Energy Sources, Part A: Recovery, Utilization, and

Environmental Effects

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Oxidative desulfurization of Chakwal coal using

potassium permanganate, ferric sulfate, and
sodium hypochlorite

Saima Irum, Javaid Akhtar, Naseer Sheikh & Shahid Munir

To cite this article: Saima Irum, Javaid Akhtar, Naseer Sheikh & Shahid Munir (2017): Oxidative
desulfurization of Chakwal coal using potassium permanganate, ferric sulfate, and sodium
hypochlorite, Energy Sources, Part A: Recovery, Utilization, and Environmental Effects, DOI:
10.1080/15567036.2016.1222028

To link to this article: http://dx.doi.org/10.1080/15567036.2016.1222028

Published online: 15 Feb 2017.

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ENERGY SOURCES, PART A: RECOVERY, UTILIZATION, AND ENVIRONMENTAL EFFECTS
http://dx.doi.org/10.1080/15567036.2016.1222028

Oxidative desulfurization of Chakwal coal using potassium

permanganate, ferric sulfate, and sodium hypochlorite
Saima Irum, Javaid Akhtar, Naseer Sheikh, and Shahid Munir
Centre for Coal Technology, Faculty of Engineering & Technology, University of the Punjab, Lahore, Pakistan

ABSTRACT KEYWORDS
This study investigates the desulfurization of Chakwal coal (Punjab, Pakistan) Coal leaching;
using three oxidants, namely KMnO4, Fe2(SO4)3, and NaOCl. Operational para- desulfurization; Fe2(SO4)3;
meters were concentration, particle size, and pH. According to the results, KMNO4; NaOCl
KMnO4 removed 95% sulfur from coal. Similarly, Fe2(SO4)3 removed 71% and
NaOCl removed 50% sulfur. NaOCl was found to be less efficient compared to
other two oxidants. Fe2(SO4)3 and KMnO4 both removed sulfur significantly.
Fe2(SO4)3 could be considered for cleaning of low grade coals since it is
cheaper and very effective in removing sulfur from coal. The cleaned
Chakwal coal can be used in different energy recovery schemes.

1. Introduction
Pakistan is blessed with 186 billion tons of coal reserves. These reserves are enough to meet the
country’s fuel requirements for a long period of time. A less than 1% share of coal in the electricity
generation mix seems to be unreasonable figure for a country having huge reserves of fossil fuels.
The major challenges associated with Pakistani coals are high sulfur and ash contents (Wahab et al.,
2015). A pre-combustion coal cleaning can upgrade Pakistani coals for utilization in energy recovery
schemes. Various chemical processes are presently being developed employing agents such as nitric
acid, hydrogen peroxide, ozone, oxygen, chlorine, potassium dichromate, KMnO4, NaOCl, NaClO2
ferric salts, and cupric salts for the extraction of pyritic sulfur (Li and Cho, 2005; Ehsani, 2006; Liu
et al., 2008; Ishaq et al., 2011; Zhao et al., 2011; Ghauri et al., 2016).
In this study, sulfur removal was investigated using low grade Chakwal coal and a comparison
was drawn among three oxidizing agents such as KMnO4, Fe2(SO4)3, and NaOCl under identical test
conditions. The operating parameters studied were the comparison of the performance of oxidizing
agents, concentration, coal particle size, and pH of solution.

2. Experimental
Three oxidants (KMnO4, Fe2(SO4)3, and NaOCl) were selected due to their specific oxidation poten-
tials of 1.67, 1.30, and 0.94 volts, respectively. The action of oxidants was investigated to compare their
effectiveness in sulfur removal from Chakwal coal. About 20 kg bulk coal sample was collected from
Chakwal coal mine no.2. The coal mine is located at Choa Saiden Shah in the district of Chakwal (Salt
Range) in the province of Punjab, Pakistan. The estimated coal reserves of area are 100 million tonnes.
The sample was statistically obtained from run-of-mine stockpile with the help of scoops. The bulk
coal sample, containing 2–3 inch in top size was subjected to roll crusher, where from the crushed coal,
in the size range of ½ to ¼ inch was obtained. The coning and quartering process was repeatedly

