Trans. Nonferrous Met. Soc.

China 24(2014) 3716−3721

Preparation of electronic grade manganese sulfate from

leaching solution of ferromanganese slag

Sheng YAN1,2, Yun-ren QIU1

1. School of Chemistry and Chemical Engineering, Central South University, Changsha 410083, China;
2. Innovation Base of Energy and Chemical Materials for Graduate Students Training of Hunan Province,
Changsha 410083, China
Received 11 November 2013; accepted 6 June 2014

Abstract: Preparation of electronic grade manganese sulfate from ferromanganese slag, including grinding, leaching and purification,
was studied. The impurities, such as Fe3+, Al3+, Ca2+, Mg2+, heavy metal ions and Na+, K+, were removed from leaching solution by
neutralized-hydrolysis, fluorination precipitation, sulfuration precipitation and re-crystallization. Effects of pH of reaction,
temperature and dosage of the different additives on removal rates of the metallic ions in leaching solution were investigated, and the
suitable temperature, pH and the added amount of precipitating agent were obtained. The prepared manganese sulfate product, of
which the mass fractions of Ca2+, Mg2+, Na+, K+ are all smaller than 0.005%, the mass fractions of Fe3+, Al3+ and heavy metal ions
are smaller than 0.001%, and the mass fraction of Mn2+ is greater than 32%, can meet the demand of anode materials of lithium-ion
batteries.
Key words: ferromanganese slag; leaching; purification; manganese sulfate; utilization of solid waste

production cost of electronic grade manganese sulfate,

1 Introduction bringing economic benefits and avoiding the
environment pollution. WANG [6] reported that
With the development of lithium-ion battery manganese was obtained through reduction method using
industry, the electronic grade manganese sulfate for sulfur dioxide as reducing agent and sintering method
anode material of lithium-ion batteries is widely used in with ferromanganese slag as the raw material.
the production of new generation of environmentally SAFARIAN et al [7] studied the kinetics and mechanism
friendly high-energy batteries [1−3]. of the simultaneous carbothermic reduction of FeO and
Ferromanganese slag is a kind of blast furnace MnO from high-carbon ferromanganese slag. However,
manganese slag from ferromanganese alloy smelting, a no studies have been reported on the preparation of
great amount of ferromanganese slag accounted for about electronic grade manganese sulfate from ferromanganese
2−3 times as much as ferromanganese alloy each slag due to it containing many impurities, such as iron,
year [4,5]. The impurity categories included in ferro- aluminum, potassium, sodium, calcium and magnesium,
manganese slag are the same as those of manganese ore, which makes it difficult to reduce the mass
and the content of MnO is higher than that of ordinary concentrations of Na+, K+, Ca2+ and Mg2+ smaller than
manganese slag. Besides, there are no elements which 0.005%, and that of heavy metal is smaller than 0.001%.
have influence on the battery performance expect In this work, preparation of electronic grade
calcium, magnesium, iron, aluminum, potassium, sodium manganese sulfate from ferromanganese slag, including
and heavy metal. However, these impurities can be leaching and purification, was first studied, and the
removed by different purification technologies in order. suitable condition was obtained. It can give guidance to
The preparation of electronic grade manganese the industrial production of the electronic grade
sulfate from ferromanganese slag can lower the manganese sulfate from ferromanganese slag.

