Hydrometallurgy 186 (2019) 260–268

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Hydrometallurgy
journal homepage: www.elsevier.com/locate/hydromet

Novel hydro-electrometallurgical technology for simultaneous production of T

manganese metal, electrolytic manganese dioxide, and manganese sulfate
monohydrate
⁎
Gigla Tsurtsumiaa, , Djemal Shengeliab, Nana Koiavaa, Tinatin Lezhavaa, David Gogolia,
Levan Beriashvilia, Sulkhan Suladzeb, Izolda Kakhniashvilia
a
Rafael Agladze Institute of Inorganic Chemistry and Electrochemistry, Ivane Javakhishvili Tbilisi State University, Tbilisi, Georgia
b
Georgian Technical University, Georgia

A R T I C LE I N FO A B S T R A C T

Keywords: The main stages of a novel hydro-electrometallurgical technology for simultaneous production of electrolytic
Hydro-electrometallurgy manganese metal, electrolytic γ-MnO2, and manganese sulfate monohydrate (MnSO4∙H2O) were tested at a large
Membrane electrochemical reactor laboratory scale. The unified flow sheet comprised large and small process loops. The large loop included:
Electrolytic manganese concentrated sulfuric acid leaching of ore obtained by high-temperature reduction of manganese oxide ore;
Electrolytic manganese dioxide
hydrolytic and sulfide purification of MnSO4 solution; production of crystalline manganese sulfate monohydrate
Manganese sulfate monohydrate
obtained by high-temperature autoclave treatment of purified concentrated MnSO4 solution; feeding of hot spent
Heat pump
MnSO4 solution from the autoclave as anolyte to an AMI-7001S anion membrane-separated electrochemical
reactor where γ-MnO2 was produced on titanium anodes. The small process loop included preparation and
correction of the catholyte composition using MnSO4∙H2O crystallized in the autoclave, from which electrolytic
manganese metal was deposited on titanium cathodes. A heat pump was used to maintain the necessary tem-
perature difference between the anolyte and catholyte. The energy consumed by the heat pump was half that
obtained using an electrical current heating device. Electrical power consumptions for the production of man-
ganese metal, manganese dioxide, and manganese sulfate monohydrate were 9.67 Wh/g, 3.75 Wh/g, and
0.884 Wh/g, respectively.

1. Introduction
In recent years, demand for high-purity electrolytic manganese
metal (EMM), electrolytic manganese dioxide (EMD), and manganese
sulfate monohydrate (MSM) has substantially increased in the world
market. Steel, aluminum, welding electrode, and chemical product in-
dustries are the main consumers of EMM. The chemical industry is
significantly dependent on high-purity EMD. MSM, which is used as an
additive to animal food, in fungicides, and as a precursor for other
manganese salts, is in increased demand.
This increased requirement for manganese-containing products
promotes the development and implementation of new energy-efficient
technologies that require less capital expenditure. The available lit-
erature that deals with processes and production of manganese pro-
ducts by hydrometallurgical technologies was thoroughly reviewed by
Zhang and Cheng (2007a,b). Information about leaching of manganese
ores using different reagents has been reported in several studies (Nayl
et al., 2011; Sahoo et al., 2001; Zhang et al., 2018). The influence of
various factors on electrodeposition of manganese metal have been
discussed by Araujo et al. (2006), Wei et al. (2010). Lu et al. (2014)
analyzed and reviewed processes of electrodeposition of manganese
metal based on work of numerous authors. Important works about
manganese technology considering environmental issues were con-
ducted by Duan et al. (2010), and Duan et al. (2011).
Despite the identification of defined technical cycles for EMM and
EDM production, these chemicals are produced on an industrial scale
according to process schemes that differ considerably from each other.
In EMM technology, electrolysis is carried out in a non-selective dia-
phragm electrolyzer at 30–35 °C in a MnSO4 solution that includes the
necessary buffer additive of 150–180 g/L(NH4)2SO4; metal manganese
(α-Mn) is deposited on the cathode at 50–60% current efficiency, while
oxygen, which has no industrial application, is released at the anode.
Specific electrical energy consumption for EMM production is
7000–8000 kWh/t (Agladze et al., 1975). In EMD technology,

⁎
Corresponding author.
E-mail address: giglat@yahoo.com (G. Tsurtsumia).

