environment using zinc matte as a reductant. Environmental Technology 22 (8), 881887. Kukula, M., Sikora, B., 1977. Hydrometallurgical recovery of manganese from slags. II. Purification of solution and electrolysis. Rudy i Metale Niezelazne 22 (8), 411417. Li, J., 2000. Effects of several factors on simultaneous leaching of zinc sulfide ore concentrates and manganese ores. Guizhou Gongye Daxue Xuebao, Ziran Kexueban 29 (3), 1014. Li, X., Zhou, Q., Yang, J., Jiang, X., 1997. Reduction leaching of ocean poly metallic nodules with dilute hydrochloric acid solution. Kuangye Gongcheng 17 (2), 5052.
158
W. Zhang, C.Y. Cheng / Hydrometallurgy 89 (2007) 137159 Pahlman, J.E., Khalafalla, S.E., 1988. Leaching of domestic manganese ores with dissolved sulfur dioxide. U.S. Bureau of Mines Report of Investigations, Twin Cities, US. Pahlman, J.E., Rhoades, C.A., Chamberlain, P.G., 1987. Dual leaching method for recovering silver and manganese from domestic manganiferous silver deposits. U.S. Bureau of Mines Report of Investigations, Twin Cities, US. Paixao, J.M.M., Amaral, J.C., Memoria, L.E., Freitas, L.R., 1995. Sulfation of Carajas manganese ore. Hydrometallurgy 39 (13), 215222. Parissis, G., Winand, R., 1992. Manganese electrodeposition from chloride, sulfate and mixed solutions, including high current densities, ATB Metallurgie 32 (12), 1619, 228. Partenov, D., Stefanova, V., Avramov, A., Chimbulev, M., 2004. Kinetics of leaching of polymetallic concretions in an aqueous solution of SO2. Izvestiya Vysshikh Uchebnykh Zavedenii, Tsvetnaya Metallurgiya (1), 1519. Pesic, B., Storhok, V.C., Binsfield, M.C., 1996. Process for recovery of Zn and Mn from Bunker Hill Water Treatment Plant sludge: Part I leaching and solution purification. In: Ramachandran, V., Nesbitt, C.C. (Eds.), Proceedings of the 2nd International Symposium on Extraction and Processing for the Treatment and Minimisation of Wastes, Minerals, Metals & Materials Society, pp. 699710. Petrie, L.M., 1995. Molecular interpretation for SO2 dissolution kinetics of pyrolusite. manganite and hematite, Applied Geochemistry 10 (3), 253267. Pisarczyk, K., 1995. Manganese and manganese alloys, 4th Edition. Kirk-Othmer Encyclopedia of Chemical Technology, vol. 15. John Wiley & Sons, New York. Popov, S.A., Klushin, V.N., Rodionov, A.I., Makotkin, A.V., Maskova, T.O., 1981. Study of equilibrium characteristics of a sulfur dioxideair-aqueous suspension of manganese dioxide-based industrial byproduct system. Trudy Instituta - Moskovskii Khimiko-Tekhnologicheskii Institut Imeni D. I. Mendeleeva 119, 2427. Ptitsyn, A.N., Galkova, L.I., Ledvii, V.V., Dobyshev, B.V., Skopov, S.V., 2001a. Electrochemical manufacture of manganese dioxide from leaching of lean Mn-carbonate ores. RU Patent No. 2172791. Ptitsyn, A.N., Galkova, L.I., Ledvii, V.V., Skopov, S.V., 2001b. Recovery of metal values from chemical byproducts of spent MnZn electric batteries. RU Patent No. 2164955. Raghavan, R., Upadhyay, R.N., 1999. Innovative hydrometallurgical processing technique for industrial zinc and manganese process residues. Hydrometallurgy 51 (2), 207226. Rappas, A.S., 1985. Processes relating to the extraction of metals from laterites and ocean manganese nodules, Official Gazette, 8 Oct. Ravitz, S.F., Wyman, W.F., Back, A.E., Tame, K.E., 1946. The dithionate process for recovery of manganese from low-grade ores. American Institute of Mining Metallurgical Engineers Metals Technology 13 (No. 6, Tech. Pub. No. 2064) 10 pp. Rodriguez, M., Rivarola, J., Ruiz, M.D., 2004. The effects of carboxylic acid addition on hydrofluoric acid autoclave leaching of a ferrocolumbite. Hydrometallurgy 74 (12), 3946. Rokukawa, N., 1990. Recovery of nickel, cobalt, and copper from ocean manganese nodules with mixed solution of ammonium carbonate and ammonium sulfite. Shigen to Sozai 106 (4), 205209. Rolf, R.F., 1969. Selective recovery of manganese and iron from ores. US Patent No. 3471285. Saha, A.K., Khan, Z.H., Akerkar, D.D., 1993. Reduction of manganese sea nodules with noncoking coal. Transactions of the Indian Institute of Metals 46 (2), 6369.
