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Hydrometallurgy 89 (2007) 160 177 www.elsevier.com/locate/hydromet

Manganese metallurgy review. Part II: Manganese separation and recovery from solution
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 Various methods for manganese separation and recovery from solution are reviewed, which are potentially applicable to leach solutions of secondary manganese sources, particularly nickel laterite waste effluents. The main methods include solvent extraction, sulfide precipitation, ion exchange, hydroxide precipitation and oxidative precipitation. These methods are briefly compared and assessed for both purification of manganese solutions and recovery of manganese from the solutions in terms of their selectivity, efficiency, reagent costs and product quality. The strategies for co-recovery of valuable metals including nickel and cobalt are discussed. Among these methods, oxidative precipitation with cheap oxidants such as SO2/O2 mixture is highly selective for recovery of manganese and the most promising method recommended for future research and development. Solvent extraction with cheap extractants is next for selective extraction of manganese, purification of manganese solutions or co-recovery of other valuable metals. The cost of base needed for neutralisation in solvent extraction is a major consideration. Carbonate precipitation is more selective for manganese than hydroxide precipitation with respect to magnesium impurity. Manganese carbonate is a favourable form for further processing to final manganese products, but its applicability will largely depend on the relative concentrations of manganese to magnesium and calcium impurities. Sulfide precipitation and ion exchange offer useful means for purification and/or co-recovery of other base metal impurities. 2007 Elsevier B.V. All rights reserved.
Keywords: Manganese; Separation; Recovery; Solvent extraction; Precipitation

1. Introduction Manganese separation and recovery from solutions are crucial to make a process economically viable. This is particularly important to separate metal values and recover manganese in the solutions from secondary manganese materials including Mn-bearing steel scraps, spent electrodes, waste electrolytes, spent catalysts, and from industrial mineral processing waste effluents.
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.2007.08.009

Industrial waste effluents containing a substantial amount of manganese are a potential source of manganese. For example, most manganese contents in sphalerite flotation concentrates are leached together with zinc and rejected to the waste effluents in its downstream processing. In recent years, an increasing world demand for nickel and cobalt has motivated the development of processes for the treatment of nickelcobalt laterite ores. In Western Australia, several laterite plants are in commercial operation, including the Cawse and Murrin Murrin projects, and more recently the Ravensthorpe project of BHP Billiton. Worldwide, more than ten nickel

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projects are in different stages of development. In all these plants, manganese is one of the impurities that are leached together with nickel and cobalt and disposed in the subsequent separation processes. Different separation strategies are used in the downstream processes by different plants and projects. The total recoverable manganese from laterite waste streams has been estimated to be more than 45,000 t per annum in Western Australia alone and 121,500 t per annum worldwide, which are valued at US $71.5 million per annum and $193 million per annum, respectively (Zhang and Cheng 2006). The value estimations are based on the latest statistics on Mn metal average international prices (US $1590/t for Mn metal) (Corathers and Arguelles 2007). The challenge to recovery of manganese from these waste solutions lies in the relatively low manganese concentration (15 g/L) together with large amounts of impurities, e.g. about 10 g/L magnesium in a typical nickel laterite waste effluent. Selectivity, reagents costs, efficiency and product quality are important economical factors for developing a method or a process. In Part I, various leaching processes for manganese ores and secondary materials are reviewed. Part II of this review covers various separation and recovery methods including solvent extraction, ion exchange, and hydroxide, carbonate, sulfide, and oxidative precipitations. Their applicability is briefly discussed. The aims of this literature review are to search methods and techniques which are potentially applicable for the separation and recovery of manganese from industrial streams and to suggest suitable methods and processes for further research and development. 2. Solvent extraction of manganese In hydrometallurgical processing of manganesecontaining materials, the leach liquors often contain divalent iron, manganese, copper, nickel, cobalt and zinc along with other impurities. Solvent extraction plays a vital role in purification and separation of manganese. A number of organic SX reagents have been used for fundamental research, focusing on the phosphorus acid and carboxylic acid cation exchange reagents. 2.1. Metal ion selectivity and manganese speciation in cation exchange reagents 2.1.1. D2EHPA-phosphoric acid extractant D2EHPA, di-2-ethylhexyl phosphoric acid, is by far the most widely used extractant for manganese. Sato and Nakamura (1985) investigated solvent extraction of divalent metals: Mn, Co, Ni, Cu, Zn Cd, and Hg, from

sulfuric acid solutions by D2EHPA. The distribution coefficient was found to be dependent on the concentrations of acid and D2EHPA, suggesting that these metals were extracted through a cation-exchange mechanism: M 2 2HA2 MA4 H2 2H
P P P

where M denotes Mn, Co, Ni, Cu, Zn, Cd and Hg, P HA = D2EHPA in the organic phase and MA4 H2 the metalorganic complex in organic solution. The metal extraction lies in the order: ZnNCdNMnNCuNCoNNiNHg:

Cheng (2000) reported a similar extraction order for Zn, Mn, Cu, Co and Ni with D2EHPA in the presence of Ca and Mg (pH50 in bracket): Zn1:70Ca1:72NMn2:71Cu2:80 NCo3:7Ni3:82NMg4:3: In chloride medium, the kinetics of both forward and backward extractions of manganese with D2EHPA were investigated by Biswas et al. (1996, 1997) using a single drop technique. The formation of 1:1 complex of Mn2+ P with HA 2 (dimeric anion) at the interface was proposed to be the rate limiting step. In the range of 0.040.50 mol/ L D2EHPA and aqueous pH range of 1.03.0, the process is under mixed chemical and diffusion control. The activation energy depends on the back-extraction parameters and is of the order of 2040 kJ/mol. In sulfate medium, the extraction kinetics of Mn(II) with D2EHPA in n-hexane was investigated by Hughes and Biswas (1993) using a rotating diffusion technique in the pH range 2.703.57. With the concentration of Mn(II) 0.5 mol/L and that of the organic extractant 1.13 mol/L, the formation of a 1:1 complex in the aqueous film was identified to be the rate-limiting step. In the lower temperature region ( 25 C), the activation energy was about 20 kJ/mol, indicating a mixed diffusion and chemically controlled mechanism. The extraction kinetics of Mn(II) from 0.1 M sulfate medium by D2EHPA solution in kerosene was again studied by Biswas and Mondal (2003) using the Lewis Cell (stirred cell) and Hahn Cell (non-stirred cell) techniques. The rate constant values and activation energy was found to vary significantly with the phase contacting techniques. Alkylphosphoric acids related to D2EHPA have also been studied. Wang and Nagaosa (2002) investigated the extraction of divalent metal ions using Di-2methylnonylphosphoric acid (D2MNPA) in heptane at

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an aqueous ionic strength of 0.10 mol/L (NaClO4) at 25 C. The extraction order of metals is: CdMnNCuNCoNNi The metal complexes extracted were found to be all monomeric species by using a slope analysis method. A curve fitting method was used to determine the types of P metalorganic complexes extracted. MnA2 3HA and P MnA2 4HA complexes were found for Mn(II). 2.1.2. Ionquest 801/P507/PC 88A-phosphonic acid extractant Metal pH isotherms with 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester (PC88A) were investigated in both sulfate and chloride media by Dreisinger and Cooper (1984). The extraction orders differ in different media. In sulfate medium, the order was found to be (pH50 in bracket): FeIII0:15NZn1:46NPb3:05NCu3:15NMn3:19 NCd3:37NCa3:48NFeII3:5 NCo3:55NMg4:07NNi4:85: It indicates a good possibility of separation of zinc from manganese and manganese from nickel in sulfate medium with PC 88A. In chloride medium, the isotherms of cobalt and manganese shifted significantly to lower pH values and the order became (pH50 in bracket):
FeIII0:30NZn1:28NCo2:03NMn2:64NCu2:69 NFeII2:88NPb2:93NCa2:96 NMg3:62NCd3:70NNi4:27:

2.1.3. Cyanex 272 and PIA-8-phosphinic acid The extraction of metals from a sulfate medium with Cyanex 272 in toluene was established in the order (pH50 in bracket) (Cole 2002): Zn2:51NCu4:13NMn4:60NCo4:65NMg5:59 NCa6:15NNi6:58: The pH50 values suggest that Cyanex 272 is a good extractant in terms of separation of cobalt from nickel, zinc from manganese, and manganese from nickel. The research results by Devi et al. (1997) showed that the extraction of metal ions with Cyanex 272 increased with increasing equilibrium pH and the extractant concentration up to 0.05 M. The separation factor of zinc over manganese (Zn/Mn) was pH dependent, maximum at pH 3.5 and minimum at pH 5.7. The P extracted species were determined to be ZnA2 3HA P and MnA2 3HA . 2.1.4. Carboxylic acid extractants The extraction of Mn, Cu, Co, and Ni in nitric medium with Versatic 911 acid in benzene was reported (Shibata et al., P 1974; Shibata and Nishimura, 1979). P MnA2 4HA and MnA2 2HA2 were observed to be the predominant extracted species of manganese. The extraction reaction of these metals was endothermic and temperature had a significant effect on extraction of Co2+ and Mn2+ (Mukai et al., 1975). The extraction of Mn(II) from NH4Cl solutions with heptanoic acid was studied by Apostoluk (1989). It was found that the prevailing species in the organic phase were mononuclear Mn(II) complexes, but when Mn(II) concentration in the system was 10.0 mM, the organic P phase contained MnA2 2HAj complexes, where j = 1, 2 or 3. 2.2. Applications of SX for manganese separation/ removal Manganese is closely associated with zinc ores and nickelcobalt laterite ores and leached together with these metals. Solvent extraction plays an important role in separation of these metal values from manganese, in which manganese is left as an impurity in the raffinate. The major solvent extraction processes developed are reviewed below. 2.2.1. Separation of manganese from cobalt and nickel The reported extractants for the separation of manganese from cobalt and nickel are summarised in Table 1.

These shifts increase the ease of separation of manganese from nickel and the separation of manganese from magnesium, but reduce that of separation of zinc from manganese. The extraction order was also found to depend on the ratio of the molar concentrations of the extractant to the metal in the organic phase (Thakur, 1998). At low loading, the extraction order was established as Mn N Cu N Co N Ni and the equilibrium reaction proceeded via Eq. (2): M 2 2HA2 M HA2 2 2H
P P

At high loading, the extraction order became Cu N Mn N Co N Ni and the following equilibrium reaction predominates: M 2 HA2 MA2 2H
P P

W. Zhang, C.Y. Cheng / Hydrometallurgy 89 (2007) 160177 Table 1 Summary of Mn separation from Co and Ni and recovery from manganese solutions Extractant D2EHPA-phosphoric acid Remark Mn removed for Co EW in the pilot Mn SX circuit Continuous operation for separation of Mn from Co at pH 4.2 Extn. order: Zn Ca N Mn N Cu N Co N Ni N Mg Optimum pH 3.5 for Mn from Ni at 4060 C Optimum pH 3 for Mn from Co at 23 C Fe(III) N Zn N Pb N Cu N Mn N Cd N Ca N Fe(II) N Co N Mg N Ni Mn over Mg and Ni Bulong process: Co, Cu, Zn and Mn from Ni, Ca and Mg Co and Mn from Ni at pH 6 and 50 C Zn N Cu N Mn N Co N Mg N Ca N Ni Separation of Mn from Ca and Ni D2EHPA best with Mn/Co max at pH 4.45 D2EHPA N PC88A N Cyanex 272 Reference Dry et al. (1998) Feather et al. (1999) Hoh et al. (1984) Cheng (1999, 2000)

163

PC 88A-phosphonic acid Cyanex 272-phosphinic acid

Dreisinger and Cooper (1984)

D2EHPA PC88A Cyanex 272

Taylor and Cairns (1997) Hubicki and Hubicka (1996) Cole (2002) Devi et al. (2000)

In the Kakanda project of the Democratic Republic of Congo, after leaching, copper SX and iron removal, manganese was removed from the leach solution using D2EHPA before cobalt electrowinning (Dry et al., 1998; Feather et al., 1999). The pilot manganese SX circuit consisted of three extraction stages, one scrubbing stage and two stripping stages. A bleed stream of the stripped organic phase was treated with 6 M HCl in one re-strip stage to control the accumulation of ferric ion in the organic solution. Hoh et al. (1984) performed a continuous mixersettler operation for separation of manganese from cobalt in sulfate solution by D2EHPA. A high degree of separation could be achieved by controlling the solution pH at 4.2. Four extraction stages at O/A = 2 and two stripping stages at O/A = 1 were used to separate manganese from cobalt. Devi et al. (2000) compared separation of divalent manganese and cobalt from sulfate solutions using sodium salts of D2EHPA, PC 88A and Cyanex 272 in kerosene. Manganese and cobalt pH isotherms with the three extractants indicated a preferential extraction of manganese over cobalt. The selectivity of manganese over cobalt by PC 88A and Cyanex 272 was too small to be used for their separation. In the case of D2EHPA, the separation factor of manganese over cobalt was maximum (79.3) at equilibrium pH of 4.45. The order of manganese extraction with the three extractants was D2EHPA N PC88A N Cyanex 272. D2EHPA was the most suitable extractant for separation of manganese from cobalt. The separation of copper and manganese from cobalt and nickel in synthetic nickel laterite leach solution was studied by Cheng (1999, 2000) with D2EHPA. It was

found that relatively high temperatures in the range of 40 60 C and pH at 3.5 were favourable for separation of manganese from nickel while a low temperature at 23 C and pH 3 was optimum for separation of manganese from cobalt. A complete removal of manganese and copper from the aqueous solution was achieved by multiple stage extraction and scrubbing of the loaded organic solution with manganese solution. After one stage of contact, only about 3 ppm Co and Ni were present in the organic solution. The Bulong Nickel Operation in Western Australia, processed a nickelcobalt laterite ore and produced highgrade nickel and cobalt cathode products (Taylor and Cairns, 1997). In this process, cobalt, copper, zinc and manganese were separated from nickel, calcium and magnesium by solvent extraction with Cyanex 272. The nickel in the raffinate was separated from calcium and magnesium by solvent extraction with Versatic 10 and then electrowon. The strip solution from Cyanex 272 containing cobalt, copper, zinc and manganese subjected to sulfide precipitation, solids/liquid separation and acid re-leach to separate cobalt, copper and zinc from manganese. The zinc was eliminated by solvent extraction with D2EHPA and the copper by ion exchange (IX). The cobalt was then recovered from the purified solution by electrowinning. Compared with the direct solvent extraction approach (see below), the Bulong process is inefficient because of the twice extraction of the large volume of dilute feed solution, subsequent sulfide precipitation and re-leach to separate cobalt from manganese. Purification of a nickel sulfate solution containing impurities such as Co, Zn, Cu, Mn and Fe was also carried out by Hubicki and Hubicka (1996) using Cyanex 272. After two stages of extraction at a phase