https://doi.org/10.1016/j.hydromet.2019.04.028
Received 14 January 2019; Received in revised form 17 April 2019; Accepted 23 April 2019
Available online 25 April 2019
0304-386X/ © 2019 Published by Elsevier B.V.
G. Tsurtsumia, et al.
electrolysis is carried out in a diaphragm-free electrolyzer at 91–93 °C
in acidified MnSO4 solution; γ-MnO2is deposited on the anode with
97–98% current efficiency, while hydrogen, which has no industrial
application, is released at the cathode. Specific electrical energy con-
sumption for EMD production is 2000–2500 kWh/t (Japaridze, 1987).
To deposit manganese metal on the cathode, the manganese sulfate
electrolyte has to contain 150–180 g/L (NH4)2SO4, but to obtain γ-
MnO2 on the anode, NH4+ ions cannot be tolerated in the electrolyte
because they rapidly deteriorate the electrotechnical properties of EMD
and make it unusable for chemical power sources, which is the main
area of application of this product. The temperature regimes of the two
electrolysis processes also differ considerably: the optimum tempera-
ture for EMM production is 30–35 °C, while EMD is obtained at
91–93 °C. These different electrolyte compositions and temperature
regimes eliminate the opportunity for simultaneous production of these
two products in an electrochemical reactor divided by an ordinary
mechanical diaphragm.
We achieved simultaneous production of EMM and EMD in a ther-
mostable anion-selective membrane electrochemical reactor
(Tsurtsumia et al., 2015, Agladze et al., 2008). Use of the thermostable
AMI-7001S anion membrane in the electrochemical reactor prevented
transfer of NH4+ ions (which are harmful to the anodic process) from
the cathodic to anodic compartment and made it possible to obtain both
products in a single electrochemical reactor. The voltage on the mem-
brane electrolyzer was approximately the same as that for EMM pro-
duction in an ordinary diaphragm electrolyzer. Under conditions of
preserving the same value of specific electrical energy consumption per
tonne of EMM, approximately 2.6 t EMD was simultaneously obtained
on the anode, taking into account the electrochemical equivalent and
current efficiencies of the cathodic and anodic products. Considering
that the specific electrical energy consumption for separate production
of EMD is 2000–2500 kWh/t, then the electrical energy saved due to
simultaneous electrolysis was 5200–6500 kWh/t. Through the sy-
nergistic implementation of anodic and cathodic processes in a single
electrochemical reactor, it was possible to achieve significant reduction
in electrical energy consumption.
The opportunity for simultaneous production of EMM and EMD in
the anion-selective membrane electrochemical reactor enabled us to
develop a new unified hydro-electrometallurgical technological scheme
that also envisages the production of MSM. The process flow sheet
consists of large and small interconnected loops (Fig. 1).
The large loop includes: (i) preparation of solutions with a high
content of manganese sulfate via concentrated sulfuric acid leaching of
MnO-containing raw material obtained from high-temperature reduc-
tion of manganese oxide ores; (ii) hydrolytic and sulfide purification of
the resulting MnSO4 solution to remove cations of Fe3+, Ni2+, Co2+,
and other metals; (iii) obtaining crystalline MnSO4∙H2O through high-
temperature autoclave treatment of a concentrated solution of purified
MnSO4; (iv) delivery of hot spent MnSO4 solution from the autoclave to
the anode compartment of the electrochemical reactor divided by an
AMI-7001S anion membrane, where γ-MnO2 is obtained on the anode
at 91–92 °C with 98–99% current efficiency. The small loop comprises
use of crystalline MnSO4∙H2O obtained in the autoclave for correction of
the catholyte composition, purification of solutions prepared from
technical (NH4)2SO4 by (NH4)2S, and delivery of pure manganese-am-
monium sulfate solution to the cathode compartment of the same re-
actor, where EMM is obtained on the cathode at 30–35 °C with 60%
current efficiency.
The novelty of the proposed unified hydro-electrometallurgical
process lies in the fact that, after the stages of ore leaching and pur-
ification, a concentrated manganese sulfate-containing solution passes
to autoclave treatment. A portion of crystalline MSM, obtained from
autoclave crystallization, is delivered to the catholyte circulation pro-
cess loop with the aim of providing Mn2+ ions to the EMM feed; the
remaining portion of MSM is an end product. Hot mother solution of
manganese sulfate exiting the autoclave is used as anolyte for EMD
261
Hydrometallurgy 186 (2019) 260–268
production. The spent manganese sulfate solution from the anolyte
compartment, which contains an increased quantity of sulfuric acid as a
result of the electrolysis reactions, is mainly returned to leaching of the
reduced ore. Small portions are used for acidifying the purified man-
ganese sulfate solution that is delivered to the autoclave (with the aim
of avoiding hydrolysis) and for adjustment of catholyte pH.
An important novelty of this technology is the use of a heat pump
for maintaining two quite different temperature regimes in the cathodic
and anodic compartments of the membrane electrochemical reactor in
the process of coproduction of EMM and EMD. An ecologically accep-
table cooling agent, R-600a (isobutane), was used as the refrigerant.
This paper presents: a) results of large-scale laboratory tests of the
most important stages of this hydro-electrometallurgical process
scheme; b) assessment of the thermal efficiency of the heat pump used
for maintaining the different temperature regimes in the membrane
electrochemical reactor at a load of 20A; c) results of integrated large-
scale laboratory tests.
2. Experimental
2.1. Materials, analysis, and procedures
Reduced manganese oxide ore produced by Rustavi Manganese
Chemical Georgia LLC was used as the source raw material. Its com-
position is given in Table 1.
The reduced ore was ground and sieved to < 0.1 mm. Leaching was
conducted using concentrated sulfuric acid at stirring speeds of 350,
550, 750, 950, 1200, and 1400 rpm at solid:liquid ratios of 1:20 and 1:5
(mass:volume). The results showed that no further increase in manga-
nese leaching rate occurred once the agitation speed of the impeller was
950 rpm; therefore, this agitation speed was employed for all leaching
experiments.
The reduced manganese ore was leaching by concentrated sulfuric
acid (93.64% H2SO4; density:1.83 g/cm3) in a 2 L flask equipped with a
mechanical stirrer, electric heater, pH electrode (MP512 Precision pH
meter, Shanghai San-Xin Instrumentation, Inc., China), and equipment
for delivery of concentrated sulfuric acid. Distilled water (1.5 L), heated
to 50–65 °C, was placed into the 2 L flask, to which 93.64% H2SO4 was
delivered drop wise under conditions of vigorous mixing by mechanical
stirrer (950 rpm) to maintain a pH of 2. Simultaneous delivery of con-
centrate of a defined mass (particle size < 0.1 mm) and acid made it
possible to maintain the pH and temperature conditions by means of the
water released as a result of the reaction and the electric heating.
Constant volume in the reaction vessel (1.5 L) was maintained by ad-
dition of distilled water. Chemical analysis of the concentration of
leached Mn2+ was conducted every 15 min by taking a 2 mL sample.
MnO + H2 SO4 ⟶MnSO4 + H2 O (1)
2+
The Mn concentration in solution was determined via the well-
known Reinhardt's method of chemical analysis (Kreshkov, 2006),
while the ammonium sulfate concentration was determined via Kjel-
dal's method (Harris, 2010).
To remove Fe3+ impurities from the hot suspension obtained after
leaching, the pH was adjusted from 2 to 3.5 by addition of reduced ore.
The content of iron in the solution was checked using ferri–ferrocyanide
reagents (Kreshkov, 2006). To remove nickel, cobalt, and other heavy
metal ions from the filtrate after filtration of the resulting suspension,
sodium sulfide of reactive purity (Na2S∙nH2O) was used. After addition
of approximately 2 g/L Na2S∙nH2O, the suspension was heated to 70 °C
for 1 h under conditions of vigorous mixing. Nickel, cobalt, copper,
molybdenum, and other sulfides precipitated from solution and gave a
black color to the suspension. After addition of a new portion of sodium
sulfide to the solution, a pink suspension, due to manganese sulfide
formation, was obtained via decantation. This indicated completion of
purification of the solution from impurities. After cooling and filtration
of the suspension, a manganese sulfate solution was obtained that was
G. Tsurtsumia, et al. Hydrometallurgy 186 (2019) 260–268