Lindermann, W., Dombrowsky, C., Sewing, D., Muller, M., Engel, S., Joppien, R., 1994. The BATENUS process for recycling battery waste. In: Harris, B., Krause, E. (Eds.), Proceedings of Impurity Control and Disposal in Hydrometallurgical Processes- 24th Annual Hydrometallurgical Meeting, CIM, Canadian Inst. Mining, Metallurgy and Petroleum, pp. 197204. Louis, P., Martin, J.P., 1976. Increased current efficiency during the electrodeposition of manganese from sulfate electrolytes, Report - National Institute for Metallurgy (South Africa), vol. 1859. 27 pp. Lu, H., Zou, X., 2001. A comprehensive utilization process for black manganese-silver ores by pyrite reducing method. Rare Metals (Beijing, China) 20 (3), 142146. Mantell, C.L., 1944. Anodes for the electrowinning of Mn. US Patent No. 2340400. Mantell, C.L., Ferment, G.R., 1969. Electrowinning manganese. US Patent No. 3455799. Mantell, C.L., Hammerquist, W.L., 1944. Mg control in Mn electrowinning. US Patent No. 2348742. Maslenitskii, N.N., Mil'ner, R.S., Belikov, V.V., 1969. Laboratory study of dithionate treatment of three samples of low-grade manganese slimes. Obogashchenie Rud (Sankt-Peterburg, Russian Federation) 14 (2), 45. Mittal, N.K., Sen, P.K., 2003. India's first medium scale demonstration plant for treating poly-metallic nodules. Minerals Engineering 16 (9), 865868. Mohanty, P.S., Ghosh, M.K., Anand, S., Das, R.P., 1994. Leaching of manganese nodules in ammoniacal medium with elemental sulfur as reductant. Transactions of the Institution of Mining and Metallurgy Section C - Mineral Processing and Extractive Metallurgy, 103, C151C155. Mukherjee, A., Raichur, A.M., Natarajan, K.A., 2004. Recent developments in processing ocean manganese nodules-a critical review. Mineral Processing & Extractive Metallurgy Review 25, 91127. Naik, P.K., Das, S.C., Sukla, L.B., 2002. Extraction of manganese from low-grade Nishikhal ore using pyritiferous lignite in acidic medium. Minerals & Metallurgical Processing 19 (2), 110112. Naik, P.K., Nathsarma, K.C., Das, S.C., Misra, V.N., 2003. Leaching of low-grade Joda manganese ore with sulfur dioxide in aqueous medium. Transactions of the Institutions of Mining and Metallurgy, Section C: Mineral Processing and Extractive Metallurgy 112 (2), C131C134. Naik, P.K., Sukla, L.B., Das, S.C., 2000. Aqueous SO2 leaching studies on Nishikhal manganese ore through factorial experiment. Hydrometallurgy 54 (23), 217228. O'Keefe, T.J., 1984. Techniques for evaluating electrolytes for metal recovery. Journal of Electroanalytical Chemistry and Interfacial Electrochemistry 168 (12), 131146. Omarov, N.S., Beisembaev, B.B., 1996. Use of pyrite flotation concentrate as a reducing agent for manganese leaching from oxidized ores. Kompleksnoe Ispol'Zovanie Mineral'Nogo Syr'Ya (6), 8285. Osawa, K., 1973. Electrolytic winning of manganese metal. JP Patent No. 48042767. Pagnanelli, F., Sambenedetto, C., Furlani, G., Vegli, F., Toro, L., 2007. Preparation and characterisation of chemical manganese dioxide: effect of the operating conditions. Journal of Power Sources 166, 567577. Pahlman, J.E., Khalafalla, S.E., 1979. Selective recovery of nickel, cobalt, manganese from sea nodules with sulfurous acid. US Patent No. 4138465.