Foundation item: Project (2013ZX0754-001) supported by China National Critical Project for Science and Technology on Water Pollution Prevention and
Control
Corresponding author: Yun-ren QIU; Tel: +86-731-88879616; E-mail: [email protected]; [email protected]
DOI: 10.1016/S1003-6326(14)63520-2
 Sheng YAN, et al/Trans. Nonferrous Met. Soc. China 24(2014) 3716−3721 3717
filtration, then washed with deionized water. In order to
2 Experimental further reduce the mass fraction of Na+ and K+, the
obtained crystal was re-dissolved, and the target product
2.1 Material and analysis method was obtained by re-crystallization and drying. The flow
Manganese fluoride (MnF2) and sulfuric acid chart is shown in Fig. 1.
(H2SO4) were of industrial grade, sodium sulfide (Na2S)
and manganese carbonate (MnCO3) were of analytical
3 Results and discussion
purity. Ferromanganese slag used in the experiment was
came from a smelter in Hunan, which was analyzed by
XRD and the results were listed in Table 1. Mass 3.1 Removal of iron, aluminum and silicon ions
concentrations of various ions were analyzed by an Iron, aluminum and silicon ions are the main
inductively coupled plasma-atomic emission associated elements of ferromanganese slag, so iron,
spectrometer (ICP-AES) aluminum and silicon ions should be removed at first.
Elimination of iron and aluminum ions can be obtained
Table 1 Major composition of ferromanganese slag (mass by adjusting a certain pH and temperature to form the
fraction, %) colloids of Fe3+ and Al3+ as Fe(OH)3 and Al(OH)3,
MnO MgO CaO Fe2O3 Al2O3 respectively, and the colloid can adsorb silicate in
16.32 4.63 33.56 4.23 11.42
leaching solution, while Mn2+ remains in solution.
Figure 2 exhibits the effect of temperature of
ZnO PbO CuO SiO2
reaction on mass concentration of silicon in filtrate under
0.78 0.44 0.37 27.1
the conditions of stirring rate of 500 r/min, pH 5.5. With
the increase of temperature from 20 to 95 °C, the mass
2.2 Experimental procedure concentration of silicon in filtrate continuously
The preparation of electronic grade manganese decreases. When the reaction temperature is greater than
sulfate from ferromanganese slag is described as follows. 80 °C, the mass concentration of silicon is smaller than
200 g of ferromanganese slag powder ground to 250 μm 2 mg/L in filtrate, which can meet the production of
or less was added to 700 mL of 30% H2SO4 solution, and
electronic grade manganese sulfate. So the optimal
reacted for 3 h at 80 °C under stirring. The leaching
temperature of reaction is 80−95 °C.
solution with mass concentration of Mn2+ of about 35 g/L,
However, the pH needs to be controlled strictly to
was obtained by filtration. Solid MnCO3 was added to
avoid the manganese loss due to precipitation of
the leaching solution to adjust pH so that the hydroxide
manganese hydroxide [7,8]. Figure 3 exhibits the effect
precipitation of Fe3+ and Al3+ could be formed, and the
precipitated hydroxides were removed by filtration. The of pH on mass concentration of Fe3+ and Al3+ in filtrate.
obtained filtrate was evaporated till mass concentration The leaching solution was treated by adding solid
of Mn2+ arrived at 92−94 g/L. Then, a certain amount of MnCO3 to adjust pH from 4 to 6 at 80−90 °C for 1.5 h.
solid MnF2 was added to the concentrated solution so The equation of metal hydroxide precipitation can
that the fluoride precipitation of Ca2+ and Mg2+ could be be expressed as follows:
formed, and the precipitated fluorides were removed by Mn++nOH− M(OH)n (1)
filtration. And then, a certain amount of solid Na2S was
added to the filtrate so that sulfide precipitation of heavy The equilibrium constant can be written as
metal ions could be formed, and the precipitated sulfides
1 1
were removed by filtration. Finally, the filtrate was K= = (2)
[M n + ][OH]n Ks
evaporated, the crystal of MnSO 4 was obtained by