Fig. 1. Conceptual flow sheet of the novel hydro-electrometallurgical technology for simultaneous production of EMM, EMD, and MSM.

almost completely purified from heavy metals.
By dilution of this concentrated purified manganese sulfate solution
and addition of technical-grade ammonium sulfate, the solution des-
tined as the catholyte was treated by concentrated ammonium sulfide.
The latter was obtained by addition of 25–30% H2SO4 to sodium sulfide
and passage of released H2S gas through a 20% ammonia water of until
its complete saturation. Purification using ammonium sulfide was
conducted in a similar manner to that of sodium sulfide described
above. The purification process was carried out for 1 h at 70 °C in a
porcelain reactor under conditions of vigorous mixing. The pink
suspension formed after cooling to room temperature was filtered using
filter paper (Whatman 41, pore saze 20–25 μm).
MSM was obtained using a Chinese-manufactured autoclave (GSH-
3L magnetic seal reactor), the internal surface of which was coated with
polytetrafluorethylene. The stirrer was manufactured from Teflon and
agitated using an electric motor. A Teflon cylinder was compactly
placed into the autoclave and a filtering fabric belt tightly fixed on its
lower end. MSM, crystallized at a defined temperature and pressure,
was deposited on the filter fabric of the Teflon cylinder. After opening a
ball-type valve at the bottom exit of the autoclave, hot mother solution