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Table 2 Summary of Ni, Co separation and recovery from manganese solutions Extractant Cyanex 301 (20%) and TBP (5%) in Exxsol D-80 Cyanex 301-Goro process Cyanex 301, Cyanex 302 with Aliquat 336 Carboxylic acid- hydroxyoxime Versatic 911-(LIX 63, 64, 64 N, 65 N, and 70) Carboxylic acid-aldoximes (non chelating) Versatic 10 and LIX 63 (CSIRO DSX synergist system) Remark N 99.9% Co and Ni only 0.2% Mn but needs strip with 56 M HCl at 5060 C Reference Tsakiridis and Agatzini (2004) Price and Reid 1993; Mihaylov et al., 1995; Bacon and Mihaynov, 2002 Tait 1992; Jakovljevic et al., 2004

Cyanex 301 more efficient than Cyanex 302 Ni and Co from Mn, Ca and Mg First observed synergism for Ni with 3 pH unit shift Flett and West 1971; Tammi, 1976 Synergism for Ni and Co Separation of Ni, Zn and Co from Mn, Ca and Mg pH50 (MnNi) = 1.96 Preston (1983, 1985)

Cheng and Urbani 2005a,b; Cheng 2006

pH50 (MnCo) = 2.53 Versatic 10-alkylpyridine synergist N 99.9% extraction for Ni, Co, Zn, Cu and neodecanoic acid Versatic 10-decyl-4-pyridinecarboxylic acid Reject Mn impurities in raffinate (CSIRO DSX synergist system) Pyridine (BNPP) and sulphonic acid Useful for separation at very acidic solution (HDDNS) (pH b 0.5), but needs strong acid to strip Ni and Co

Preston and Du Preez (2000) Cheng and Urbani 2005c; Cheng et al., 2005 Zhou and Pesic (1997)

ratio of 1:1, pH 6 and 50 C, the manganese and cobalt content in the purified NiSO4 solution decreases several hundred times compared to the initial content. The purified nickel sulfate contained 10 ppm Co, 1 ppm Zn, 0.5 ppm Fe, Cu and Mn. 2.2.2. Separation of cobalt and nickel from manganese The reported extractants for the separation of cobalt and nickel from manganese are summarised in Table 2. Synergist effect on nickel extraction by mixtures of carboxylic acid and a hydroxyoxime was observed in early 1970s (Flett and West, 1971; Tammi, 1976). The synergistic systems were further studied by Preston (1983, 1985). Recently, a number of synergistic SX systems comprising carboxylic acids and oxime reagents were developed to recover nickel and cobalt and separation from manganese, magnesium and calcium impurities in the nickel laterite leach solutions (Cheng and Urbani 2005a,b; Cheng 2006). For the system containing Versatic 10 (an alkyl monocarboxylic acid) and LIX63, the difference in pH50 values between manganese, and nickel and cobalt was 1.96 and 2.53 pH units, respectively, indicating easy separation of nickel and cobalt from manganese impurities. Synergist systems containing carboxylic acids, and alkyl pyridines and pyridinecarboxylate esters as synergists have been intensively studied by Preston and coworkers. The pyridinecarboxylate ester synergists with carboxylic acid extractant, Versatic 10, were found to cause appreciable synergistic shifts for the extraction of Ni and Co (Preston and du Preez, 1994; du Preez and

Preston, 2004). With n-octyl 3-pyridinecarboxylate, the synergistic shifts decreased in the order: NiNCoNCdNCuFeIINMnNZn And with Acorga DS5443A or CLX50 (a pyridine dicarboxylate ester manufactured by Avecia) in the order: NiNCuNCoNFeIINCdNMnNZn With an alkylpyridine synergist, large synergistic shifts were found for nickel, e.g. from 1.04 pH units with Versatic 10 alone to 3.48 pH units for its mixture (Preston and du Preez, 2000). The selectivity series for the extraction of divalent metals from sulfate media by the above-mentioned mixture lied in the order (pH50 in bracket): Cu3:16NNi4:73NZn4:94NCo5:41NFeII5:65 NMn6:45NCa7:96NMg8:43: This series suggests that in the recovery of nickel from laterite leach liquors, the mixed extractant systems would allow the early rejection of manganese, ferrous iron, calcium and magnesium to the raffinate, whilst the more valuable impurity metals (copper, cobalt and zinc) would report to the nickel strip liquor. Based on the earlier work, the direct solvent extraction (DSX) process (Fig. 1) has been developed to directly separate nickel and cobalt from manganese, magnesium and calcium without intermediate precipitation (Cheng

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Fig. 1. A conceptual flowsheet of the direct SX Process for nickel laterites (Cheng et al., 2004).

et al., 2004; Cheng and Urbani, 2005c). The core of the DSX process is the synergistic solvent extraction technology using Versatic 10 as extractant in combination with a synergist including decyl-4-pyridinecarboxylic acid (4PC) (Cheng and Urbani, 2005c; Cheng et al., 2005) and LIX 63 (Cheng and Urbani, 2005a,b; Cheng, 2006). Batch and semi-continuous tests using the system containing Versatic 10 and 4PC and nickel laterite pilot plant solutions from BHP Billiton were carried out. Excellent selectivity for nickel and cobalt over Mn, Mg and Ca were demonstrated. The pH50 of cobalt was found to be 5.47 and the pH50 of manganese 6.63, resulting in a pH50 of 1.17 pH units between manganese and cobalt, suggesting a good separation of cobalt and nickel from manganese, magnesium and calcium. Fast extraction and stripping kinetics were also observed. In semi-continuous extraction tests, the organic synergist solution effectively extracted all of the cobalt, zinc and copper and 99.97% of the nickel, leaving most of manganese, magnesium, calcium and chloride in the raffinate. About 96% of the co-extracted manganese, 100% of the co-extracted magnesium and 61% of the coextracted calcium were scrubbed in the semi-continuous scrubbing tests. A synergistic extraction system involving a pyridinebased chelating extractant, 2,6-bis-[5-n-nonylpyrazol-3yl] pyridine (BNPP) and dinonyl naphthalene sulfonic acid (DNNSA) has also been reported for selective extraction of nickel and cobalt at pH 0.5 from impurities such as Fe, Mn, Ca, Mg and Al (Zhou and Pesic, 1997). The extraction sequence of the metals (pH50 in bracket) is: Cub0:0NNib0:0NCob0:0NZn0:15 NFeII0:6NFeIII0:65NNMn1:51 NCa2:4NAl3:1NMg

