M INING

SCIENCE AND
TECHNOLOGY
Mining Science and Technology 20 (2010) 0877–0881
www.elsevier.com/locate/jcumt

Preparation of chemical manganese dioxide

from manganese sulfate
FU Jiangang*, HE Zhangxing, WANG Hui, LIANG Wei, GUO Chao
College of Chemistry and Chemical Engineering, Central South University, Changsha 410083, China

Abstract: Chemical Manganese Dioxide (CMD) was prepared by an alkali-oxidation method. There are several virtues to this
environmental friendly and clean process, including the nontoxic and harmless reagents and products, easy operations, no pollutants,
easily obtained raw materials and moderate reaction conditions. The synthesized manganese dioxide was characterized by XRD and
SEM. The particles were small, consisting primarily of Į-MnO2 and Ȗ-MnO2. Experimental results showed that the optimum
conditions were: MnSO4·H2O to NaOH ratio, 1.0:2.4; catalyst concentration (catalyst TF-2), 6% of the MnSO4; initial solution pH,
11; reaction time and temperature, 20 min and 80°C; air flow, 0.20 m3/h; and, agitation rate, 700 r/min. The conversion of MnSO4
can exceed 80% under these optimum conditions.
Keywords: MnSO4; alkali-oxidation; chemical manganese dioxide; clean process

1 Introduction high reactivity, large capacity, small investment costs,

low energy consumption and easy maximization of
Manganese dioxide is available in several types equipment.
including Chemical Manganese Dioxide (CMD), Common preparation methods of manganese
Electrolytic Manganese Dioxide (EMD), Natural dioxide now include the thermal decomposition
Manganese Dioxide (NMD) and Active Manganese method, the oxidation method using a strong oxidant,
Dioxide (AMD)[1-7]. Synthetic CMD forms black the reduction of high-valence manganese salts and the
acicular crystals or a non-stereotype powder and has direct oxidation method[8-15]. The thermal decomposi-
two crystal forms: ȕ-MnO2 and Ȗ-MnO2. CMD, like tion method is divided into the thermal decomposi-
EMD, is mainly used in the manufacture of dry cell tion of nitrate or the thermal decomposition of
batteries. In addition, CMD is used in the manufac- carbonate salts. In recent years the preparation of
ture of magnetic materials and in the electronics, CMD and the study of its properties have attracted
glass, ceramics and dye-stuffs industries, or is used as great attention in many countries. The development
an oxidant. Recent advances in the nation’s battery of high-quality CMD is a long-term research project
industry have resulted in an annual production of over in Belgium, Japan, the USA and Canada. China’s
25 billion dry cell batteries. About 70% of these are research and trial production of CMD started in the
zinc-manganese batteries, the production of which 1960’s and the scale of most factories is rather small,
consumes up to 400000 tons of manganese dioxide about 600 t/a. Compared to the developed countries
annually. Consequently, the demand for high-quality research on CMD in China has just started up. The
EMD and CMD exceeds the available supply. output of CMD is less than 1/50 of the total output of
Although EMD has excellent properties for use in the the USA, Japan and Belgium. Therefore, it is of
battery industry the overall process using EMD as practical significance, related to exploiting man-
raw materials has some defects. These include long ganese ore resources and promoting the development
distance technologic process, high electricity of a high-quality alkali-manganese battery industry,
consumption and great investment costs. CMD has to enlarge basic research and to develop new
many advantages when compared to EMD such as processes related to CMD. This paper describes the
use of manganese sulfate as a raw material for the
Received 09 March 2010; accepted 02 June 2010
synthesis of CMD by the alkali-oxidation method.
*Corresponding author. Tel: 86 13973134937 The goal is the development of an available raw
E-mail address: [email protected] material, simple operation and a clean process.
doi: 10.1016/S1674-5264(09)60299-4
878 Mining Science and Technology Vol.20 No.6

2 Experimental finished. The filter cake was reacted, with agitation,

in sulfuric acid solution for one to two hours. After
2.1 Materials and apparatus this it was then filtered and washed with water until
Materials: reagents, including manganese sulfate the pH of the filter cake was 5. CMD was isolated
and sodium hydroxide, are analytical reagent grade. after drying, grinding and sieving. The concentration
The catalyst is made in our laboratory. of MnO2 was determined by the ferrous sulfate
Apparatus included: a super constant temperature method.
bath (DKB-501A, Shanghai Jinghong Laboratory
Instrument Co., Ltd); an electronic constant speed 3 Results and discussion
stirrer (JHS-1/90, Hangzhou Instrument Electrical 3.1 Effect of alkali on conversion
Machinery Factory); a glass rotor flow meter
16.90 g of MnSO4·H2O and 1.0 g of catalyst (TF-2)
(LZB-10, Yuyao Yinhuan Flowmeter Co., Ltd); an oil
along with 100 mL of water were put into the reactor
free gas compressor (WM-4, Tianjin medical
and completely dissolved. The reaction conditions
Appliance II); a pH meter (pHS-30, Shanghai Weiye
were: temperature, 75°C; stirring speed, 700 r/min;
Instrument Factory); and, a reactor with lid fabricated
air flow, 0.20 m3/h. The pH was controlled with
in house.
saturated sodium hydroxide solution and the reaction
2.2 Principles time was 120 min. The effect of alkali on conversion
The potential of manganese in its different valence was investigated in this experiment. The results are
states is shown in Fig. 1: shown in Fig. 2.