CONTACT Shahid Munir director.cct@pu.edu.pk Centre for Coal Technology, Faculty of Engineering & Technology, University
of the Punjab, Lahore, Pakistan.
Color versions of one or more of the figures in the article can be found online at www.tandfonline.com/ueso.
© 2017 Taylor & Francis Group, LLC
2 S. IRUM ET AL.

employed till eight lots of 2.5 kg were obtained. The 2.5 kg lots were separately crushed and ground to
make test samples in the size range of 250, 150, 105, 74, and 63 µm for chemical leaching tests and
sealed in air tight plastic bags.
For each experiment, 20 g of the coal sample was oxidized with 100 mL solution of each oxidizing
agent either KMnO4, Fe2(SO4)3, and NaOCl. Experiments were carried out in a three necked flasks fitted
with a reflux condenser at 80°C, 1 h time duration and 500 rpm. After experiment, the treated coal was
filtered from residual water and washed with hot distilled water. The filtered contents were dried at 105°C
overnight and sealed in air tight bags. Volatile matter, moisture, and ash of original coal sample were
determined using standard ASTM methods, D3175, D3173, and D3174, respectively. The gross calorific
value was determined using a Leco AC 500 calorimeter, Berlin, Germany. The total sulfur contents of the
original and treated coal samples were measured using a carbon sulfur analyzer Leco SC-144 DR, USA.
According to proximate results of Chakwal coal, its moisture, volatile matter, ash, and sulfur contents
were 5.15%, 32.6%, 23%, and 5.0%, respectively. Its gross calorific value was 3031 Kcal/kg.

3. Results and discussions

3.1. KMnO4 as an oxidant
Figure 1 describes the effect of KMnO4concentration on removal of sulfur at different particle sizes.
It was found that finer particle size and high concentration of KMnO4 both favored the sulfur
removal. Combined effect of particle size and KMnO4 concentration is evident in Figure 1.
At 5% KMNO4 concentration, sulfur removal increased from 27% to 50% by decreasing particle
size from 250 to 63µm (Figure 1). At 25% concentration, sulfur removal increased from 67% to 94%
by decreasing particle size from 250 µm to 63 µm. It is inferred that 25–27% variations in sulfur
removal were due to variations in particle size. Similarly, 40–45% variations in sulfur removal were
due to KMNO4 concentration. The maximum sulfur removal was found to be 94% with operating
variables of 63 µm particle size and 25% KMNO4 concentration.
The concentration of KMNO4 was found to be a strongly influencing variable. The effect of
KMNO4 on sulfur removal could be attributed to its strong oxidation potential to oxidize sulfur from
coal. The effect of particle size could be associated to exposed surface area. The fine particles enable
good mass transfer and easier diffusion of KMNO4 through pores of coal particles. Besides, fine coal
particles provide better interfacial interaction among KMNO4 and pyrite particles compared to
coarser ones (Attia and Fung, 1993). The rate of diffusion of both KMNO4 solution and sulfate

100

80
% sulfur removal

60

40

20
5% 10% 15% 20% 25%
0
0 50 100 150 200 250 300
mesh size

Figure 1. Effect of particle size on % sulfur removal from coal at various concentrations of KMnO4. Solid liquid ratio (20% W/V),
temperature 80°C, reaction time 1 h, atmospheric pressure, stirring speed 500 rpm.
 ENERGY SOURCES, PART A: RECOVERY, UTILIZATION, AND ENVIRONMENTAL EFFECTS 3