This synergistic system showed good separation of nickel and cobalt from manganese in highly acidic solutions. However, the stripping of cobalt and nickel needs strong HCl acid. The stripping kinetics of nickel is slow and needs both strong HCl and high temperature. A better direct SX process to separate nickel and cobalt from the major impurities (Mn, Mg and Ca) in the highly acidic nickel leach solution of the Goro Process in New Caledonia has been developed by Inco Ltd (Price and Reid, 1993; Mihaylov et al., 1995; Bacon and Mihaynov, 2002). After the removal of copper by IX, the leach solution is subjected to solvent extraction using Cyanex 301 (bis-(2,4,4-trimethylpentyl)-dithiophosphinic acid) to reject the major impurities, Mn, Mg and Ca. Cobalt, nickel and zinc are stripped using 6 M HCl. The zinc is then separated by IX and the cobalt is separated from the nickel by SX using tertiary octyl amine (TOA). After pyro-hydrolysis of the concentrated NiCl2 solution, nickel is recovered as nickel oxide and HCl is recycled for stripping and cobalt is precipitated as carbonate. Problem with Cyanex 301 is its affinity for copper, making it impossible to strip and hence complete removal of copper is necessary. Therefore, the major disadvantages of the Goro Process lie in the need to use ion exchange for complete copper removal before the solvent extraction and the need for 6 M HCl and high temperatures (5060 C) for stripping the metals. Consequently, the use of 6 M HCl in stripping forces the nickel recovery via pyrohydrolysis route. 6 M HCl may not be necessary strong and expensive if it is recycled and regenerated. Tsakiridis and Agatzini (2004) recently studied a simultaneous extraction and separation of cobalt and nickel from manganese and magnesium in sulfate

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Table 3 Summary of Zn separation and recovery from manganese solutions Extractant D2EHPA Remark Zn/Mn maximum at pH 3 and A/O = 2 pH 1.83.0 for Zn; pH 3.36.5 for Mn Optimum pH 2.75 for Zn from Mn pH 2.5 for Zn; pH 4.5 for Mn Fe(III) N Cu N Zn N Ni Co N Ca N Mn Easy separation of Zn from Mn Separation of Co/Zn from Mn (Baja Mining Boleo Project) N 90% Zn extraction in 45 stages pH 5.25.5 Reference Ritcey and Lucas (1971) Urbanski (1988) Cho and Dai (1994) Salgado et al., (2003) Tait et al. (1995) Dreisinger et al. (2005) Bressa et al., (1979) Buttinelli and Giavarini (1982)

Cyanex 272 LIX1104 Versatic 10-LIX 63 (CSIRO Synergistic SX) TBP (3050 g/L NaCl) Naphthenic acid

solutions using Cyanex 301. The results showed that the extractant Cyanex 301 in the presence of TBP could be used for the separation of cobalt and nickel from manganese and magnesium in sulfate solutions with an improved stripping efficiency. Cyanex 301 (20%) and TBP (5%) in Exxsol D-80 could extract cobalt and nickel by 99.9% and 99.7%, respectively, in one stage at pH 2.0 and 50 C. After scrubbing with 1 M HCl at pH = 2.0, manganese co-extraction in the loaded Cyanex 301 could be reduced to 0.2%, whereas no magnesium extraction occurred in the pH range 1.02.0. Cobalt and nickel stripping from the loaded organic phase by 5 M HCl reached 99.6% and 99.2%, respectively, in one stage at 50 C and phase ratio O/A = 2/1. Tait (1992) compared the extraction behaviour of Cyanex 301, Cyanex 302 and their binary extractant mixtures with Aliquat 336 toward Cu, Zn, Fe(III), Fe(II), Co, Ni, and Mn in sulfate solutions. Cyanex 301 was found more efficient as an extractant than Cyanex 302, and was able to effect extraction at greater acidities. The presence of base Aliquat 336 resulted in a decrease in its extraction power. This could be ascribed to the high stability of the acid-base couple which must dissociate to effect extraction. Jakovljevic et al. (2004) also investigated the solvent extraction and stripping characteristics of Cyanex 301 binary extractant systems for recovery of cobalt and nickel from chloride solutions. These binary extractant systems consisted of the mixtures of Cyanex 301 with basic extractants Primene JMT, Amberlite LA-2, Alamine 336 and Aliquat 336. The Cyanex 301-amine systems all demonstrated that cobalt and nickel could be selectively extracted from calcium, manganese and magnesium. Among the amine extractant systems, Cyanex 301-Aliquat 336 was found most promising. A decrease in cobalt stripping was observed when the hydrochloric acid concentration was increased from 2 to 4 M. The hydrochloric acid concentration had a reverse effect on nickel.

2.2.3. Separation of zinc from manganese The reported extractants for separation of zinc from manganese are summarised in Table 3. Salgado et al. (2003) reported a process for recovery of zinc and manganese from spent alkaline batteries by solvent extraction with 20% (v/v) Cyanex 272 dissolved in Escaid 110 at 50 C. The process is of particular importance for separation of zinc and manganese metals. The leach solution contained 18.96 g/L Zn and 12.95 g/L Mn. The bench scale results showed that the organic system is selective for zinc at pH 2.5, leaving manganese in the raffinate. This method has been proposed to treat residues from both zinccarbon and alkaline batteries because metal compositions of these batteries are quite similar. Buttinelli and Giavarini (1982), Buttinelli et al., (1985) developed a process for the recovery of H2SO4, zinc and manganese from zinc spent electrolytes. In this process, sulfuric acid was extracted by an iso-butyl alcohol. Zinc was extracted by D2EHPA, leaving manganese in the solution or zinc and manganese coextraction by 1 M naphthenic acid in kerosene after partial neutralization to pH 5.2-5.5. The stripped solution containing zinc and manganese could be directly recycled to the zinc electrowinning circuit. In Baja Mining Corporation's Boleo project, zinc and cobalt were recovered in a pilot plant operation using CSIRO synergistic solvent extraction technology in a DSX process (Dreisinger et al., 2005). The feed solution contained 23 g/L Mn, 0.13 g/L Co and 0.6 g/L Zn. Cobalt and zinc were separated from the manganese. About 69% zinc was selectively stripped from the organic solution at pH 3.0 using weak sulfuric acid and recovered as zinc sulfate by evaporation while the cobalt and remaining zinc were further bulk stripped at pH 1.0. The Zn and Co in the strip liquor was separated by SX extraction with Cyanex 272 at pH 3 for zinc and pH 5 for cobalt which was then recovered by electrowinning after stripping.

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A process was patented by Urbanski (1988) for the recovery of zinc, manganese, and magnesium salts from aqueous solutions of their mixtures, especially from spent zinc electrolyte. In this process, the spent zinc electrolyte containing Zn, Mn, Mg, and optionally NH4 was first subjected to selective extraction of zinc at pH 1.83.0 using D2EHPA. The organic phase was stripped using H2SO4. Then, the zinc-free electrolyte was subjected to selective extraction of manganese at pH 3.36.5 using D2EHPA. The organic phase was stripped using a mineral acid solution. A study of solvent extraction with DEHPA showed that zinc in the leach solution from an acid mine drainage sludge sample could be extracted without Ni, Co and Mn up to a pH of 2.75 (Cho and Dai, 1994). A combined chemical precipitation with solvent extraction for separation of nickel and cobalt from sulfuric acid leaching solution of ocean polymetallic nodules was reported by Jiang et al. (1998) The leach liquor containing Ni, Co, Mn and Zn was subjected to selective extraction of Zn from Mn with P204 (Chinese version of D2EHPA), followed by scrubbing and stripping to yield zinc sulfate solution. Nickelcobalt separation was achieved using Cyanex272. The compositions of the resultant sulfate solutions had b 20 ppm impurity. Ritcey and Lucas (1971) developed a process for recovery and separation of manganese and zinc from calcine leach liquor. In this process, the separation of copper was accomplished by using LIX 63 with very little zinc and no manganese extraction in the equilibrium pH range of 0.81.5. After removal of the copper using LIX 63 at a pH range of 0.81.5, zinc was extracted at pH 3.0 using 20% D2EHPA and 2% TBP in kerosene. The maximum separation of Zn/Mn was observed at pH 3.0 at an A/O ratio of 2. Any co-extracted manganese was removed by scrubbing with ZnSO4 solution. The extraction of metals with LIX 1104 (branched hydroxamic acid) dissolved in toluene and aqueous sulfate solutions has been investigated by Tait et al. (1995). The extraction of metals was found to be of the following order (pH50 in bracket): FeIIINCu2:3NZn5:0NNi5:5Co5:5 NCa5:9NMn6:5 Slope analysis showed that LIX 1104 forms chelates of ML2 with manganese, cobalt, zinc and cadmium and ML2 (HL) with nickel and copper. Table 3 gives the pH50 values at which 50% extractions were achieved under the conditions of 0.02 M metal ions, 1 M Na2SO4, and 25 C. It shows an ease of separation of zinc from manganese and a good possibility of separation of nickel and cobalt from manganese.

