Technical Note

Effect of complexing agents in the desulphurization of coal by H

2
SO
4
and
H
2
O
2
leaching
E.T. Pecina

, L.F. Camacho, C.A. Herrera, D. Martnez

UAdeC, Universidad Autnoma de Coahuila, Escuela Superior de Ingeniera, Nueva Rosita, Coah., Mxico, C.P. 26850, Mexico
a r t i c l e i n f o
Article history:
Available online 25 November 2011
Keywords:
Coal
Hydrometallurgy
Leaching
Reaction kinetics
a b s t r a c t
The pyritic sulphur extraction from a sub-bituminous coal in an oxidizing aqueous media was examined.
The results show that the pyritic coal desulphurization in H
2
SO
4
solutions and in presence of H
2
O
2
could
be effectively increased to 89% by the addition of complexing agents such as quercetin, phosphoric, oxalic
and citric acids. According to the above, the current study might contribute to establish a new alternative
process to eliminate pyritic sulphur from coal concentrates.
2011 Elsevier Ltd. All rights reserved.
1. Introduction
The utilization of high sulphur coals has been an industrial con-
cern, because of the emission of SO
2
to the atmosphere in combus-
tion, which causes severe air pollution and formation of acid rain,
encouraging the research of coal desulphurization previous to cok-
ing and power generation processes.
The research of coal desulphurization in aqueous media has in-
volved the evaluation of many oxidizing agents such as acids, ferric
salts, potassium permanganate, oxygen, ozone, hydrogen peroxide
and bacteria (Ozbayoglu, 1998; Borah et al., 2001; Cara et al., 2005;
Borah, 2006; Alam et al., 2009; Dvalos et al., 2009). These meth-
ods are based in the anodic dissolution of pyrite in acidic oxidizing
solutions. Pyrite dissolution by hydrogen peroxide in highly acidic
solutions is characterized by the following reaction (Antonijevic
et al., 1997):
FeS
2
7:5H
2
O
2
H

Fe
3
2HSO

4
7H
2
O 1
Hydrogen peroxide reaction products are water and oxygen,
which clearly represent an environmental advantage over other
oxidizing agents.
Synthetic compounds, such as chelating and complex forming
agents, are employed in many industrial applications because of
their capabilities of binding metal ions and dissolving precipitates
and minerals. The action of these complexing/chelating reagents is
a good option to increase the efciency of the leaching process.
Key factors for selection of complexing agents that must be consid-
ered are: biodegradability or low toxicity and a complexing action
exerted under acidic pH. Oxalic acid is a reducer and also a complex-
ing agent that has been used in the iron oxide leaching during the
treatment of silica and clay mineral (Panias et al., 1996); citric acid
has been added in the leaching of lead metallurgical slag (Ettler
et al., 2004); and phosphoric acid has been applied in the leaching
of sheelite concentrate (Gurmen et al., 1999). Some of these agents
have exerted a benecial impact in the leaching efciency of sphal-
erite (Pecina et al., 2008). Quercetin is a avonoid frequently used as
a dietetic supplement, and forms iron complexes and oxidizes itself
with the production of hydrogen peroxide (El Hajji et al., 2006); its
bio-degradability makes this agent adequate to be considered in
the present study.
Based on our literature review, there is any study about the com-
plexing agents in coal desulphurization in sulphuric acid/hydrogen
peroxide solutions. According to the above, the current study might
contribute to establisha newalternative process to eliminate pyritic
sulphur from coal concentrates.
2. Experimental
2.1. Mineral sample and reagents
A sub-bituminous coal from the carboniferous region of Coahu-
ila, Mexico was collected. The dry characterization of the coal indi-
cated a content of 30.3% Ash, 3.05% S (2.45% of pyritic sulphur and
0.6% organic sulphur) and a caloric power of 5727 kcal/kg. 5% of
solids a particle size between 74 and +43 lm was employed in
the experiments. Reagents of analytical grade and distilled water
(10
6
X
1
cm
1
) were used in the tests.
0892-6875/$ - see front matter 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.mineng.2011.10.011

Corresponding author. Tel./fax: +52 861 614 1248.