Fig. 1 Flow chart of preparation of electronic grade manganese sulfate

3718 Sheng YAN, et al/Trans. Nonferrous Met. Soc. China 24(2014) 3716−3721
3.2 Removal of calcium and magnesium ions
Generally, it gets difficult to remove calcium and
magnesium ions from the solution containing
manganese, because the chemical properties of Ca2+ and
Mg2+ are similar to those of Mn2+ [10]. The different
technologies of purification such as crystallization at
high temperatures, solvent extraction and adsorption onto
active carbon can remove about 90 % of Ca2+ and Mg2+
from manganese sulfate solution, but the mass
concentrations of Ca2+ and Mg2+ in solution cannot meet
the demand of the anode material of lithium-ion batteries.
Thus, a suitable way needs to be found to effectively
remove calcium and magnesium impurities from the
solution containing manganese.
Fig. 2 Effect of temperature on mass concentration of silicon The filtrate, of which Fe3+ and Al3+ had been
removed, was treated by adding solid MnF2 and
controlling the reaction condition to remove Ca2+ and
Mg2+. Figure 4 exhibits the effect of pH of fluorination
reaction on mass concentrations of Ca2+ and Mg2+ in
filtrate under the condition of adding 1.3 times the
theoretical amount of MnF2, temperature 90 °C and time
1.5 h. With the increase of pH from 4.0 to 6.5, the mass
concentration of Ca2+ decreases from 88 mg/L to 7 mg/L,
and that of Mg2+ decreases from 96 mg/L to 10 mg/L.
When the pH is smaller than 4, the precipitations of Ca2+
and Mg2+ as CaF2 and MgF2 respectively are not
complete because F− reacts with H+ to form HF and its
dissociation constant (KHF=7.4×10−4) is relatively small
[11]. When the pH is greater than 6, the mass
Fig. 3 Effect of pH on mass concentrations of Fe3+ and Al3+ in concentrations of Ca2+ and Mg2+ are smaller than 14
filtrate mg/L in filtrate. But the excessively high pH could cause
the loss of manganese. Thus, the optimal pH of
where Ks is the solubility product, and M is Fe, Al or Mn. fluorination reaction is 6.
Equation (2) can be written as
1 Ks
pH = 14 + lg (3)
n [M n + ]

According to Eq. (3) and the practical

concentrations of Fe3+, Al3+ and Mn2+ in leaching
solution, the pH values of the starting precipitation of
Fe3+, Al3+ and Mn2+ are 1.6, 2.8 and 6.5, respectively.
Therefore, the pH is not greater than 6.5. Figure 3 shows
that with the increase of the pH from 4 to 6, the mass
concentration of Fe3+ decreases from 56 mg/L to 1.6
mg/L and that of Al3+ decreases from 112 mg/L to 1.8
mg/L. When pH is greater than 5.5, the mass
concentrations of Fe3+ and Al3+ are smaller than 2 mg/L,
which can meet the production of electronic grade Fig. 4 Effect of pH of fluorination reaction on mass
manganese sulfate. Thus, the suitable pH is 5.5−6.0. concentrations of Ca2+ and Mg2+ in filtrate
However, it is very difficult to filtrate for the
formation of Fe(OH)3 colloidal solution at room Figure 5 exhibits the effect of fluorination reaction
temperature. When the temperature is greater than 80 °C, temperature on mass concentrations of Ca2+ and Mg2+ in
the precipitation of Fe(OH)3 is easily separated by filtrate under the condition of adding 1.3 times the
filtration [9]. Thus, the suitable temperature is 80−90 °C. theoretical amount of MnF2, pH 6 and time 1.5 h. With
 Sheng YAN, et al/Trans. Nonferrous Met. Soc. China 24(2014) 3716−3721 3719
2+
the increase of fluorination reaction temperature from Mg are smaller than 14 mg/L, which can meet the
60 °C to 95 °C, the mass concentration of Ca2+ decreases production of electronic grade manganese sulfate. While,
from 74 mg/L to 5 mg/L and Mg2+ from 92 mg/L to 8 nMnF2 is greater than 1.2, and the mass concentrations of
mg/L, because the fluorination reactions are endothermic, Ca2+ and Mg2+ do not decrease. Thus, 1.2 times the
heating is conducive to the generation of CaF2 and MgF2, theoretical amount of MnF2 is suitable.
and CaF2 and MgF2 have superior filter performance at
higher temperatures [12,13]. When the fluorination 3.3 Removal of heavy metal ions
reaction temperature is greater than 90 °C, the mass The filtrate, of which Ca2+ and Mg2+ had been
concentrations of Ca2+ and Mg2+ are smaller than 14 removed, was treated by adding solid Na2S to remove
mg/L in filtrate, which can meet the production of heavy metal ions based on the different sulfide
electronic grade manganese sulfate. Thus, the optimal solubilities of metals at a certain condition [14, 15]. The
fluorination temperature is 90−95 °C. effect of pH on mass concentrations of heavy metal ions
in filtrate is illustrated using Ni2+ as example because the
solubility product of NiS is larger than that of other
heavy metal sulfides such as CuS, CdS, PbS, ZnS and
CoS. Figure 7 exhibits the effect of pH on mass
concentration of Ni2+ in filtrate by adding 1.4 times the
theoretical amount of Na2S during reaction of 1.5 h at
90 °C.