Bressa et al. (1979) investigated the recovery of zinc and its separation from manganese and magnesium in acidic and industrial solutions (ZnCl2 and ZnSO4) by solvent extraction with Tributylphosphate (TBP) in kerosene. Adding NaCl (3040 g/l) was found to be necessary, and extraction could be carried out at room temperature with a mixture containing kerosene 20 30%. Except for iron, the separation was very selective. The separation of iron, manganese and zinc using Alamine 336 in xylene from hydrochloric leaching solutions of manganese nodules containing cobalt and nickel has been reported by Ahn et al. (2003). In the presence of minimum 5.0 M chloride ion, cobalt could be selectively extracted from nickel due to cobalt chloro-complex in solution, but co-extracted with the impurity metals such as Cu, Fe, Mn and Zn. Manganese and nickel were effectively removed in the scrubbing step with 6.0 M HCl solution, and copper, iron and zinc by controlling the concentration of chloride ions in the cobalt stripping step. 3. Purification of manganese solutions 3.1. Sulfide precipitation of metals from Mn2+ solution The precipitation of metal sulfides and separation is based on different sulfide solubilities of metals at a certain pH and temperature. Gaseous hydrogen sulfide (H2S) or sodium sulfides (Na2S) or ammonium sulfide (NH4)2S is usually employed in the precipitation of metal sulfides. The thermodynamic equilibria involved in the sulfide precipitation can be expressed as: H2 Sg 2H S2 Kp H 2 S2 PH2 S
1 M n S
n 2 2

n M n S2 MSn=2 2

1 KS

where Ks is the solubility product of the metal sulfide. These relationships can be written in the forms: n pH log Kp log PH2S logS2 2 n logM n log KS logS2 2 6 7

For a given PH2S, each can be plotted on a sulfide solubility diagram as shown in Fig. 2 (Based on Monhemius, 1977).

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Fig. 2. Sulfide solubility diagram at 25 C (Based on Monhemius, 1977).

It can be seen that the line of Mn2+ is far to the right hand side of the diagram, indicating that manganese sulfide is more soluble than most other metal sulfides. This offers a theoretical basis for separation of Mn2+ from other metals such as Cu2+, Zn2+, Co2+, Ni2+, and Fe2+ in hydrometallurgical processes, where other metal ions are precipitated as metal sulfides while Mn2+ ions remain in solution. Sulfide precipitation for purification of MnSO4 solutions was used in electrodeposition of manganese by Hannay and Walsh (1944). The MnSO4 solution was freed of impurities such as Ni, Co, Zn, Pb, As, Sb, Fe, Cu and Cd by the treatment with H2S at pH 56 and at a temperature not higher than 25 C. Roehrborn and Amirzadeh-Asl (1994) reported the sulfide precipitation for the separation of zinc from manganese in the leach solution of the sludges from the processing of raw zinc liquor. The zinc in the solution was precipitated with Na2S solution to pH 57, leaving manganese in solution for subsequent recovery. The sulfide precipitation has been commercially practiced in Murrin Murrin nickel laterite processes (Motteram et al., 1996). The separation of nickel, cobalt, copper and zinc from manganese, magnesium and calcium impurities is achieved in one step sulfide precipitation and manganese is discarded. The nickel, cobalt, copper and zinc in the precipitate are re-leached under pressure with oxygen followed by solvent extraction with Cyanex 272 to separate the zinc, cobalt and nickel. The nickel and cobalt are recovered by reduction with hydrogen. Jandova et al. (2005) studied a controlled sulfide precipitation for recovery of copper and nickelcobalt concentrates from the liquors originating from leaching manganese deep ocean nodules in FeSO4H2SO4H2O solutions. The metal ions studied include Co2+, Cu2+, Fe2+, Ni2+, Mn2+ and Zn2+. Promising results were

obtained when copper and nickelcobalt concentrates were precipitated with 5.5% solution of (NH4)2S. Copper precipitation was conducted at pH 1.0 and nickelcobalt precipitation at pH 3.0 at the laboratory temperature, and leaving manganese in solution for possible recovery or discharge. 3.2. Adsorption and ion exchange A method using ion exchange for purification of manganese sulfate solutions was reported by Kholmogorov et al. (1997). It was found that cobalt sorption increased with pH increase up to 5.5. The cobalt and manganese separation was achieved by substituting the manganese ions with cobalt ions at pH more than 3.5 using chelating resins ANKB-35 and AMF-2M. The cobalt content in the resulting manganese sulfate solutions was below 0.6 mg/l. Kudryavtsev et al. (1991) used a polyethylenepolyamine-type ion exchanger for separation of cobalt and manganese in sulfate solutions. The ion exchanger was pre-treated with mineral acids at pH 33.5. Amino-carboxylic amphoteric ion exchangers were tested (Kononova et al., 2000) for the separation of nickel from the Mn(NO3)2H2O system. The examined ion exchanger included aminocarboxylic amphoteric ion exchangers AMF-1T, AMF-2T, AMF-2M, ANKB-35 as well as carboxylic cation exchanger KB-2T. Of the exchangers examined, the ion exchanger AMF-2T was found to be the best for the selectivity of Ni(II) over Mn(II). Diniz et al. (2005) has reported an uptake of copper, nickel, cobalt, lead, iron and manganese from manganese chloride leach solution onto the chelating resin Dowex M4195 in the column experiments. The solution contained 85 mg/L Cu, 100 mg/L Ni, 47.5 mg/L Co, 40 mg/L Pb, 6.0 g/L Fe, 47.5 g/L Mn with 1.0 M free acid and 3.6 M

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Fig. 3. A solubility diagram of metal hydroxides at 25 C (Based on Monhemius, 1977).