E-mail address: teresa.pecina@uadec.edu.mx (E.T. Pecina).
Minerals Engineering 29 (2012) 121123
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2.2. Methodology
A base or neat solution was prepared with 10% H
2
SO
4
and 10%
H
2
O
2
, which correspond to the optimum desulphurization condi-
tions determined in previous tests (Pecina et al., 2008). Quercetin,
citric, oxalic and phosphoric acids were evaluated as complexing
agents in concentrations of 100 and 1000 ppm. Experiments in ab-
sence (neat solution) and presence of complexing agents were exe-
cuted following the combination of two levels of temperature (25
and 50 C) and treatment time (60 and 120 min). Pulp agitation
was achieved by using a magnetic stirring device. At the end of
the experiment the sample was ltered and the solution chemi-
cally analyzed.
2.3. Fe determination
The indirect method (conversion of dissolved iron from pyrite
to reacted inorganic sulphur) was applied. The good accuracy of
this procedure was revealed in previous work (Dvalos et al.,
2009). The Fe analysis of solutions was carried out by sampling
1 mL of the target solution (in contact with the coal) and com-
bined with a solution of potassium thiocyanate (100 mg/L SCN

).
The total iron of the solution was determined by ultraviolet
spectroscopy following the procedure of APHA-AWWA 4500-CN
M method.
3. Results and discussion
3.1. Effect of complexing agents in the pyritic sulphur elimination
Fig. 1 summarizes the results of the pyritic sulphur extraction
tests. The gure shown a dark and grey line that connects the
points related to the pyritic desulphurization process in absence
of complexing agents. The dark points above the dark line belong
to the best conditions at 120 min; below the line are located the re-
sults (in black), which represents no desulphurization improve-
ment. The data for a time of 60 min was shown in grey, and the
same consideration is made about the points above/below the line.
The results of 120 min treatment (dark points in the gure) and
of a concentration of 100 ppm, show that the oxalic acid and quer-
cetin generate the highest elimination of the pyritic sulphur, at a
temperature of 50 C and 25 C, respectively. Final inorganic desul-
phurization was in the order of 89% (oxalic) and 88% (quercetin).
However, the overall range of improvement (see Table 1) given by
the oxalic acid is only of 28%, which is quite low of the desulphuri-
zation enhancement produced by the quercetin (51.3%). When the
concentration of agents was raised to (1 g/L) 1000 ppm, only citric
acid generates a slight improvement, 61% of pyritic sulphur extrac-
tion and 9.1% of range of improvement, in the desulphurization pro-
cess at 50 C.
The results of 60 min treatment (grey points in Fig. 1), indicate
that 100 ppm of quercetin improves the coal desulphurization at
25 Cwitha nal 76%of pyritic sulphur extractionandthe best range
of improvement (75.8%). A less important increase in the efciency
was obtained at 50 C with both agent concentrations (100 and
1000 ppm), the increase of the pyritic sulphur elimination (range)
goes from 10% to 26.3%. The descending order of the complexing
agents effect is: quercetin > citric acid > phosphoric acid > oxalic acid.
Although, the reactions and mechanism of the interaction of the
complexing agents and the pyrite is beyond the purposes of this
work, it could be stated that complexing agents inuence the reac-
tion stage as a result of ionic complex formation from the reactant
contained in the solid substrate. In the former context, Nowack
(2003) stated that the dissolution of a mineral phase by chelating
or complexing agents can be explained in terms of a ligand ex-
change process and the concentration of the surface bound ligands.
In an oxide mineral, the ligands weaken the metaloxygen bonds
and enhance the release of the metal ions from the mineral. In
the case of oxalic acid, Panias et al. (1996) stated that the non-
reductive dissolution mechanism of iron oxides involves the sim-
ple desorption of the adsorbed surface ferric complexes, and spec-
ies that, the iron subtraction is accomplished only in the surface
active sites, the number of which increases with the pH reduction.
0
200
400
600
800
1000
0
20
40
60
80
100
25
30
35
40
45
50
P
y
r
i
t
i
c
s
u
l
p
h
u
r
e
x
t
r
a
c
t
i
o
n
,
%
Tem
perature, C
C
o
n
c
e
n
t
r
a
t
i
o
n
,
p
. p
.
m
.
1
1
1
2
1
1-5
2
3
2
4
3
4
5
5
5
3
4
5
1-4
2
1
3, 4
5
1
4
3
2,5
2-5
Reactiontime:
60 min
120 min
1. Neat
2. Citric
3. Oxalic
4. Phosphoric
5. Quercetn
Fig. 1. Effect of complexing agent type in the pyritic sulphur extraction. Grey line is
related to 60 min of conditioning time, dark points to 120 min. The lines connect
the neat solution.
Table 1
Desulphurization results performed in absence and presence of the complexing agents and analysis of the range of improvement (I).
100 ppm 1000 ppm
T = 25 C T = 50 C T = 25 C T = 50 C
60 min 120 min 60 min 120 min 60 min 120 min 60 min 120 min
1. Neat 0.2 36.7 10.6 61.0 0.2 36.7 10.6 61.0
2. Citric 0.3 3.6 0.4 55.7 1.0 0.6 35.1 70.1
3. Oxalic 0.7 28.3 21.2 89.0 0.4 0.2 21.2 69.5
4. Phosphoric 0.4 18.7 21.7 65.1 0.5 0.1 31.0 31.0
5. Quercetin 76.0 88.0 36.7 49.7 0.1 0.4 36.9 59.4
IC 0.1 33.1 10.2 5.3 0.8 36.1 24.5 9.1
IO 0.5 8.4 10.6 28 0.2 36.5 10.6 8.5
IP 0.2 18.0 11.1 4.1 0.3 36.6 20.4 30.0
IQ 75.8 51.3 26.1 11.3 0.1 36.3 26.3 1 to 6
Neat: In absence of complexing agents; IC (range between the citric and the neat desulphurization in percentage). IC = citricneat; IO = oxalicneat; IP = phosphoricneat;
IQ = quercetinneat. Negative values indicate a smaller desulphurization that the obtained with the neat solution.
122 E.T. Pecina et al. / Minerals Engineering 29 (2012) 121123
Similar processes would be occurring onto pyrite surface with the
complexing agents examined, given that iron ions released from
pyrite surface during the oxidative leaching are oxidized to ferric
ions, then forming complexes Fe
III
L
n3
aq
with the agents (H
n
L).
In the case of pyrite, sulphur oxidizes to oxy-sulphuric species
(S
x
O
y
), the overall surface complexation and sulphur oxidation is
proposed to be:
S
2
Fe
2
L
n