Table 1
Results of chemical analysis of the product obtained through high-temperature reduction of manganese oxide ore produced in the Rustavi Mn Chemical Georgia LLC.
Mn total (%) Al (%) Ba (%) Ca (%) Fe (%) H2O (%) Mg (%) Na (%) K (%) Co Cu Ni

ppm

59.3 0.63 0.60 0.50 0.80 0.4 0.24 0.04 0.10 140 250 1.030

262
G. Tsurtsumia, et al.
was rapidly filtered under the influence of pressure and accumulated in
a heat-insulated quartz vessel. After pressure release, the autoclave
cover was opened and crystallized MSM was unloaded along with the
filtering device. The MSM was dried to constant mass in a furnace at
100 °C.
Spectral analyses of the original solution taken for high-temperature
autoclave treatment, spent mother solution exiting the autoclave, and
the obtained MSM were conducted using a microwave plasma atomic-
emission spectrometer MP AES 4200, Agilent, USA.
Electrolysis was conducted in an electrochemical reactor that
comprised three anolyte compartments connected to each other and
two catholyte compartments placed between them, assembled from
polypropylene sheets. Heat exchange between the anolyte and cath-
olyte was performed using an anion membrane (AMI-7001S anion ex-
change membrane; Membranes International Inc., USA) located be-
tween four dividing perforated polypropylene baffles. The total
catholyte volume of the reactor was 6.8 L; the anolyte volume was
10.81 L. Electrolysis was conducted via passage of direct current (DC)
using a DC power supply-type rectifier (Power Station pe 1018-2-SNT;
DC output:15 V/30A; Plating Electronic GmbH, Germany). Titanium
plates were used as cathodes and titanium cylinders as anodes. The
electrolysis parameters were: applied current I = 20 A; cathodic current
density ic = 3.5 A/dm2; anodic current density ia = 0.92 A/dm2; vol-
tage V = 5.95 V. A detailed description of the electrolysis methodology
is given by Tsurtsumia et al. (2015).
3. Results of large-scale laboratory tests
3.1. Leaching of reduced manganese oxide by concentrated sulfuric acid
The process envisages production of purified concentrated manga-
nese sulfate solution, because MSM required for the catholyte is crys-
tallized out through autoclave treatment of such solution and the hot
spent mother solution exiting the autoclave provides the anolyte for the
electrochemical reactor.
The reaction of reduced ore with concentrated sulfuric acid is highly
exothermic and proceeds rapidly in the case of vigorous stirring. During
the initial stage of research, it was established that leaching of the re-
duced ore caused silic acid H4SiO4 formation under surplus acid con-
ditions, which complicated the subsequent suspension filtration pro-
cess. Carrying out the leaching process in a stirred reactor at controlled
pH with simultaneous feeding of reduced ore and acid proceeded more
effectively.
Because the leaching process was carried out at 70 °C and controlled
pH, it was important to know the dependence of pH on temperature to
compare and control pH during the purification and solution prepara-
tion processes. It was established that the pH of the leached pulp re-
duced with increase in temperature (Fig. 2).
Experimental results for leaching of the reduced manganese oxide
5.2
pH 5.0
4.8
4.6
4.4
4.2
4.0
3.8
3.6
3.4
15 25 35 45 55 65
t,oC
Fig. 2. Dependence of pulp pH on temperature.
Hydrometallurgy 186 (2019) 260–268
ore by concentrated sulfuric acid conducted using the laboratory device
at 55 and 70 °C are given in Table 2.
The temperature rise from 55 to 70 °C increased the average rate of
manganese leaching by 1.59 times during the first 5 min. Extraction was
initially high (89.05% at 55 °C; > 94% at 70 °C). An increase in the
solid:liquid ratio reduced the extent of manganese extraction. Table 2
shows that 195 mL of 93.64% H2SO4 was consumed for concentrate
leaching: this was 5% in excess of the stoichiometric requirement.
The leaching process was also carried out under the same conditions
in a 50 L porcelain reactor equipped with a mechanical stirrer, quartz
heater, thermometer, and pH electrode. To obtain a solution containing
110 g/L Mn2+, a theoretical mass of 7420 g concentrate was required,
given that it contained 59.3% total manganese. The stoichiometric re-
quirement of 93.64% H2SO4 was 4.575 L. Practically, 4.804 L of H2SO4
was consumed, giving a 5% stoichiometric excess.
The results of the laboratory tests carried out at both scales showed
that it was possible to carry out the leaching process at 70 °C and pH 2
with simultaneous supply of reagents to the reactor due to the following
reasons: a) the rate and extent of leaching were high; b) formation of
acid-containing vapor from the suspension surface was relatively low
and, more importantly, it was possible to minimize energy consumption
to maintain a temperature of 70 °C in the reactor using heat released
from the reaction.
3.2. Preparation of purified manganese sulfate solution
Adjustment of the pH of the pulp obtained after leaching of the
reduced ore to 3.6–4.0 resulted in the formation of colloidal iron hy-
droxide particles, removal of which by filtration was difficult. An anion-
type Separan flocculant (separan AP 30, USA) was used to achieve rapid
settling of the manganese sulfate-containing pulp. Many formulations of
Separan flocculants are known: the sodium salt of polyacrylic and
polymetacrylic acids, an anionic-type polyelectrolyte, was an effective
flocculant within the limits of pH 3–7.
To establish the impact of the Separan additive on the pulp settling
rate, visual observation of the settling process was conducted under
optimum conditions (70 °C, pH 2). The pH of the leach pulp was ad-
justed to 3.6 by addition of ore (70 °C). Under these conditions, iron
was converted to insoluble hydroxides (qualitative analysis for the
presence of both di- and trivalent iron ions in solution was negative).
The obtained pulp was divided into two parts, one taken for compar-
ison, while Separan (0.1 g/L) was added to the second. The settling
process was visually observed with time under conditions of constant
temperature. Pulp settling was considered complete when a visually
transparent solution was obtained. Test results are given in Table 3.
Separan addition reduced the particle sedimentation time by a factor of
9 at 20 °C and by a factor of 32 at 70 °C.
A plastic γ-modified manganese deposit was obtained at 60% cur-
rent efficiency via electrolysis from manganese ammonium sulfate so-
lution produced by Separan addition and further sulfide purification.
This form of manganese, as known from literature (Sulcius et al., 2013),
is only obtained from clear solutions. The result of this experiment
clearly indicated that use of the Separan additive (0.1 g/L) to ensure
rapid removal of iron hydroxide had no impact on the electrodeposition
of manganese metal from solutions obtained by subsequent sulfide
purification. Use of Separan for acceleration of pulp settling after
leaching is important from the viewpoint of process intensification.
3.3. High-temperature autoclave treatment of manganese sulfate solution
and electrolyte preparation using spent mother solution for hot anolyte
The technology envisages obtaining MnSO4∙H2O crystals by high-
75 temperature autoclave treatment of purified concentrated MnSO4 so-
lution. A portion of the MnSO4∙H2O crystals was used for catholyte
composition correction and the hot spent MnSO4 solution (55–60 g/L
MnSO4; 5–10 g/L H2SO4) exiting the autoclave was fed as anolyte to the
263
G. Tsurtsumia, et al. Hydrometallurgy 186 (2019) 260–268