total chloride. The results indicate a sequence of affinity of metals in the order: CuNNiNPbNFeNCoNMn The results demonstrated the ability to remove contaminants to an extent satisfying the quality criteria required for the utilisation of the manganese chloride solution for preparing manganese chemicals. The column elution tests confirmed that a two-stage elution scheme, whereby sulfuric acid was first used to elute iron, nickel and cobalt from the resin, and then a subsequent ammonium hydroxide elution recovered almost all of the copper. 4. Precipitation of manganese compounds 4.1. Hydroxide precipitation The precipitation of metals in solutions as metal hydroxides is the most common way to remove metals from solutions in hydrometallurgical processes. The equilibrium of a metal hydroxide precipitation can be expressed by the general equation: M n nOH M OHn The equilibrium constants can be written as: K1 1 1 M n OH n KS 9 8

precipitation while separation of Zn2+ from Mn2+ is possible but that of Co2+, Ni2+ from Mn2+ is difficult by a hydroxide precipitation method. Thus, in hydrometallurgical separation processes, hydroxide precipitation alone does not provide a useful means for separation and recovery of manganese. Generally, hydroxide precipitation in separation and/or recovery of manganese is only useful in some special cases in combination with other methods. One practical strategy is to use hydroxide precipitation for valuable metals together with manganese followed by selective leaching to separate valuable metals from manganese. This is used in the Cawse laterite process (Manson et al., 1997), which comprises the following steps: (1) Precipitation of copper, zinc, nickel and cobalt together with some of the manganese as hydroxides using MgO. (2) Leaching with ammonia in the presence of air and CO2 to selectively dissolve the nickel, cobalt, copper and zinc in the precipitate as ammine complexes in the leach liquor, leaving manganese in the leach residue as manganese carbonate or oxides. (3) Nickel and copper are separated from cobalt and zinc by SX with LIX84I. The nickel is recovered by electrowinning while cobalt, together with zinc, is precipitated as sulfide. In CESL nickel laterite process, a similar principle is used for separation of nickel and cobalt from manganese with the ammonia carbonate re-leach (Jones and Moore, 2001). The major advantage of this strategy is the elimination of a large volume of the feed solution at a very early stage from the process circuit by hydroxide precipitation of the metals. However, the operation cost with respect

where Ks is the solubility product. The equilibria of metal hydroxide precipitation can be presented graphically in a solubility diagram Fig. 3 (based on Monhemius, 1977). From the diagram, it is predicted that Fe3+, Al3+, Pb2+ and Cu2+ can be readily separated from Mn2+ by hydroxide

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to the re-leach and subsequent separation processes is high. A different strategy was investigated for separation and recovery of cobalt and manganese from spent bromide oxidation catalysts by Clark et al. (1996). Instead of hydroxide precipitation followed by selective leaching with ammonia, a selective precipitation of manganese with ammonia was used. The spent catalysts containing 27 31% Co, 2533% Mn, 014% Fe together with Cr, Cu and Ni, were leached with 4 M HCl at 80 C for 4 h. The leach liquor was then purified with successive neutralisations: (1) Addition of NaOH to remove iron and chromium as hydroxide at pH 2. (2) Addition of ammonia to precipitate manganese from an aerated solution leaving cobalt as a Co (III) hexammine complex in the solution. (3) Recovery of cobalt from this solution by chemical or electrochemical processes. Compared with the first strategy, the selective precipitation simplifies the process by omitting the releach step. However, more ammonia would be used for stabilising the valuable metals as hexammine complex if the solution volume is large. For the case of laterite processing with a large volume of leach liquor, the first strategy is advantageous in saving expensive ammonia at the expense of comparatively cheap neutralisation agent. 4.2. Ammonia/carbonate precipitation of MnCO3 Carbonate precipitation of manganese is an important practical process for recovery of manganese. The use of ammonia in the carbonate process, instead of sulfide precipitation, provides an alternative strategy for separation of other valuable metals such as nickel and cobalt from manganese. In this case, manganese precipitates out as solid manganese carbonate while cobalt and nickel are stabilised in the solution as ammine complexes. Several such processes have been reported in the literature. INCO (Illis and Brandt 1975) developed a process for selective recovery of metal values from sea nodules containing Mn 24.2%, Fe 5.8%, Ni 1.2%, Cu 0.85%, and Co 0.17%. The process comprised a reductive roasting followed by leaching with 38% NH3 and 1 6% CO2 to extract nickel, cobalt and copper into solution whilst most of soluble manganese was stabilised in solid residue by forming MnCO3 compound which was then re-leached and recovered by crystallisation and calcination. In processing nickel laterite ores, a similar strategy has been adopted by Queensland Nickel (QNI) (Reid and

Price, 1993; Price and Reid, 1993; Skepper and Fittock, 1996). After roasting the ore to reduce the nickel and cobalt to their metallic form, both metals are leached with an ammoniacal carbonate solution. The manganese leached into the solution is minimised by forming stable manganese carbonate precipitate. The dissolved nickel, cobalt and zinc are separated by a series of selective solvent extractions followed by precipitation of nickel from the strip liquor as nickel carbonate and cobalt as sulfide. Kono et al. (1986) studied separation and recovery of Mn, Cu, Ni and Co from sulfurous acid leach liquor of sea nodules. In this process, Cu, Ni, Co, and Mn were completely leached with 0.2 M H2SO3 while 30% of iron was undissolved. After oxidation by aeration, Fe2+ was precipitated as Fe(OH)3 at pH 4.34.4. Subsequently, manganese was precipitated as MnCO3 by addition of (NH4)2CO3, while Cu, Ni, and Co in the solution were stabilized as ammine-complexes with NH3. 4.3. Oxidative precipitation of MnO2 Oxidative precipitation of manganese as insoluble manganese oxides, mainly MnO2, has found a wide application for removal of manganese impurity from Zn, Co, and Ni processing circuits. Manganese dioxide (MnO2) is a strong oxidising agent with the standard reduction potential being 1.224 V. It needs a stronger oxidant to oxidise Mn(II) to higher valence oxides, initially Mn3+and then MnO2. Various oxidants for Mn(II) have been studied and applied to the practical processes, including ozone, SO2/O2 oxidising mixture, Caro's acid, peroxydisulfuric acid, hypochlorite and chlorate. 4.3.1. Ozone as oxidant Bolton et al. (1981) reported a process for removing manganese from an aqueous acidic sulfate solution containing zinc and manganese without removing a substantial amount of zinc from the solution. The solution had a free acid of 0.12 M, and contained 5170 g/L Zn and 125 g/L Mn. The process comprised treating the solution with ozone to oxidise manganese to manganese dioxide and removing manganese dioxide from the solution. The process was further patented for removal of both manganese and chloride ions from aqueous acidic zinc sulfate solutions (Bolton et al., 1982). In this process, acidified aqueous ZnSO4 solutions were treated with ozone for the sequential precipitation of manganese as MnO2, and removal of chloride as chlorine gas. The process was proposed for the treatment of spent electrolytes from H2SO4 leaching of ZnS ores. For example, O2 containing 57.5 mg/L O3 was passed countercurrently through a solution containing H2SO4

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150 g/L, Zn 50 g/L, Mn 3.74 g/L and Cl 107 mg/L in a three-cell series at approximately 23 C. The manganese removal occurred mainly in the first and second cell, but chloride removal occurred in the second and third cell. The final solution contained Mn 30 mg/L and Cl 3 mg/L. The ozone oxidant is an effective but rather expensive oxidant for Mn(II) and thus is less feasible than cheaper oxidants such as SO2/O2 mixture. 4.3.2. Chloric acid, chlorine dioxide and hypochlorite as oxidants Chloric acid (HClO3) was used in a patented process to separate zinc oxide and manganese oxide by Cawlfield and Ward (1995). The process comprised the following basic steps: (1) Reacting a mixture of zinc oxide and manganese oxide with an aqueous chloric acid solution wherein the chloric acid was in molar excess of the manganese oxide to form a chlorine gas phase, a solid phase containing manganese dioxide and a solution phase containing zinc chloride. (2) Separating the solid phase containing manganese dioxide from the liquid phase. (3) Recovering the zinc metal from the electrolytic cell. Yuan et al. (2000) studied oxidation and recovery of manganese in the leaching solution from a manganese ore using chloric salt (NaClO3) as the oxidant for Mn(II) in the acidic solutions. Optimum conditions were stepwise addition of the oxidant at a NaClO3:ore ratio of 0.25:1 (w/w), a acid:ore ratio of 0.540.55:1 (w/w), and liquid:solid ratio of 3:1, and a reaction time of 6 h. More than 90% of manganese was recovered under the optimum conditions. Chlorine dioxide (ClO2) oxidant was used by Park et al. (2005) for selective leaching of nickel and cobalt from the precipitated manganese hydroxide. The process is selective because manganese is dissolved and reprecipitated as MnO2 under the strong oxidising conditions while nickel and cobalt tend to be preferentially leached into the solution. In the patent by Ferron (2003), a process was reported involving oxidative separation of cobalt and manganese from nickel in a leach solution containing Ni, Co, Fe, and Mn. The process involved: (1) Removing the iron from solution by oxidation and partial neutralisation; (2) Removing cobalt and manganese from the solution by oxidation and precipitation at pH from 1 to 4 with hypochlorite, and