W. Zhang, C.Y. Cheng / Hydrometallurgy 89 (2007) 137159 Sahoo, R.N., Naik, P.K., Das, S.C., 2001. Leaching of manganese from low-grade manganese ore using oxalic acid as reductant in sulfuric acid solution. Hydrometallurgy 62 (3), 157163. Sanigok, U., Bayramoglu, M., 1988. Bench-scale manganese sulfate production from low-grade pyrolusite ores. - Part III. Chimica Acta Turcica 16 (1), 920. Shibata, J., Baba, Y., 1995. Development of recovery process of valuable metals from waste lithium battery. Minerals, Metals and Materials Society/AIME (USA) 257261. Sole, K.C., Feather, A.M., Cole, P.M., 2005. Solvent extraction in southern Africa: an update of some recent hydrometallurgical developments. Hydrometallurgy 78 (12), 5278. Suliakas, A., Yanitskii, I.V., Juseviciene, G., 1973. Behavior of selenite or selenate additions of an anode during electrodeposition of manganese. Lietuvos TSR Mokslu Akademijos Darbai, Serija B: Chemija, Technika, Fizine Geografija (4), 4754. Sventsitskii, A.T., Nosenkov, A.N., Trunev, S.V., Dmitrevskii, B.A., Treushchenko, N.N., Yur'eva, V.I., Ivanova, N.Y., 2003. Acidic redox leaching of lean manganese ores, slimes, and dust from ferroalloy furnaces. RU Patent No. 2213155. Szabo, L.J., 1976. Recovery of metal values from manganese deep sea nodules using ammoniacal cuprous leach solutions. US Patent No. 3983017. Taylor, T., 1993. Electrolytic manganese dioxide production by Australian Manganese Company Limited, Newcastle. Australasian Mining and Metallurgy, Clunies Ross House, Victoria, Australia 2 (Monograph No.19), 12371238. Thomas, G., Whalley, B.J.P., 1958. The leaching of manganese from pyrolusite ore by pyrite. Canadian Journal of Chemical Engineering 36, 3743. Veglio, F., Beolchini, F., Gasbarro, A., Toro, L., Ubaldini, S., Abbruzzese, C., 1997. Batch and semi-continuous tests in the bioleaching of manganiferous minerals by heterotrophic mixed microorganisms. International Journal of Mineral Processing 50 (4), 255273. Veglio, F., Toro, L., 1994a. Reductive leaching of a concentrate manganese-dioxide ore in acid-solution stoichiometry and preliminary kinetic-analysis. International Journal of Mineral Processing 40 (34), 257272. Veglio, F., Toro, L., 1994b. Fractional factorial-experiments in the development of manganese-dioxide leaching by sucrose in sulfuric-acid-solutions. Hydrometallurgy 36 (2), 215230.
159
Vu, H., Jandova, J., Lisa, K., Vranka, F., 2005. Leaching of manganese deep ocean nodules in FeSO4H2SO4H2O solutions. Hydrometallurgy 77 (2005), 147153. Wanamaker, E.M., Hammerquist, W.L., Morgan, Jr., W.D. 1951. Molybdenum control in manganese electrowinning. US Patent No. 2538995. Wanamaker, E.M., Morgan, Jr., W.D. 1943. Catholyte purification in the electrowinning of Mn. US Patent No. 2325723. Ward, C., Cheng, C.Y., Urbani, M.D., 2004. Manganese - from waste to high-tech material. Publications of the Australasian Institute of Mining and Metallurgy, pp. 241246. 2/2004. Ward, C.B., 2005. Acidic leaching of manganese from lean oxide ores with extraction stage for purity. WO Patent No. 2005012582. Welsh, J.Y., Sochol, I., 1978. Recovering metal values from marine manganese nodules, Official Gazette, 31 Oct. Welsh, J.Y., 1973. Recovering high-purity, free-flowing, crystalline manganese dioxide from impure manganese nitrate solutions. US Patent No. 3780158. Welsh, J.Y., 1978. Recovering manganese dioxide crystals from manganese nitrate solutions. RO Patent No. 63988. Yaozhong, L., 2004. Laboratory study: simultaneous leaching silverbearing low-grade manganese ore and sphalerite concentrate. Minerals Engineering 17 (910), 10531056. Yavorskaya, G.M., Arsentev, V.A., Kucher, V.L., Kovaleva, O.V., 1992. Redox leaching of manganese from oxide feed materials. SU Patent No. 1733492. Yoon, B.H., Kim, D.R., 1986. Recovery of manganese from electrolytic zinc anodic slime and from scrap dry cells. Kumsok Pyomyon Choli 19 (1), 1319. Yucel, O., Ari, M.E., 2001. Carbothermic smelting of Tavas manganese ore. Turkey, High Temperature Materials and Processes 20 (56), 345351. Zhang, W., Cheng, C.Y., 2006. Manganese metallurgy, recovery and control a literature review. Part I: Manganese Metallurgy CSIRO Minerals, Australia, DMR - 2809. Ziyadanogullari, R., Buyuksahin, M., 1995. Recovery of MnSO4 from low-grade pyrolusite ores, and of MnSO4 and silver from manganese-silver ores. Separation Science and Technology 30 (3), 477486.