Fig. 5 Effect of fluorination temperature on mass

concentrations of Ca2+ and Mg2+ in filtrate

Figure 6 exhibits the effect of the added amount of

MnF2 on mass concentrations of Ca2+ and Mg2+ in filtrate
under the condition of the pH 6.5, temperature 90 °C and
time 1.5 h, where nMnF2 is the mass ratio of practical
amount of MnF2 to theoretical amount by reaction Fig. 7 Effect of pH of sulphuration reaction on mass
equation. When nMnF2 is smaller than 1.2, the concentration of Ni2+ in filtrate
precipitations of Ca2+ and Mg2+ as CaF2 and MgF2
respectively are not complete due to the lack of F−. When The thermodynamic equilibrium involved in the
n MnF 2 is 1.2−1.4, the mass concentrations of Ca 2+ and sulfide precipitation can be expressed as follows [16,17]:
M2Sn 2Mn++nS2−, Ksp=[Mn+]2[S2−]n (4)
+ − −8
H2S(aq) H +HS , K1=10 (5)
− + 2− −12.9
HS H +S , K2=10 (6)
+ 2−
H2S(aq) 2H +S ,
[H ] [S 2 − ]
+ 2
K= = K1 K 2 = 10 − 20.9 (7)
[H 2S]

where Ksp is the solubility product of metals sulfide; K,

K1 and K2 are dissociation equilibrium constants. These
relationships can be written as
1 1 1
pH = 10.45 + lg K sp − lg[M n + ] − lg[H 2S] (8)
2n n 2

Fig. 6 Effect of added amount of MnF2 on mass concentrations

According to Eq. (8), the pH of fluorination reaction
of Ca2+ and Mg2+ in filtrate
relates to not only the solubility product of metal
3720 Sheng YAN, et al/Trans. Nonferrous Met. Soc. China 24(2014) 3716−3721
sulfides, but also the practical mass concentration of filtered at 95−100 °C and the obtained crystal of
metal ions. The mass concentration of manganese is MnSO4·H2O was washed and dried at 110 °C. 51 g of
relatively greater than that of other heavy metal ions in MnSO4·H2O was obtained, and the recovery rate of
solution, and the excessively high pH may cause the loss manganese was 88%. The mass fractions of Na+ and K+
of manganese. Figure 7 shows that the mass greatly decreased. The mass fractions of Na+ and K+
concentration of Ni2+ decreases from 11 mg/L to 1.6 before and after re-crystallization are shown in Table 2,
mg/L with the increase of pH from 3.5 to 6.0. When the and the quality of prepared sample is shown in Table 3.
pH is greater than 5.5, the mass concentration of Ni2+ is
smaller than 2 mg/L, which can meet the production of Table 2 Mass fractions of Na+ and K+
electronic grade manganese sulfate. Thus, the optimal pH Item w(Na+)/% w(K+)/%
of fluorination is 5.5−6.0. Before re-crystallization 0.0254 0.014
Figure 8 exhibits the effect of the added amount of
After re-crystallization 0.0033 0.0026
Na2S on the mass concentration of heavy metal ions in
filtrate after reaction for 1.5 h under 90 °C and pH 6,
where nNa2S is the mass ratio of practical amount of Na2S Table 3 Enterprise standard of electronic grade manganese
to theoretical amount by reaction equation. The mass sulfate (mass fraction, %)
concentration of Ni2+ decreases from 9 mg/L to 1.4 mg/L Item Mn Ca Mg Na K Fe
as nNa2S increases from 1.1 to 1.5. When nNa2S is smaller Standard ≥32 ≤0.005 ≤0.005 ≤0.005 ≤0.005 ≤0.001
than 1.3, the precipitation of Ni2+ as NiS is not complete Sample 32.21 0.0033 0.0024 0.0032 0.0029 0.0006
because a small part of S2− reacts with H+ to form H2S.
Item Al Pb Zn Cu Ni
When nNa2S is greater than 1.3, and the mass
Standard ≤0.001 ≤0.001 ≤0.001 ≤0.001 ≤0.001
concentration of Ni2+ is smaller than 2 mg/L, which can
meet the production of electronic grade manganese Sample 0.0007 0.0002 0.0002 0.0003 0.0004
sulfate. Thus, 1.3 times the theoretical amount of Na2S is
suitable. 4 Conclusions