(3) Conventional nickel recovery from the resultant solution. One problem of using chloric acid or chlorine in the process is its highly corrosive nature and the costs for its control and handling would be high. 4.3.3. Sulfur dioxide/oxygen as oxidant Sulfur dioxide/oxygen (SO2/O2) at a correct ratio is a strong oxidant for Fe(II) and Mn(II). Manganese is precipitated as MnO2/Mn2O3 spontaneously using SO2/ O2 gas mixtures in the pH range of 36. The mixture can also oxidise Co(II) and Ni(II) at pH above 5 and 7, respectively. The study by Zhang et al. (2002) showed that the rate of Mn(II) oxidation with SO2/O2 was the first order with respect to SO2 partial pressure up to 5.7% SO2 at 80 C and half order with respect to [H+]. The rate of oxidation of Mn(II) was slow at pH b 3 and increased rapidly at pH N 4. Any Fe(II) present was oxidised and precipitated before Mn(II) removal. The selectivity of manganese precipitation at pH 36 was consistent with thermodynamic data for the MnNi/Co H2O systems. The SO2/O2 oxidant is comparably cheap and easy to make or extract from smelter off-gas. These characteristics have made it a competitive oxidant and found a wide application for separation or removal of manganese from valuable metals such as nickel, cobalt and zinc. Several processes have been patented as described below. Kniprath (1970) was the first to develop a method for simultaneous precipitation of MnO2 or CoOOH at pH 5 with oxygen or air and a reducing agent, e.g. SO2 or Na2SO3. The method was useful in purification of nickel liquors containing Fe, Mn, Co, and other metals, from electrolytic copper refining. Thus, 416 mL/min O2 and 183 mL/min SO2 were passed into a litre of solution containing 2 g Mn2+ (as sulfate) at 50 C and pH 5.0 adjusted by addition of NaOH. After 2 h, manganese was precipitated quantitatively as MnO2.H2O. Okajima (1975) disclosed a process for the treatment of manganese nodules, in which, manganese and iron were oxidatively precipitated as respective oxides by aeration of the solution containing 50 g/L Na2SO3. The solid leach residue, after combining it with the precipitate was used for making ferromanganese containing 43% Mn and 16% Fe. The ferromanganese can be readily enriched for metallurgical applications. An addition of chloride and use of the mixture of SO2/Air improved the separation of iron and manganese (Okajima, 1977). Manganese could be effectively separated from zinc solutions with optimum mixture of SO2 (0.510%) and O2

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at 4080 C and pH 35, preferably pH 34 to minimise loss of zinc by coprecipitation (Ferron, 2000; Demopoulos et al., 2001). A distribution of nucleation sites in the reaction such as MnO2 crystals enhances the reaction. The process is suitable for decreasing the manganese impurity in acidic solution for zinc electrowinning. Similar principles can also be applied for separation of manganese from cobalt in cobalt leach solutions (Ferron and Turner, 2000; Lunt et al., 2003). In the copresence of iron and manganese in the cobalt solutions, iron (II) can be first oxidised with the SO2/O2 gas mixture at 60 C and then precipitated by hydrolysis at pH control 2.53.5, followed by oxidative precipitation of manganese in the second stage. Optionally, air can be used in the mixture with 0.12% SO2. 4.3.4. Persulfate as oxidant The oxidation of manganese by peroxy-monosulfuric acid (Caro's acid) and peroxy-disulfuric acid (H2S2O8) was reviewed by Burkin et al. (1981), and Burkin and Chouzadjian (1983). The oxidation by these oxidants can be expressed by the following reactions: Oxidation by Caro's acid Mn2 H2 SO5 H2 OYMnO2 2H H2 SO4 10 and oxidation by peroxy-disulfuric acid Mn2 H2 S2 O8 2H2 OYMnO2 2H 2H2 SO4 11 Caro's acid was used for the recovery of manganese from aqueous acidic leach solutions (Burkin and Chouzadjian, 1979). The developed process consisted of: (1) Oxidation of Mn(II) to the Mn(IV) state in 2 stages at 7090 C with 110160% of stoichiometric amount of Caro's acid relative to that of manganese; (2) Neutralisation of the residual Caro's acid with a neutralizing agent (preferably a hydroxide) in one or more stages at 100133% of stoichiometric amount; (3) Separation of the precipitated manganese salt from the preferred solutions at Caro's acid/H2O2 ratio of 30:1. Wang and Zhou (2002) investigated a hydrometallurgical process for the recovery of cobalt from zinc plant residue, in which ammonium peroxy-disulfate ((NH4)2S2O8) was used for oxidative precipitation of

iron and then manganese as MnO2. It was found that chloride ion seriously affected the precipitation of manganese, which was attributed to the reduction of the manganese oxide. The standard redox potential of Mn3O4/Mn2+ pair is 1.76 V and that of Cl2/Cl pair is 1.39. Therefore, the manganese oxide can be thermodynamically reduced to Mn2+ by chloride. The oxidation reduction reaction between Mn2+ and ammonium peroxydisulfate was proposed to proceed according to Eq. (12): 3Mn2 NH4 2 S2 O8 4H2 O Mn3 O4 NH4 2 SO4 H2 SO4 6H 12

The above reaction indicates that the addition of ammonium peroxy-disulfate will cause a decrease of pH, which may affect the precipitation significantly. The acid can be neutralised by the addition of a dilute sodium carbonate solution. Furthermore, at pH 4.04.5, precipitation of iron and manganese could be completed by applying sufficient ammonium peroxy-disulfate solution. Sarma et al. (1987) and Nathsarma and Sarma (1987) reported a process for the recovery of Ni, Co, and Cu and oxidative precipitation of the iron and manganese with potassium persulfate in solutions from three different raw materials: lateritic nickel ores, copper converter slag and Indian Ocean manganese nodules. This removal also resulted in some loss of cobalt due to its adsorption on the manganese dioxide matrix. 5. Evaluations of methods for manganese recovery Fig. 4 graphically summarises the major routes for recovery of manganese from solutions containing one or more of metal impurities such as Fe, Zn, Cu, Ni, and Co. The applicability of a route for recovery of manganese or other valuable metals from a solution depends on a number of cost sensitive factors, including the concentration of manganese in the solution, levels of other impurities, and purity of final manganese products. A general evaluation of each route is outlined below. Solvent extraction. Little work has been reported in the literature for the recovery of manganese using solvent extraction in the manganese industry. Solvent extraction systems can be applied to both the recovery of manganese and separation of other metal impurities. DEHPA has been identified and is the cheapest of the reagents for selective extraction of manganese over other impurities, e.g. Ni, Co and Mg. However, DEHPA cannot separate manganese from Ca. Synergistic SX systems offer better selectivity for purification of manganese solution, but they are generally more costly due to involving expensive synergists such as hydroxyoxime and pyridinecarboxylate