products (SO4
2 ) (Eqs. 1 & 2) through pores has positive effect on desulfurization of coal (Ghauri
et al., 2016). The formation of MnO2 and jarosite (KFe3(SO4)2(OH)6) could block the pores of coal
and inhibit the transfer of oxygen from oxidizing agent to the pyrite surface or through diffusion in
pores of the coal (Attia and Fung, 1993). Therefore, finer particle size would be necessary to achieve
higher desulfurization efficiency.
MnO4
þ 2H2 O þ 3e
! MnO2 þ 4OH
(1)
þ þ3
K þ 3Fe þ 2SO4
2 þ 6OH
! KFe3 ðSO4 Þ2 ðOHÞ6ppt # ðJarositeÞ (2)
Figure 2 shows the effect of pH on sulfur removal at different KMNO4 concentrations. The acidic
pH ~ 3.5 exerted insignificant effect on sulfur removal. The percentage sulfur removal remained
<50% even at 25% KMNO4 concentrations at this pH. FeS2 converts to elemental sulfur during
oxidation in acidic pH. The elemental sulfur does not remove during filtration and become part of
leached coal Therefore, acidic pH is considered as unsuitable for sulfur removal by KMNO4.
As shown in Figure 2, a maximum sulfur removal of 92% was observed at neutral pH and 25%
KMNO4 concentration. There was significant increase in sulfur removal for all KMNO4 concentra-
tion at neutral pH. This pH can be referred as suitable for oxidation of coal using KMNO4. It is due
to the reason that neutral pH allows quick settling of jarosite (Eq. 2) without layering unreacted
pyrite (Li and Cho, 2005; Ghauri et al., 2016). It is evident from Figure 2, that alkaline media (pH
9–11) did not support sulfur removal. The reason might be that in alkaline medium, either some
hydrated products or hydroxides produced had covered the pyrite particles, so that pyrites were
unexposed to react with KMnO4 solutions.
The poor performance of KMnO4 in both acidic and alkaline media is also reported in (Attia and
Fung, 1993). The oxidation of coal using KMNO4 can be carried out efficiently in neutral medium.

3.2. Fe2(SO4)3 as an oxidant

The effect of concentration of Fe2(SO4)3 and coal particles size on sulfur removal is shown in
Figure 3. It was found that the concentration and the particle size both have exerted significant effect
on sulfur removal. For 5% concentration, the removal of sulfur was insignificant. High concentration
of Fe2(SO4)3 was necessary to achieve >50% sulfur removal. A maximum of 71% sulfur removal was
achieved using Fe2(SO4)3, Fe2(SO4)3 concentrations beyond >15% were found unsuitable for sulfur
removal. As shown in Eqs. (3 & 4), elemental sulfur, FeSO4 and H2SO4 are formed during Fe2(SO4)3/

80

60
% sulfur removal

40

20

5% 10% 15% 20% 25%

0
0 50 100 150 200 250 300
mesh size

Figure 2. Showing % sulfur removal against pH values at various concentration of KMnO4. Solid liquid ratio (20% W/V),
temperature 80°C, reaction time 1 h, atmospheric pressure, stirring speed 500 rpm.
4 S. IRUM ET AL.

60

% sulfur removal
40

20

5% 10% 15% 20% 25%

0
0 50 100 150 200 250 300
mesh size

Figure 3. Showing % sulfur removal against particle size at various concentrations of Fe2(SO4)3: solid liquid ratio (20% W/V),
temperature 80°C, reaction time 1 h, atmospheric pressure, stirring speed 500 rpm.

FeS2 oxidation. Both FeSO4 and elemental sulfur would form a layer around FeS2 and inhibit the
mass transfer of oxidizing agent to substrate. Moreover, it is quite possible that Fe+3 ions are
converted to Fe+2 ions at excess concentration of Fe2(SO4)3 thereby creating a layer around FeS2
(Lewis and Drickamer, 1968). Therefore, concentrated Fe2(SO4)3 solution might decrease removal of
sulfur. This discussion could be the reason for low percentage removal of sulfur in case of 20% and
25% Fe2(SO4)3 (Figure 3).
The grinding of coal exerted positive impact on removal of sulfur. In case of Fe2(SO4)3, the
smallest particle size (63 µm) was found effective for sulfur removal compared to coarser
particle sizes. Finely grounded FeS2 particles could be attached easily by Fe2(SO4)3. As a result
high percentage of sulfur removal could be achieved at fine grinding (Hamersma et al., 1976).