ads
4:5O
2
2H

Fe
II
L
n2
aq
2SO
2
4
H
2
O 4e

2
Efuent of the process would have ferric complexes and sulphate
ions that could be precipitated by pH basication.
4. Conclusions
The results stated above show that the pyritic coal desulphuri-
zation can effectively be achieved by the addition of complexing
agents such as quercetin, oxalic phosphoric and citric acids in
H
2
SO
4
and H
2
O
2
solutions. The overall pyritic sulphur content
was reduced by 89% and 88% under the optimum conditions given
by 100 ppm of oxalic acid or quercetin, at temperatures of 50 and
25 C, respectively. For 74/+43 lm of particle size of the sub-bitu-
minous coal in test with 5% of solids. The major issues that must be
overcome in order to successfully use complexing agents at indus-
trial level are related to the optimization of solids content and con-
centration of complexing agent. In spite of this, there is no doubt
that the resulting improvement of the aqueous oxidizing process
brings a new chemical aspect to consider when an oxidative disso-
lution process of a refractory mineral (e.g., pyrite) is under devel-
opment. For communities with high dependence of the coal
mining operations, economical improvement and a positive social
impact are derived from the coal desulphurization, by allowing
the integration of high sulphur sub-bituminous coal in the coking
process for the steel industry or in power generation.
Acknowledgements
Authors are grateful for the nancial support through the nan-
cial support granted by PROMEP and by the fund 4004 from the
Universidad Autonma de Coahuila (Mxico).
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