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Fig. 4. Simplified possible routes for recovery of Mn from waste effluents.

esters. The main operating cost by solvent extraction is the base for pH adjustment. Ammonia is the most appropriate neutralisation agent in terms of cost and convenience for use in solvent extraction. The cost of anhydrous ammonia is about 16% of the selling price for the manganese metal product, based on the current manganese metal price (US $1590 per tonne). This seems acceptable to the industry. Therefore, solvent extraction may offer an alternative to hydroxide and carbonate precipitation for recovery of manganese from the industrial effluents. Sulfide precipitation. Sulfide precipitation is not considered for use for recovery of manganese from industrial waste solutions because of some unfavourable attributes. First, this method requires pollution control and management. Second, it needs stages to separate from other impurities. Last, but most importantly, the manganese sulfide is not a favourable product for the manganese industry, needing further conversion. However, it provides a useful means for optional purification of small amounts of metal impurities such as Cu, Zn, Ni and Co before the step for production of highly pure manganese CMD, EM and EMD products. It has found wide applications for purification of solutions from leaching polymetallic manganese nodules, ZnMn bearing sludges, battery wastes, organic wastes, and manganese-bearing laterite ores. Ion exchange. Ion exchange is a useful method for purification of manganese solution to separate metals

including Cu, Fe, Co, Ni and Pb. Compared with sulfide precipitation method, ion exchange is more environmentally friendly and easier to control. However, a resin has a limited capacity for adsorption of particular metals and therefore more suitable for removal of trace amounts of metal impurities for preparation of highly pure manganese solutions. Hydroxide precipitation. Manganese can be precipitated as manganese hydroxide, Mn(OH)2 which is then slowly oxidized to a mixture of hydrated manganese oxides in the presence of air, or which can be calcined at 300450 C with aeration to yield MnO2. However, the precipitation requires solution pH above 9 and is less selective. Based on the stability constants reported by Monhemius (1977), the selectivity of Mn from Mg and Ca can be expressed by reactions (13) and (14): MgOH2 Mn2 MnOH2 Mg2 CaOH2 Mn2 MnOH2 Ca2 Log K 1:44 13

Log K 7:36

14

The values of the equilibrium constants K indicate that the selectivity for manganese hydroxide is thermodynamically more favourable with respect to Ca than Mg. However, this is not desirable for the separation of

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manganese in the waste effluents which usually contain much more Mg (N 10 g/L) than Ca (b 1 g/L). In a practical application, substantial amount of magnesium is expected to be co-precipitated. Furthermore, for the production of purer manganese product, more expensive base reagents such as ammonia or sodium hydroxide are preferred to lime which would form calcium sulfate and co-precipitate with manganese. In hydrometallurgical processes, hydroxide precipitation alone does not provide a useful means for separation and recovery of manganese. Generally, hydroxide precipitation in separation and/or recovery of manganese is only useful in some special cases. One strategy is to precipitate manganese and other valuable metals as mixed hydroxides which is then leached by acid in the presence of an oxidant for Mn(II). This results in insoluble MnO2 and soluble value metals (Zn, Cu, Ni and Co) in solution. Carbonate precipitation. Carbonate precipitation of manganese as manganese carbonate can occur at pH about 8.5 and the selectivity for manganese is thermodynamically more favourable with respect to magnesium than calcium. This is indicated in reactions (15) and (16) (Stability constants based on Lide 2007): MgCO3 Mn2 MnCO3 Mg2 Log K 5:48 15 CaCO3 Mn2 MnCO3 Ca2 Log K 2:35 16 This would be suitable for the separation of manganese in solutions containing more magnesium than calcium impurities compared with hydroxide precipitation. In addition, manganese carbonate is a favourable form which can, after drying, be sold directly to the manganese industry or further processed for production of CMD, EM and EMD. In separation process, carbonate salts or carbon dioxide together with ammonia can selectively precipitate manganese as manganese carbonate while copper, nickel and cobalt are stabilised in solution as ammine complexes. However, for the industrial waste solutions containing relatively low manganese and high magnesium, the coprecipitation of magnesium and calcium may be considerable and need further purification steps for production of highly pure manganese products. Therefore, the applicability of carbonate precipitation for recovery of manganese would depend on the concentration of manganese relative to that of impurities such as magnesium and calcium.

Oxidative precipitation. Oxidative precipitation of manganese as insoluble MnO2/Mn2O3 is highly selective, especially when the solutions are free from iron. Small amounts of nickel and cobalt may be coprecipitated through oxidative precipitation and/or adsorption mechanism, depending on the solution pH and the types of oxidants used. The co-precipitated nickel and cobalt could be further separated and recovered as by-products and may provide additional benefits as nickel and cobalt are more valuable metals than manganese. The main concern for use of oxidative precipitation method is the cost of some oxidants such as ozone, Caro's acid, and peroxy-disulfuric acid. This may not justify its use for recovery of manganese from a solution containing a low manganese concentration, e.g. laterite waste solutions containing 15 g/L manganese. The SO2/air oxidising mixture is a relatively cheap oxidant which is considered to be the most suitable oxidant for recovery of manganese from waste solutions. In the separation of manganese from other valuable metals such as zinc, cobalt and nickel, the unique feature of the oxidative precipitation is that manganese can be selectively separated at lower pH range 36. 6. Conclusions Solvent extraction is a promising alternative to the precipitation methods for recovery of manganese from solutions. DEHPA has been identified as the cheapest of the reagents for selective extraction of manganese over other impurities including Ni, Co, and Mg. The main operating cost is the base for pH adjustment, for which ammonia appears to be acceptable to the industry based on the current prices of manganese products and ammonia reagent. Manganese sulfide is an unfavourable form for manganese industry and not suitable for manganese recovery but sulfide precipitation has been widely applied for purification of manganese solutions and for the preparation of highly pure manganese solution for production of CMD, EM and EMD. Ion exchange is only suited for the removal of small amounts of impurities due to a limited capacity of a resin. Hydroxide precipitation is usually used for removal of iron and aluminium impurities in manganese solutions, but it is less selective and is not suitable for the recovery of manganese from a solution containing a relatively large amount of magnesium. Carbonate precipitation is more selective and provides a more suitable form of manganese product for further processing. However, for the waste solutions containing low manganese and high magnesium, its product quality and further purification costs are the major concerns.

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Oxidative precipitation offers the best selectivity for recovery of manganese as MnO2/Mn2O3 over other metals including Zn, Ni, Co, Mg and Ca in a pH range of 36. The manganese oxides precipitated are expected to be relatively pure and may need minimum purification or processing for production of CMD product. For industrial waste solutions containing residual Ni and Co, the co-recovery of Ni and Co values is possible through adsorption mechanism or co-precipitation as their oxide forms at higher pH range. The key issue for its application is the cost of oxidants, for which the SO2/ O2(Air) mixture is an effective and cheap oxidant. Both oxidative precipitation and solvent extraction are recommended for future research and development for recovery of manganese from industrial waste solutions. Acknowledgements The authors would like to thank CSIRO Minerals library staff for collecting some references and Dr David Muir for reviewing this paper and providing valuable comments. References
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