FeS2 þ 4:6 Fe2 ðSO4 Þ3 þ 4:8 H2 O ! 10:2 FeSO4 þ 4:8 H2 SO4 þ 0:8S (3)

FeS2 þ14Feþ3 þ8H2 O ! 15Feþ2 þ2HSO4
1 þ14Hþ (4)

Figure 4 describes the effect of pH on sulfur removal using Fe2(SO4)3. As shown, sulfur removal
was favored in neutral pH but dropped in alkaline or acidic medium. The maximum of sulfur
removal of 71% was achieved using Fe2(SO4)3 in neutral pH.
The reactions shown in Eqs. (5 & 6) describe the unsuitability of acid and basic medium during
oxidation of FeS2 with Fe2(SO4)3 (Paykani and Mardan, 2016). In acidic medium, the conversion of
Fe+3 ions to Fe(OH)3 is significant. Fe(OH)3 once formed settle down as gelatinous mass on surface
of FeS2. The higher the concentration of Fe2(SO4)3, the more are the chance for the formation of Fe
(OH)3. In alkaline pH, the abundance of OH− force Fe2+ to form Fe(OH)2, which would adhere to
FeS2 surface as gelatinous mass, thereby reducing its oxidation.
The neutral medium does not allow the formation of Fe(OH)3 or Fe(OH)2. This might due to
reason that the abundance of H+ ions and OH− ions would be insignificant in neutral pH. Therefore,
high sulfur removal efficiency is expected in neutral pH using Fe2(SO4)3 as an oxidant.

Feþ3 þ 3OH
! FeðOHÞ3 ðpH2 to 4Þ acidic medium (5)

Feþ2 þ 2OH
! FeðOHÞ2 ðpH7to9Þ basic medium (6)

 ENERGY SOURCES, PART A: RECOVERY, UTILIZATION, AND ENVIRONMENTAL EFFECTS 5

90

75

% sulfur removal
60

45

30
5% 10% 15% 20% 25%
15
2.0 4.0 6.0 8.0 10.0 12.0
pH

Figure 4. Showing % sulfur removal against various pH values at various concentrations of Fe2(SO4)3: solid liquid ratio (20% W/V),
temperature 80°C, reaction time 1 h, atmospheric pressure, stirring speed 500 rpm.

3.3. NaOCl as an oxidant

According to Figure 5, the sulfur removal kept increasing as the concentration of NaOCl was
increased from 5% to 20%. However, the sulfur removal decreased when 25% concentration of
NaOCl was used. The maximum of 50% sulfur removal was achieved with 20% NaOCl. The fine
grinding of coal particles favored the removal of sulfur.
The mechanism for reaction of NaOCl with organic sulfur in coal is to form sulfonyl chloride
(RSClO−), soluble sulfonate (RSO3H) and sulfates (SO4−2) as shown in Eq. (7). Pyritic sulfur could be
removed through formation of Fe(OH)3 shown in Eq. 8 (Li and Cho, 2005). Eq. 8 represents
interesting information, as pyrites are converted to soluble SO4−2, and insoluble Fe(OH)3. Excess
formation of Fe(OH)3 might inhibit the sulfur removal efficiency. Low sulfur removal was observed
25% NaOCl solution. This might be due abundance of Fe(OH)3 that may surround FeS2 particles
inhibit further oxidation. Moreover, excessive concentration would increase chlorine content and as
a result the reactivity of pyrites with NaOCl may decrease resulting in overall decrease of sulfur

80

70
% sulfur removal

60

50

40

30
5% 10% 15% 20% 25%

20
2.0 4.0 6.0 8.0 10.0 12.0
pH

Figure 5. Showing % sulfur removal against particle size at various concentrations of NaOCl: solid liquid ratio (20% W/V),
temperature 80°C, reaction time 1 h, atmospheric pressure, stirring speed 500 rpm.
6 S. IRUM ET AL.

