Minerals Engineering 24 (2011) 11851187

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Minerals Engineering
journal homepage: www.elsevier.com/locate/mineng

Bioprocessing of pyrite concentrate from coal tailings for the production

of the coagulant ferric sulphate
Angli Viviani Colling, Jean Carlo Salom dos Santos Menezes, Ivo Andr Homrich Schneider
Universidade Federal do Rio Grande do Sul, Programa de Ps-Graduao em Engenharia de Minas, Metalrgica e Materiais, Centro de Tecnologia, Av. Bento Gonalves, 9500,
Bairro Agronomia, CEP: 91501-970, Porto Alegre, RS, Brazil

a r t i c l e i n f o a b s t r a c t

Article history: The aim of this work was to produce a high concentration ferric sulphate solution from coal pyrite tailings
Available online 29 April 2011 that could be used as coagulant for water and wastewater treatment. At laboratory scale it was performed
the oxidation of pyrite in an aqueous medium in a packed bed leaching column in an oxidizing environ-
Keywords: ment with the presence of acidophilic bacteria (Acidithiobacillus ferrooxidans) as well as nutrients for bac-
Coal terial growth. It was indicated that an aqueous solution rich in ferric sulphate can be produced which was
Tailings found suitable for application in water treatment plants.
Wasteprocessing
2011 Elsevier Ltd. All rights reserved.
Bioleaching
Ferric sulphate

1. Introduction Another way to produce the same chemical coagulants, without

Brazilian run-of-mine (ROM) coal contains high levels of impu-
rities (rock minerals and pyrite). Thus further concentration proce-
dures are required in most cases to reach the conventional
Brazilian power station standards. Approximately, 5060% of the
ROM coal is deposited as waste at tailings management facilities.
It is believed that there are more than 300 million tonnes of coal
tailings in deposits in the south of Brazil, generating large amounts
of acid mine drainage (AMD).
Active treatment processes using sodium hydroxide or lime are
applied for the neutralization of AMD in Brazil. The metal precipi-
tates are removed in settling ponds, conventional settling tanks,
lamellar tanks, and dissolved air otation units (Silva and Rubio,
2009; Silveira et al., 2009). The sludge typically contains 25% sol-
ids and high concentrations of iron and aluminium along with min-
or concentrations of manganese, zinc, and other metals, and
represents another environmental problem.
Recent research has shown that it is possible to produce poly-
ferric sulphate and poly-alumino-iron sulphate coagulants by
selective precipitation of the metals present in the AMD (Rao
et al., 1992; Menezes et al., 2009, 2010). This alternative allowed
elimination of sludge generation (or reducing the sludge waste vol-
ume/quantity) and producing a valuable chemical reagent. How-
ever, the process implies in pH adjustment, metal precipitation
as hydroxides, and in acidic dissolution of the sludge.
the addition of chemical reagents, is to directly process the tailings
to recover and dissolve the pyrite by a hydrometallurgical process.
It is known that the acidophilic bacteria, e.g. Acidithiobacillus ferro-
oxidans, can increase the rate of pyrite oxidation and dissolution by
several times (Kontopoulos, 1998; Brett and Jillian, 2003; Johnson
and Hallberg, 2003) and that they can be very signicant in the bio-
processing of coal tailings for the production of ferric coagulants.
It should be mentioned that coagulation is a physicochemical
process that causes the aggregation of colloidal particles present
in water, facilitating its removal. This process is widely used in
the treatment of water for public supply and for the treatment of
industrial efuents. The reagents most commonly used are alumin-
ium sulphate (AS), poly-aluminium sulphate (PAS), poly-alumin-
ium chloride (PAC), ferric sulphate (FS), poly-ferric sulphate
(PFS), ferric chloride (FC), and poly-ferric chloride (PFC) (Bratby
1980; Tchobanoglous et al., 2003; Metcalf and Eddy, 2003).
The aim of this work was to produce a ferric sulphate coagulant
by bioleaching of the pyrite present in coal tailings (FS-B/CT) and
then compared its effectiveness with a conventional poly-ferric
sulphate (PFS) coagulant in the water treatment process.
2. Materials and methods
2.1. Coal tailings sample

Corresponding author. Tel.: +55 51 3308 9966; fax: +55 51 3308 7116. The leaching experiments were carried out using a pyrite con-
E-mail addresses: angeli.colling@ufrgs.br (A.V. Colling), jean.menezes@ufrgs.br centrate obtained by gravimetric processing of a coal tailing rich
(Jean Carlo Salom dos Santos Menezes), ivo.andre@ufrgs.br (I.A.H. Schneider). in pyrite from the Brazilian coal eld of Santa Catarina (SC). The