Table 2
Changes of leaching rate and degree of extraction of reduced ore concentrate at 55 and 70 °C under conditions of: pH 2; concentrate particle size < 0.1 mm; stirring
rate 950 rpm.
t°C Time τ Added volume of Mass of reduced manganese Mass of manganese in Mass of manganese Average rate of leaching Degree of extraction
(min) 93.64% H2SO4 V oxide concentrate m, g added concentrate C (g) dissolved in solution G (g) processes ΔG/Δτ (g/min) G/C⋅100 (%)
(mL)

55 5 22 16.40 9.725 8.66 1.73 89.05

10 32 28.76 17.055 15.35 1.34 90.0
15 42 37.76 22.392 21.04 1.14 93.96
25 55 56.78 33.67 30.41 0.94 90.32
40 69 79.41 47.090 43.95 0.90 93.33
55 82 102.43 60.741 55.25 0.82 90.95
70 97 123.63 73.313 66.86 0.77 91.20
90 113 150.97 89.525 80.67 0.69 90.11
110 130 184.21 109.237 92.98 0.62 85.12
140 148 224.39 133.063 108.95 0.53 81.88
170 167 262.40 155.603 124.05 0.50 79.72
200 187 289.5 171.674 138.73 0.49 80.81
210 195 293.4 173.986 143.45 0.47 82.45
70 5 24 24.41 14.475 13.75 2.75 94.99
10 22 43.87 26.019 24.25 2.1 93.2
15 43 61.66 36.564 32.5 1.65 88.88
25 65 88.48 52.89 46.8 1.43 88.48
40 79 126.18 74.825 63.75 1.13 85.2
55 108 161.59 95.823 78.0 0.95 81.4
70 132 185.88 110.23 91.05 0.87 82.6
90 158 220.98 131.041 107.85 0.84 82.3
110 180 254.6 150.98 124.45 0.83 82.4
120 195 293.4 173.986 132.85 0.84 76.36