φ AO N
η (%)

φ AO N

CMnSO4
Fig. 1 Potential of manganese in different valence states

The diagrams show that the potential difference

between Mn2+ and MnO2 is high in acidic conditions. Fig. 2 Effect of pH on conversion (Ș)
On the other hand, it is easy to oxidize Mn(OH)2 to
MnO2 in alkaline conditions. The possible reactions Manganese sulfate solutions are strongly acidic.
are: Hence the saturated manganese sulfate presents a
strong acidity but the reaction to obtain CMD must be
2Mn 2+ +4OH  +O 2 → 2MnO 2 +2H 2 O (1)
kept alkaline. Fig. 2 shows that the pH of the solution
2+
4Mn +8OH +O 2 → 4MnOOH+2H 2 O

(2) has a great effect on the conversion, the highest
conversion being 45% higher than the lowest. When
4MnOOH+O 2 → 4MnO 2 +2H 2 O (3) the mole ratio of MnSO4 to NaOH is 1:2 the solution
2MnOOH → MnO 2 +Mn(OH) 2 (4) pH is about 9. As alkali concentration is increased
Mn2+ is more easily reduced and the reaction speed
The total reaction is summed up as:
increases. The conversion is maximum when the pH
Mn 2+ +2OH  → Mn(OH)2 ⎯⎯
air
→ MnO2 (5) is 11. As the alkali concentration increases further
Mn2+ changes into the form Mn(OH)2 and precipi-
2.3 Methods
tates from solution, which is adverse to further
Temperature was controlled by a super constant reaction. When the pH is too high the activity of
temperature bath. The reaction mixture was stirred by synthetic manganese dioxide is strengthened and the
an electronic constant speed stirrer. Air was supplied adsorption capacity for Mn2+ and impurity ions is also
in the following way: air was passed into a buffer strengthened. This leads to an increase in low-valent
bottle (with a valve to control the flow) using an oil manganese ions being absorbed and, therefore, the
free compressor. It then entered a flow meter and amount of synthetic manganese dioxide produced
passed into a distribution tube in the reactor. decreases. If MnSO4 was titrated into the reactor the
Saturated manganese sulfate and sodium hydroxide conversion is the same at pH 13 to 14 where the
solutions were added to the reactor with the reaction is strongly alkaline. Therefore, the optimal
quantitative catalyst. Heating with agitation then pH is seen to be 11.
commenced as the pH of the solution was adjusted
according to experimental requirements. 3.2 Effect of temperature on conversion
After mixing the solution first turns from ivory to The percent conversion (see Fig. 3) shows that the
brown-black and deposits appear. The reaction conversion of MnSO4 increases as the temperature
solution was then filtered after the reaction was increases from 50 to 80 °C; it is highest (82%) at 80
FU Jiangang et al Preparation of chemical manganese dioxide from manganese sulfate 879

°C. Increasing temperature enhances mass transfer conversion was 20%. The intermediate, Mn(OH)2, is
and enhances and strengthens molecular collisions so a floc so agitating facilitates solution contact and
the speed of the reaction increases and the conversion reactant transmission between the three phases; this
rises. As the temperature continues to increase the accelerates the reaction. However, excess agitation
percent conversion starts to decrease. This is because may splash the solution out: 700 r/min was found
the oxidation of Mn(II) is a non-homogeneous appropriate.
reaction involving the gas, liquid and solid phases. At
high temperatures the solubility of air in the liquid
phase decreases, which makes the gas concentration
drop; this hinders the reaction. Therefore, the

η (%)
experimentally determined best reaction temperature
is 80 °C.
CMnSO4

Fig. 5 Effect of reaction time on conversion (Ș)

η (%)

CMnSO4

Fig. 3 Effect of temperature (T) on conversion (Ș) η (%)