1) Iron and aluminum ions in the leaching solution

are removed with neutralization-hydrolysis by adjusting
pH using solid MnCO3, under suitable conditions of pH
5.5−6.0, temperature 85−90 °C and time 1.5 h. The mass
concentrations of Fe3+ and Al3+ are smaller than 2 mg/L.
2) Calcium and magnesium ions in the leaching
solution are removed with fluoride precipitation by
adding solid MnF2, under suitable conditions of 1.2 times
theoretical amount of MnF2, pH 6, temperature 90−95 °C
and time 1.5 h. The mass concentrations of Ca2+ and
Mg2+ are smaller than 14 mg/L.
3) Heavy metal ions are removed with sulfide
precipitation by adding solid Na2S, under suitable
Fig. 8 Effect of added amount of Na2S on mass concentration conditions of 1.3 times theoretical amount of Na2S, pH
of Ni2+ in filtrate 5.5−6.0, temperature 90−95 °C and time 1.5 h. The mass
concentration of heavy metal ions is smaller than 2
3.4 Removal of sodium and potassium ions mg/L.
200 mL of filtrate, of which heavy metal ions had 4) Sodium and potassium ions are removed with
been removed and mass concentration of Mn2+ was 94 re-crystallization at temperature of 95−100 °C, and the
g/L, was evaporated till 10 mL or so under stirring at mass fractions of Na+ and K+ are all smaller than
temperature from 95 °C to 100 °C; the concentrated 0.005%.
suspension was filtered at 95−100 °C; the obtained
crystal of MnSO4·H2O was washed with 95−100 °C References
deionized water and dried at 110 °C. The mass fractions
[1] MANTHIRAM A. Materials challenges and opportunities of lithium
of Na+ and K+ of the obtained product were greater than
ion batteries [J]. The Journal of Physical Chemistry Letters, 2011,
0.005% (see Table 2). Thus, the obtained product was 2(3): 176−184.
dissolved again with deionized water, the obtained [2] MURALIGANTH T, STROUKOFF K R, MANTHIRAM A.
solution was evaporated till 5 mL, the suspension was Microwave-solvothermal synthesis of nanostructured Li2MSiO4/C
 Sheng YAN, et al/Trans. Nonferrous Met. Soc. China 24(2014) 3716−3721 3721
(M=Mn and Fe) cathodes for lithium-ion batteries [J]. Chemistry of [11] SAFAEEFAR P, ANG H M, KURAMOCHI H, ASAKUMA Y,
Materials, 2010, 22(20): 5754−5761. MAEDA K, TADE M O, FUKUI K. Measurement and correlation of
[3] HU Guo-rong, ZHANG Xin-long, PENG Zhong-dong. Preparation the solubility of MnSO4·H2O in ethanol + water + MgSO4· 7H2O
and electrochemical performance of tantalum-doped lithium titanate solutions [J]. Fluid Phase Equilibria, 2006, 250(1−2): 64−69.
as anode material for lithium-ion battery [J]. Transactions of [12] LIU Hong-gang, ZHU Guo-cai. Removal of Ca(II), Mg(II) from
Nonferrous Metals Society of China, 2011, 21(10): 2248−2253. leaching solution of low-grade manganese ore by precipitation with