Table 3 Table 4
Visual observations of the pulp settling process. Experimental results of obtaining of MSM crystals through high-temperature
autoclave treatment of manganese sulfate containing solutions.
Pulp parameters Without separan With separan (0.1 g/L)
№ Volume of Tem. in Pressure Volume of Mass of
Pulp temperature, °C 20 70 20 70 solutions autoclave in solution from the produced dry
Pulp pH 5.0 3.6 5.0 3.6 supplied to the (t°C) autoclave autoclave and MnSO4·H2O
Total time of pulp setting process, h 18 16 2 0.5 autoclave and P (kPa) concentration of (g)
concentration of manganese
manganese
membrane reactor.
V (L) CMn2+ V (L) CMn2+
Obtaining MSM via the autoclave method is based on the solubility
(g/L) (g/L)
dependence of manganese sulfate on temperature. Manganese sulfate
solubility is reduced with temperature rise (Fig. 3) (Abuladze, 1969). 1 2.8 115 150 405.3 2.03 32.0 770.0 ± 3.2
It was established via preliminary studies that mechanical stirring 2 2.8 115 140 293.84 2.09 44.20 686.3 ± 3.4
3 2.8 115 138 253.3 2.16 57.26 590.5 ± 3.5
and autoclave heating are necessary to crystallize powdered, finely
4 2.8 87.25 150 405.3 2.09 30.5 534.5 ± 3.1
crystalline monohydrate; otherwise, the hydrate will be obtained in a 5 2.8 87.25 145 303.975 2.23 61.7 306.9 ± 3.3
hardened form, which is difficult to unload from the autoclave. 6 2.8 87.25 140 253.3 2.22 73.75 227.0 ± 3.4
Results of the final test conducted in the autoclave are given in 7 2.8 87.25 135 222.9 2.47 86.6 73.74 ± 3.5
Table 4. Each test was carried out in triplicate and the values presented
are arithmetic means. In bold, optimal conditions are chosen for the process
After high-temperature (138 °C) and 253.3 kPa (2.5 atm) pressure
treatment of manganese sulfate solution (115 g/L Mn2+; 5–8 g/L H2SO4), it was loaded into the autoclave: 590.5 g MnSO4∙H2O was
crystallized out in dry form and hot solution exiting the autoclave
contained 57.26 g/L Mn2+ and 10 g/L H2SO4, which was quite accep-
table as anolyte feed. The hot solution (91–92 °C) was used as the an-
olyte in the membrane electrochemical reactor for γ-MnO2 electro-
deposition.
It follows from the test results that to obtain an autoclave-treated
solution for anolyte with the necessary composition and crystalline
MSM, the treatment of manganese sulfate concentrated solutions in
which the Mn2+ content varied within the limits of 85–115 g/L Mn2+,
was profitable from an economic point of view.
Results of Spectral analyses of the original solution taken for high-
temperature autoclave treatment, spent mother solution exiting the
autoclave, and the obtained MSM are given in Table 5.
Iron, magnesium, potassium, and sodium cation impurities re-
mained in the spent solution and were transferred to some extent to the
crystallized monohydrate; the only exception was calcium that pre-
Fig. 3. Dependence of the solubility of manganese sulfate on temperature
sented in the MSM crystals, presumably in the form of the less soluble
(Abuladze, 1969).

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Table 5
Results of chemical analysis of products obtained through high-temperature autoclave treatment of manganese sulfate solutions.
Type of sample Mn2+ Fe3+ Ca2+ Mg2+ K+ Na+

g/L or % ppm ppm ppm ppm ppm

Composition of original solution taken for autoclave treatment 115 g/l 17 1023 508 152 3200
Composition of spent mother solution exiting of the autoclave 73 g/l 14 1195 545 176 3480
Composition of dry manganese sulfate monohydrate 32.50% 12 2280 553 62 1604

Fig. 4. Scheme of incorporation of thermal pump into the electrochemical reactor divided by the anionic AMI 7001S membrane.

sulfate. implementation of a new technology.