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Hydrometallurgy 89 (2007) 137 159 www.elsevier.com/locate/hydromet

W. Zhang, C.Y. Cheng / Hydrometallurgy 89 (2007) 137159

W. Zhang, C.Y. Cheng / Hydrometallurgy 89 (2007) 137159

W. Zhang, C.Y. Cheng / Hydrometallurgy 89 (2007) 137159

W. Zhang, C.Y. Cheng / Hydrometallurgy 89 (2007) 137159

2MnOOH SO2 2H 2Mn2 SO2 2H2 O 4 8 2MnOOH SO2 2H 2Mn2 S2 O2 2H2 O 6 9

(NH4)2SO3 bisulfiteH2SO4 Aq. SO2 Kinetic study

Low Mn ores (Percolation) Aq. SO2

Size 1.32.5 cm 1.5%-sat. [SO2] 1520 days

W. Zhang, C.Y. Cheng / Hydrometallurgy 89 (2007) 137159

W. Zhang, C.Y. Cheng / Hydrometallurgy 89 (2007) 137159

W. Zhang, C.Y. Cheng / Hydrometallurgy 89 (2007) 137159

ZnS FeS2/ZnS/PbS Ni matte Zn matte Pyriti-ferrous lignite

W. Zhang, C.Y. Cheng / Hydrometallurgy 89 (2007) 137159

W. Zhang, C.Y. Cheng / Hydrometallurgy 89 (2007) 137159

2FeOOH H2 SO4 H2 SO3 2FeSO4 3H2 O

W. Zhang, C.Y. Cheng / Hydrometallurgy 89 (2007) 137159

W. Zhang, C.Y. Cheng / Hydrometallurgy 89 (2007) 137159

W. Zhang, C.Y. Cheng / Hydrometallurgy 89 (2007) 137159

W. Zhang, C.Y. Cheng / Hydrometallurgy 89 (2007) 137159

W. Zhang, C.Y. Cheng / Hydrometallurgy 89 (2007) 137159

W. Zhang, C.Y. Cheng / Hydrometallurgy 89 (2007) 137159

W. Zhang, C.Y. Cheng / Hydrometallurgy 89 (2007) 137159

W. Zhang, C.Y. Cheng / Hydrometallurgy 89 (2007) 137159

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