[4] ETACHERI V, MAROM R, ElAZARI R, SALITRA G, AURBACH fluoride [J]. Mining & Metallurgy, 2007, 16(4): 25−28.
D. Challenges in the development of advanced Li-ion batteries: A [13] BAKHSHESHI-RAD H R, IDRIS M H, KADIR M R A,
review [J]. Energy & Environmental Science, 2011, 4: 3243−3262. DAROONPARVAR M. Effect of fluoride treatment on corrosion
[5] YANG Zhi-zhong. The current situation and developing trend of behavior of Mg−Ca binary alloy for implant application [J].
ferro-alloy of Mn-series in China [J]. China’s Manganese Industry, Transactions of Nonferrous Metals Society of China, 2013, 23(3):
2005, 23(4): 1−6. (in Chinese) 699−710.
[6] WANG Kun, CHEN Bin. Reusing and application of ferromanganese [14] XIONG Li-zhi, CHEN Qi-yuan, YIN Zhou-lan, ZHANG Ping-min,
slag [J]. Environmental Engineering, 2003, 21(6): 53−55. (in DING Zhi-ying, LIU Zhi-xiong. Preparation of metal zinc from
Chinese) hemimorphite by vacuum carbothermic reduction with CaF2 as
[7] SAFARIAN J, KOLBEINSEN L, TANGSTAD M, TRANELL G. catalyst [J]. Transactions of Nonferrous Metals Society of China,
Kinetics and mechanism of the simultaneous carbothermic reduction 2012, 22(3): 694−699.
of FeO and MnO from high-carbon ferromanganese slag [J]. [15] JANDOVA J, LISA K, VU H,VRANKA F. Separation of copper and
Metallurgical and Materials Transactions B, 2009, 40(6): 929−939. cobalt-nickel sulfide concentrates during processing of manganese
[8] VEGLIO F, TORO L. Fractional factorial experiments in the deep ocean nodules [J]. Hydrometallurgy, 2005, 77(1−2): 75−79.
development of manganese dioxide leaching by sucrose in sulphuric [16] LIANG Sha, GUO Xue-yi, FENG Ning-chuan, TIAN Qing-hua.
acid solutions [J]. Hydrometallurgy, 1994, 36(2): 215−230. Effective removal of heavy metals from aqueous solutions by orange
[9] PAGNANELLI F, GARAVINI M, VEGLIO F, TORO L. Preliminary peel xanthate [J]. Transactions of Nonferrous Metals Society of
screening of purification processes of liquor leach solutions obtained China, 2010, 20(1): 187−191.
from reductive leaching of low-grade manganese ores [J]. [17] OKTAYBAS C, ACMA E, ARSIAN C, ADDEMIR O. Kinetics of
Hydrometallurgy, 2004, 71(3−4): 319−327. copper precipitation by H2S from sulfate solutions [J].
[10] DUTRIZAC J E. Factors affecting alkali jarosite precipitation [J]. Hydrometallurgy, 1994, 35(1): 129−137.
Metallurgical Transactions B, 1983, 14(4): 531−539.

锰铁合金渣浸出液制备电子级硫酸锰
闫 升 1,2，邱运仁 1

1. 中南大学 化学化工学院，长沙 410083；

2. 湖南省能源与化工新材料研究生培养创新基地，长沙 410083

摘 要：以锰铁合金渣为原料，经研磨、硫酸浸出后，采用中和−水解、氟化沉淀、硫化沉淀和重结晶法去除浸
出液中的铁、铝、钙、镁和重金属以及钠、钾等离子以制备电子级硫酸锰。研究反应 pH、反应温度和不同添加
剂的用量对硫酸锰产品中杂质含量的影响，并得到了较优的温度、pH、沉淀剂的用量等工艺条件。结果表明：在
较优工艺条件下，所制备的碳酸锰中，Ca2+、Mg2+、Na+、K+杂质离子的含量小于 0.005 %，Fe3+、Al3+和重金属
离子的含量小于 0.001%，Mn2+的含量大于 32%，硫酸锰产品的质量满足锂离子电池正极材料的要求。
关键词：锰铁合金渣；浸出；纯化；硫酸锰；固废利用
(Edited by Xiang-qun LI)