0892-6875/$ - see front matter 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.mineng.2011.04.003
1186 A.V. Colling et al. / Minerals Engineering 24 (2011) 11851187

material was crushed and sieved, and the size fraction between
2 mm and 6 mm was used in the leaching column. The content
of pyrite in the sample was determined 51%. The X-ray analysis
of the material showed the presence of the following crystalline
compounds: pyrite (FeS2) (predominant), quartz (SiO2), kaolinite
(Al4(OH)8(Si4O10), and mica (KAl2(AlSi3O10).
the samples were left undisturbed without any agitation for a per-
iod of 10 min, to allow the solids to settle. The treated water was
analyzed for pH, turbidity, colour, metals (Fe, Al, Mn, and Zn), hard-
ness, and sulphate. All analyses followed the procedures described
in the Standard Method for the Examination of Water and Waste-
water (Eaton et al., 2005).

2.2. Reagents
3. Results and discussion

All the reagents used for analytical procedures, bacteria nutri-

The pyrite dissolution by microbial leaching process was suc-
ents, and pH adjustment additives in water treatment tests were
cessfully carried out. After 8 weeks, the iron concentration in the
of analytical grade. Distilled water was used for the preparation
leaching solution stabilized in 9.6%. This liquor was subsequently
of all solutions. Commercial poly-ferric sulphate (PFS), produced
ltered and evaporated to remove the suspended solids and to
from scrap iron by sulphuric acid digestion, was obtained from
reach the desirable iron concentration of 12.2%, allowing a FS-B/
Sulfato Rio Grande (RS/Brazil).
CT production of 790 mL kg1 (or 790 L t1).
Table 1 summarizes the characteristics of the FS-B/CT as well
2.3. Leaching experiments for ferric sulphate production
the composition of the commercial PFS sold for water treatment.
In terms of metal composition, the coagulant produced from the
The leaching experiments were carried out using a laboratory
coal tailings is similar when compared to the commercial PFS pro-
column constructed as packed bed reactor, with a sprinkling sys-
duced from iron scraps. The exception was the calcium, with a
tem, in a close circuit. The recirculation of the water was per-
higher concentration in the FS-B/CT, because was added as micro-
formed by a peristaltic pump and exible silicone hoses. The
nutrient for bacteria growing. After the ltration and evaporation
cylindrical glass column was 30 cm high and 7 cm in diameter,
steps, the presence of viable cells of A. ferrooxidans was not de-
and was lled with 1 kg of coal tailings. All other materials used
tected. The analysis of COT also indicates that the amount of extra-
in the assembly of the experimental study were sterilized in an
cellular polymers from bacterial activity is very low in the nal
autoclave at 120 C and pressure 1 kgf cm2 for 20 min.
liquor. However, the FS-B/CT contains a higher concentration of
Following columns assembly, 1 L of distilled/deionized water
sulphates.
was introduced which was recirculated at a ow rate of 2 L min1.
The results of water treatment tests are given in Table 2. Both
The bacteria inoculums were 10 mL of an acid mine drainage
coagulants were equally efcient in terms of residual amounts of
(AMD) obtained from the coal site, containing 6.8  105 cells mL1
suspended solids, turbidity, and colour. The residual amounts of
of A. ferrooxidans. The nutrients for bacterial growth were the com-
heavy metals in the treated water were very low and the lake
ponents of the medium 9 K (Eaton et al., 2005). At the end of each
water treated with all of the coagulants met the Brazilian stan-
week, the fraction of evaporated water was supplemented to 1 L
dards for drinking water.
and the water samples were collected and analyzed for total iron
The production of an iron rich coagulant from the pyrite con-
concentration (atomic absorption spectrometry), sulphate concen-
centrate from coal tailings presents both environmental and eco-
tration (gravimetric method after ignition of the residue), and the
nomic benets. Under the conditions applied in this work, it was
most probable number (MPN) of A. ferrooxidans (Eaton et al.,
possible to dissolve 48% of the pyrite in the leaching process in
2005). The medium 9 K was used for counting the bacteria in
one single leaching step. In other words, it is estimated that there
the suspension, which was specic for this microorganism.
will be a substantial reduction in the acid generation potential of
After 8 weeks of leaching (period where the concentration of
the coal tailings, minimizing the neutralization costs in AMD treat-
suspended cells of A. ferrooxidans population reached
ment plants. Another economic advantage can also be expected.
1  1011 cells mL1 and maximum extraction of iron and sulphate
Using these raw material and agricultural NPK as nutrients, the
was performed), the liquor was ltered (0.5 lm membrane) and
cost to produce FS-B/CT from the pyrite should not exceed $100
evaporated to reach the iron concentration of 12%, which was the
(US) m3 (or about R$ 200 Brazilian Reais m3) while a conven-
usual for most of the ferric sulphate (FS) coagulants commercial-
tional PFS is commonly sold at a price of $400450 (US) m3 (or
ized in Brazil. The FS-B/CT obtained from pyrite bioleaching, and
R$ 800900 m3) (Menezes et al., 2009). Considering a production
the commercial PFS were analyzed in terms of pH, dissolved metals
of 1000 t month1 of pyrite concentrate (that is reasonable for
(Fe, Al, Ca, Mn, and Zn), presence of A. ferrooxidans, TOC (total or-
small and medium size coal mining companies in Brazil) and a
ganic carbon), and sulphate. Metal analyses were carried out by
monthly coagulant potential production of 790 L t1, it would be
atomic absorption spectrometry. Sulphate concentrations were
determined by the gravimetric method after ignition of the residue.
All methods followed the Standard Method for the Examination of Table 1
Water and Wastewater (Eaton et al., 2005). The density of the Chemical composition of the ferric sulphate coagulant produced by bioleaching of the
pyrite present in coal tailings (FS-B/CT) and the poly-ferric sulphate coagulant
coagulants was determined gravimetrically in 10 mL volumetric
produced from iron scrap (PFS).
asks.
Parameter FS-B/CT PFS
2.4. Water treatment by coagulation pH 0.7 1.8
Fe (mg L1) 122,000 115,000
Studies involving water treatment were carried out with raw Al (mg L1) 3100 4419
Mn (mg L1) 1600 1585
water from Guaiba Lake (Porto Alegre, RS, Brazil) using a conven- Ca (mg L1) 2700 56.8
tional Jar Test apparatus. The coagulation procedure was carried Zn (mg L1) 24.1 22.4
out using a 1000 mL water sample. The samples of FS-B/CT and SO2
4 mg L
1
182,000 130,800
PFS were added at the same molar concentration of 0.4 mM Density (g mL1) 1.4 1.4
(Fe + Al). The pH was adjusted to 7.0 and the suspension was agi- A. ferrooxidans (cells mL1) Absent Absent
TOC (mg L1) 0.6 104
tated at 100 rpm for 5 min, followed by slow stirring at a speed
Pyrite dissolved (%) 48
of 20 rpm for 3 min. Subsequently, the agitation was stopped and
 A.V. Colling et al. / Minerals Engineering 24 (2011) 11851187 1187