80
5% 10% 15% 20% 25%
70

% sulfur removal
60

50

40

30

20
2.0 4.0 6.0 8.0 10.0 12.0
pH

Figure 6. Showing % sulfur removal against various pH values at various concentrations of NaOCl: solid liquid ratio (20% W/V),
temperature 80°C, reaction time 1 h, atmospheric pressure, stirring speed 500 rpm.

removal. Therefore, 15% to 20% concentration levels would be more suitable for removal of sulfur
from coal using NaOCl.
H2 O
R
S
R= þ 2ClO
! RSClO
þ RClO

! RSO3 H þ RCl (7)

2FeS2 þ 15ClO
þ 7H2 O ! 2FeðOHÞ3 þ 15Cl
þ 4SO4
2 þ 8Hþ (8)

Figure 6 describes the effect of pH on sulfur removal using NaOCl. The sulfur removal was the
lowest in acidic medium and favored in alkaline medium. The maximum of 50% sulfur was removed
using NaOCl. The chloride ions (Cl−) are generated from ionization of NaOCl in acidic pH. These
ions are attached to FeS2 surface in the form of Cl2 bubbles and cause hindrance to oxidation. (Li
and Cho, 2005) reported the presence of 1–2% of Cl2 in coal leached with NaOCl. Therefore, acidic
medium would not be suitable NaOCl.

4. Comparison and mechanistic aspects of oxidizing agents

Table 1 compares the effectiveness of oxidizing agents on sulfur removal under optimum operating
conditions. As evident the order of performance of oxidizing agents for sulfur removal was KMNO4 >
Fe2(SO4)3 > NaOCl. KMNO4 was found to be efficient oxidant for sulfur removal from Chakwal coal
compared to other two oxidants. NaOCl was a weak oxidizing agent therefore, required high
concentration to liberate pyrite particles compared to Fe2(SO4)3.
The mechanistic aspect of performance of the oxidizing agents would be that KMnO4 reacts with
pyritic sulfur to form Jarosite [KFe3(SO4)2(OH)6]. Jarosite, settles quickly without layering FeS2
particles in neutral pH. In acidic and basic pH, it settles as gelatinous mass and there is more chance
of attaching to FeS2 surface. In case of Fe2(SO4)3, due to release of excess Fe+3 ions gelatinous

Table 1. Comparison of performance of oxidizing agents for sulfur removal.

Operating conditions
Oxidant Concentration (%) Particle size (µm) pH Sulfur in leached coal % sulfur removal
KMNO4 25 63 7 0.24 95
Fe2(SO4)3 15 63 7 1.45 65
NaOCl 20 63 11 2.11 57
 ENERGY SOURCES, PART A: RECOVERY, UTILIZATION, AND ENVIRONMENTAL EFFECTS 7

precipitates (Fe(OH)3) start forming which adhere the unreacted pyrite particles and sulfur removal
starts decreasing (Eq. 8). Reaction of FeS2 with NaOCl produces excess chloride ions which also form
Cl2 and Cl2 bubbles adheres at surface of unreacted FeS2 particles (Eq. 8). The adhered Cl2 bubbles
reduce the oxidation of FeS2 particles.

5. Conclusions
In this study, three oxidizing agents namely KMnO4, Fe2(SO4)3, and NaOCl were tested under identical
experimental conditions for desulfurization of Chakwal coal containing 5% sulfur. KMnO4, was found
to be strong oxidizing agent, and has reduced 95.14% sulfur from bulk coal sample. NaOCl was
comparatively weaker oxidant and has reduced only 57.80% sulfur. The reagent was not found to be
technically viable. Fe2(SO4)3 was fairly good oxidizing agent and under optimum experimental
conditions and has reduced 71% sulfur. Fe2(SO4)3 being a simple, cheaper and easy to react with
pyritic sulfur can be considered as feasible oxidant for sulfur removal from low grade coals.

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