Crystalline MSM obtained through autoclave treatment was used for
preparation of manganese-ammonium sulfate solution that was used for
manganese metal electrolysis. Plastic γ-Mn was obtained from this so-
lution by electrolysis, with the current efficiency exceeding 60%. The
result of this experiment clearly showed that the monohydrate obtained
using the autoclave method was of high purity and could be used
without purification for catholyte correction.
3.4. Use of heat pump to achievedifferent temperature regimes in anode and
cathode compartments of membrane electrochemical reactor working at 20A
load
A key role is played in this hydro-electrometallurgical technology by
the membrane electrochemical reactor, on the electrodes of which two
products are simultaneously obtained: metal manganese on the cath-
odes and γ-MnO2 on the anodes. The electrolysis procedure to obtain
both products and impact of the electrolysis parameters on their current
efficiency were described indetail in (Tsurtsumia et al. (2015). An
electric coil placed into a quartz pipe was used for heating of anolyte,
while a cold water stream passing through a quartz pipe was used for
cooling of catholyte. Obtaining two products in a single reactor will
considerably improve the opportunity for successful practical
The main problems for smooth operation of the electrochemical
reactor were created not only due to the difficulties related to the use of
the anion membrane (the selectivity requirement to avoid transfer of
NH4+ ions from catholyte to anolyte and the mechanical and thermal
stability), but also because of the need to maintain significantly dif-
ferent temperature regimes in the two reactor compartments.
A heat pump was used to study the latter effect.The evaporator was
placed in the catholyte I condenser in the anolyte. R-600a (Global
Refrigerants, Singapore) was selected as the cooling agent, because it
has the best thermophysical properties in the required range and is an
ecologically acceptable reagent, possessing neither ozone depletion nor
global warming potential (Chapman, 1987). Refrigerants R-600a was
isobutane (C4H10/(CH3)2CHCH3), which is gas at 20 °C with following
physical characteristics: Boiling point −12.0 °C; melting point
−159.0 °C; vapor pressure 3 bar at 20 °C; flammability rang 1.5 to 8.5
vol% in air; auto ignition temperature 460 °C.
A diagram of the heat pump connection to the electrochemical re-
actor is shown in Fig. 4.
Heat exchange between anolyte and catholyte proceeded through
the anion membrane located between the four dividing perforated
polypropylene baffles. The following reactions take place on the elec-
trodes of the membrane electrochemical reactor:

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G. Tsurtsumia, et al. Hydrometallurgy 186 (2019) 260–268

Fig. 5. Scematic flow diagram of large-laboratory scale testing of a new hydro-electrometallurgical technology.

On the cathode: Mn2 + + 2e⟶Mn (2a) complicated, especially during a dynamic regime. From physical mod-
eling conducted at the test bench and simplified calculations (per-
2H+ + 2e⟶H2 (2b)
formed with the accuracy necessary for practical purposes), it was es-
2NH 4+ + 2e⟶2 NH3 + H2 (2c) tablished that, during the initial stage when the temperature difference
between anolyte and catholyte was minimal, thermal energy was
On the anode: Mn2 + + 2 H2 O⟶MnO2 + 4H++2e (3a) mainly directed to anolyte heating. When the difference between the
electrolytes exceeded 35 °C, the heat flow directed from the hot to the
2 H2 O⟶4H+ + O2 + 4e (3b) cold medium exceeded the heat quantity consumed for anolyte heating.
When the anolyte temperature surpassed 85 °C, i.e., a temperature
The net reaction is:
difference of 50 °C or more, water evaporation intensity from the ano-
2MnSO4 + (NH 4 )2 SO4 + 4 H2 O⟶Mn + MnO2 + 2H2 + 2 NH3 + O2 lyte increased and a significant portion of thermal energy was directly
consumed for this process, due to which the thermal load in the elec-
+ 3H2 SO4 (4)
trochemical reactor reached a maximum of 490 W per baffle, i.e., a total
In general, a complex thermodynamic process occurred in the load of 1.96 kW. In stationary mode, when the anolyte temperature
electrochemical reactor, mathematical modeling of which is very reached 92 °C and catholyte temperature was 35 °C, i.e., when