Table 2
Characteristics of raw water and water treated with the coagulants FS-B/CT and PFS at a dosage of 0.4 mM (Fe + Al) at pH 7.0.

Parameter Raw water Treated with FS-B/CT Treated with PFS Brazilian standards for drinking water
pH 6.8 7.0 7.0
Turbidity (NTU) 81.3 0.4 0.5 5
Colour (Hazen) 44 2.0 2.0 15
Fe (mg L1) 1.2 <0.04 <0.04 0.3
Al (mg L1) <0.08 <0.08 <0.08 0.2
Mn (mg L1) <0.02 <0.02 <0.02 0.1
Zn (mg L1) 0.04 <0.02 <0.02 5
Hardness (mg L1 CaCO3) 22 183 134 500
Sulphates (mg L1) 7.8 223 82.9 250

possible to produce 790 m3 of ferric sulphate (12% iron). This vol-
ume of solution would treat water for 1 month for a population
of about 470,000 people.
4. Conclusion
Through the biohydrometallurgical process studied in this re-
search, it was possible to obtain a coagulant rich in ferric sul-
phate from a pyrite concentrate obtained from coal tailings.
The water treatment tests proved that this coagulant was at
least as effective as a similar coagulant produced from iron
scraps. In addition to the coagulant production, the process has
environmental benets because it reduces the volume of waste
and decreases the amount of pyrite in the material, minimizing
the potential for generation of acid mine drainage. Thus, in the
Brazilian coal eld areas, the concentration of pyrite and the
production of ferric sulphate coagulant could provide an eco-
nomic income to the mining companies and could reduce the
cost of acidic efuents treatment.
Acknowledgements
The authors thank nancial support extended by CAPES, CNPq,
and the Brazilian Coal Net for this research.
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