CMnSO4
3.3 Effect of air flux on conversion
Fig. 4 shows how air flow affects conversion. The
air flux has little influence on conversion; the Fig. 6 Effect of agitation speed (R) on conversion (Ș)
difference between the maximum and minimum
conversion is only 10%. Conversion was maximum at 3.6 Effect of catalyst type and concentration on
the air flow of 0.20 m3/h; it trends to decrease at conversion
higher flow rates. Excessive air flow caused the
solution to splash and changed of solubility of Changes in catalyst have great effect on conversion,
oxygen. The experimentally determined optimum air as shown in Table 1. When TF-2 was the catalyst
flow was 0.20 m3/h. conversion was 81%, although conversion without
catalyst is 60.3%. The catalytic effect of TC-3 was
insignificant and the effect of EMD was between that
of TC-3 and TF-2. Therefore, TF-2 was chosen as the
catalyst for the reaction.
η (%)

Table 1 Relationship between catalyst and conversion (Ș)

CMnSO4 Type of catalyst Dose (g) Conversion (%) Yield (%)
60.30 99.0
TF-2 1.00 81.72 99.2
Fig. 4 Effect of air flux (V) on conversion (Ș) TF-2 2.00 79.20 99.0
TC-3 1.78 62.85 99.1
3.4 Effect of reaction time on conversion EMD 2.00 75.27 92.3
Fig. 5 shows the effect of reaction time on conver- EMD 1.50 77.39 94.2
sion. The results indicate that conversion increases Note: T=75 °C; pH=11; CTF-2=1%; t=120 min; Vair=0.20 m3/h;
with time. At 120 min the conversion is about 80%. It C =16%; R=700 r/min.
MnSO4
changes little after this. The experimentally deter-
mined optimum reaction time is 2 h. 3.7 Identification of CMD products
3.5 Effect of agitation on conversion 3.7.1 XRD analysis
Air blowing and agitating are favorable for mass The crystal structure of three samples was charac-
transfer. Agitation enhances mass transfer between terized by XRD. One sample had been produced in
the solid and liquid phases. Fig. 6 shows that the the presence of catalyst, one was produced without
agitation speed greatly influences conversion. catalyst and one was a purchased reagent for
Conversion increases as the agitating speed increases. reference (The commercial manganese dioxide was
The difference between maximum and minimum more than 85% MnO2 and was produced by the
880 Mining Science and Technology Vol.20 No.6

Taishan Chemical Plant, Guangdong). XRD patterns similar. This shows that the catalyst TF-2 only
from these samples are presented in Fig. 7. accelerates the conversion of manganese sulfate and
does not change the crystal form of the manganese
dioxide produced. The crystal form of the products is
,QWHQVLW\&36

constant regardless of whether a catalyst is present or

not. The lines from Ȗ-MnO2 appear at 4.0337, 2.444
and 1.6322 nm, while strong peaks from Į-MnO2
appear at 3.0628 and 2.3300 nm. This indicates that
the synthetic CMD product consists mainly of
2θ Į-MnO2 and Ȗ-MnO2.
3.7.2 SEM analysis
The SEM images of the two products produced
with catalyst are shown in Fig. 8.
,QWHQVLW\&36

The product consists mainly of massive aggregates

the grains of which are mostly small. Under a
high-alkali environment MnO2 is deposited faster
than the crystal lattice can form so many new crystal
nuclei are formed. The crystals are very thin, with a
2θ
huge BET area. However, the MnO2 particles in
suspension easily adsorb impurity ions and low-
valence, incompletely oxidized, manganese salts onto
,QWHQVLW\&36

their surface. After acid washing the particle structure

becomes loose and porous and the surface area is
large. Therefore, the obtained MnO2 consists mainly
of lumpish crystals.
2θ

Fig. 7 XRD patterns of CMD samples

Published references attribute the characteristic

peaks at 3.964, 2.420 and 1.640 nm to Ȗ-MnO2, while
the peaks at 6.80, 3.082 and 2.403 nm are attributed
to Į-MnO2. The sample with Na+ is primarily Ȗ-MnO2
with the characteristic peaks at 4.020, 2.440 and
1.625 nm. The sample with K+ is primarily ȕ-MnO2
with the characteristic peaks at 3.276, 3.140, 2.428 Fig. 8 SEM images of CMD
and 1.630 nm. The Ȗ-MnO2 is electrochemically
active. The peaks of the commercial CMD sample 3.8 Recommended synthetic process
appear at 4.0071 and 1.6308 nm with a small Į-MnO2
Complete use of raw materials and reduced waste
peak at 2.4098 nm. The CMD sample is a mixed
discharge will be obtained from the process for
crystalline material consisting mostly of Ȗ-MnO2 with
preparing CMD from MnSO4 by the alkali-oxidation
a minor Į-MnO2 component. Figs. 7a and 7b show
method shown in Fig. 9.
that the peaks from the synthetic CMDs are extremely
$LU

Fig. 9 Process for preparing CMD from MnSO4 by alkali-oxidation

FU Jiangang et al Preparation of chemical manganese dioxide from manganese sulfate 881

4 Conclusions Touhami M E. Preparation of chemical manganese

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