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G. Tsurtsumia, et al.
temperature difference between the cold and hot media was 57 °C, the
heat pump output was consumed for heat loss compensation only. In
this mode, the total heating power was 1.32 kW, while that of con-
sumed electrical energy was 1.2 kW. In the case of heating by electric
current, the total required electrical power was 2.43 kW, which was
double that of the heat pump. To maintain a stable anolyte tempera-
ture, it was necessary to deliver 839.89 W of heating power; for the
catholyte, removal of 427.53 W heat was needed.
The difference between the heating and cooling requirements was
caused by the fact that external heat losses from the hot anolyte were
high, although a large portion of heat flow entered the catholyte di-
rectly. This difference highlights the advantage of heat pump use
compared with other technical means: in any refrigerant cycle, the heat
quantity removed from the environment is always less than the heat
quantity introduced. Proceeding from this fact, the cooling agent can be
selected for such a cycle in which the ratio of obtained and abstracted
heat will be the same as that of the membrane electrochemical reactor.
In our experiment, the copper pipes of the heat pump evaporator
and condenser that were respectively placed in the catholyte and ano-
lyte were coated with polymeric electrical insulation that created
thermal resistance to heat flow. This had a negative impact on the heat
pump efficiency coefficient. A device with 1.32 kW heat power was
therefore selected for energy supply for the electrolyzer operating
mode, while a second device with the same power was turned on in
parallel to eliminate the peak thermal load in start-up mode, as shown
in Fig. 4.
The use of a heat pump in the electrochemical reactor was pro-
mising, but its efficiency can be considerably increased, by improving
the heat exchange process between the evaporator (catholyte) and
condenser (anolyte) and by selection of a coolant that is characterized
by chemical inertness and high heat-transfer properties.
4. Testing of integrated technology on large laboratory scale
The results of testing this hydro-electrometallurgical technology on
a large laboratory scale are given in Fig. 5. Results for separate stages
were recalculated according to hourly outputs.
The specific electrical energy consumptions for the targeted pro-
ducts were 9.67 Wh/g for manganese metal (α-Mn), 3.75 Wh/g for γ-
MnO2, and 0.884 Wh/g MnSO4· H2O, of which 735.1 g/h was produced,
consuming 650 W of electric energy.
5. Conclusions
1. A new hydro-electrometallurgical technology for manganese oxide
ore treatment, which envisages simultaneous production of EMM,
EMD, and MSM was tested on a large laboratory scale.
2. The unified process comprised large and small process loops con-
nected to each other. The large loop includes:
a) Preparation of solutions with a high content of manganese sulfate
via leaching of MnO-containing raw material obtained from high-
temperature reduction of manganese oxide ores by concentrated
sulfuric acid. Laboratory and large-scale tests established that
this leaching process is profitable with simultaneous feeding of
reagents to the reactor at 70 °C and pH 2.
b) Settling of iron hydroxides from the leached MnSO4 pulp was
accelerated by addition of 0.1 g/L of a Separan anionic-type
flocculant, which reduced the rate of sedimentation by a factor of
32at 70 °C. Sodium sulfide, a well-known additive in manganese
hydrometallurgy, was employed for precipitation of other metal
cations.
c) Crystalline MnSO4∙H2O was obtained by high-temperature auto-
clave treatment of a concentrated solution of purified MnSO4.
Hot spent MnSO4 solution exiting the autoclave was fed as ano-
lyte to the electrochemical reactor, where γ-MnO2 was obtained
on the anode with 98–99% current efficiency at 91–92 °C. It was
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Hydrometallurgy 186 (2019) 260–268
established that to obtain a solution via autoclave treatment with
the composition necessary for hot anolyte and crystalline MSM
production, use of a concentrated manganese sulfate solution in
which the Mn2+ content varied within the limits of 85–115 g/L
Mn2+was profitable from an economic point of view.
The small process loop, which was connected to the large loop,
comprised use of crystalline MnSO4∙H2O obtained in the autoclave for
catholyte composition correction, purification of solution prepared
from technical (NH4)2SO4 by (NH4)2S, and delivery of pure manganese-
ammonium sulfate solution to the cathodic compartment of the same
reactor, where electrolytic manganese metal was obtained on the
cathode at 30–35 °C with 60% current efficiency.
3. A heat pump was used to maintain significantly different tempera-
ture regimes in the three anode and two cathode compartments
divided by a membrane (AMI-7001S) in the electrochemical reactor.
The resulting power consumption was 1.2 kW. The alternative –
heating by electric current – required 2.43 kW, a power consump-
tion that was almost twice as high.
4. Test results for this hydro-electrometallurgical technology on a large
laboratory scale were presented, showing hourly outputs for the
separate stages. Specific electrical energy consumption was
9.67 Wh/g for manganese metal (α-Mn), 3.75 Wh/g for manganese
dioxide (γ-MnO2), and 0.8 Wh/g for manganese sulfate mono-
hydrate (MnSO4·H2O).
Acknowledgments
This work was supported by Shota Rustaveli National Science
Foundation of the Republic of Georgia (Grant No. 216704).
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