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A Visual Insight into the Oxidation of Sulfide Minerals During Bioleaching and
Chemical Leaching of a Complex Ore
Mineral Processing and Extractive Metallurgy Review: An International Journal
Volume 31, Issue 3, 2010, Pages 176 - 190
Authors: H. Devecia; T. Ballb
DOI: 10.1080/08827508.2010.482859
Abstract
A scanning electron microscope (SEM) study was performed to provide a visual insight
into the oxidation patterns of sulfide minerals during chemical and bacterial leaching
of a complex ore for 3 days. The mineral grains were studied under SEM before and
after bacterial and chemical leaching with or without the addition of ferrous iron to
generate ferric iron in situ by bacteria or chemical oxidant (MnO 2). Both mesophilic
and moderately thermophilic cultures of bacteria were used in bioleaching tests. A
limited oxidation of sphalerite and pyrite, similar to those in acid leaching (control),
was observed to occur when no ferrous iron was added. However, the initial addition
of ferrous iron into bioleaching media was shown to significantly improve the oxidation
of sphalerite and pyrite. Galena was readily oxidized in the presence or absence of
bacteria. Sphalerite was oxidized more extensively/selectively than chalcopyrite and
pyrite, consistent with their respective nobility/electrochemical activity. Provided that
chemical/biological oxidation of sphalerite was intensive, a sulfur-rich layer appeared
to form on mineral surface. But, no such layer on pyrite surfaces was discernable.
Supplementary bioleaching data were also provided to support SEM observations and
to further elucidate the bioleaching characteristics of these sulfide phases. It can be
inferred from this study that the oxidation of sulfides proceeds most discernibly via
“indirect mechanism” and the generation of ferric iron by bacteria in sufficient
quantity is essential for the effective oxidation of sulfide minerals.
In this study the degree of bacterial attachment of the main microorganisms involved
in the bioleaching of metal sulfides and their influence on the dissolution rate and final
metal extractions were determined. Three different mineral sulfides were bioleached:
chalcopyrite (CuFeS 2 ), sphalerite (ZnS) and pyrite (FeS 2 ). A mixed culture of
mesophilic bacteria ( Acidithiobacillus and Leptospirillum spp.) was tested at 35°C and
thermophilic bacteria ( Sulfolobus spp.) were tested at 68°C. The results confirmed
that a relationship exists between attachment and mineral dissolution rates. The
bioleaching process can be divided into three stages. An initial stage with extensive
bacterial attachment to the pyritic phase, which is of major importance in order to
obtain high dissolution rates (since attached cells liberate Fe 2+ by contact bioleaching
and oxidize Fe 2+ to Fe 3+ avoiding iron accumulation at the surface). In a second stage
the bacterial attachment diminishes due to the saturation of the surface by the
attached cells. This limitation, together with the presence of Fe 2+ in solution,
produces an increase in the concentration of free cells, which use Fe 2+ as an energy
source. Finally, in a third stage, a balance between free and attached cells is reached,
giving rise to a cooperative mechanism. In this case, the attached cells attack the pyrite
phase of the mineral generating Fe 2+ . This in turn is oxidized by the free cells in
solution, regenerating the oxidizing agent (Fe 3+ ) for the indirect bioleaching of the
mineral.
The effects of anaerobic digestion and initial pH on the bioleaching of metals from
sewage sludge were investigated in shake flask experiments. A strain of
Acidithiobacillus thiooxidans was employed in the assays using secondary and
anaerobic sludges, which resulted in similar solubilization yields of the metals
chromium, copper, lead, nickel, and zinc for both the sludges investigated. The effect
of initial pH (7.0 and 4.0) on metal bioleaching was assayed by using the anaerobic
sludge inoculated with indigenous sulfur-oxidizing thiobacilli. Although the time
required to reach the end of the experiment (final pH close to 1.0) was shortened at
initial pH of 4.0, final metal solubilization was not significantly different for both initial
pH values, resulting in higher solubilization yields for copper, nickel, and zinc (higher
than 80%). Chromium and lead presented solubilization yields close to 50%. The results
obtained in this work showed that the metal bioleaching process can be applied to
sewage sludge regardless of the type of sludge and without the requirement of pH
adjustment.
The sulphur-based bioleaching process using sulphur-oxidizing bacteria (SOB) has been
demonstrated to be a feasible technology for removing heavy metals from
contaminated sediments, but the excess sulphur application will lead to the re-
acidification of bioleached sediments. The objective of the present study was to
examine the effect of sulphur concentration on the bioleaching of heavy metals from
contaminated sediments, with the ultimate purpose of minimizing the sulphur
addition. The results showed that the inoculation of 7% of indigenous SOB, containing
3.6 108 colony forming units (CFU) mL-1, and addition of elemental sulphur as a
substrate (0.5 to 7.0 g L-1) resulted in a sharp decrease in sediment pH from an initial
pH 8.0 to pH 1.4-2.4 and an increase in ORP (oxidation-reduction potential) from -10
mV to 500 mV within 10 days of bioleaching. Although the increase in sulphur
concentration enhanced the rates of pH reduction and ORP elevation, the bioleaching
process with the addition of 3.0 g L-1 of sulphur was already sufficient to reach
conditions of acidity (pH < 2.0) and ORP (500 mV) necessary for a satisfactory removal
of metals, and, at day 10, 71.8% of Cu, 58.2% of Zn, and 25.3% of Cr were removed
from the sediments. During the bioleaching process, Zn removal increased with a
reduction in pH, whereas the removal of Cu and Cr increased not only with a reduction
in pH but also with an increase in ORP. Results of sequential selective extraction
indicated that the final levels of metal removals were dependent on their speciation
distribution in the original sediments, and after bioleaching those unremoved metals in
the bioleached sediments mainly existed in the residual fraction.
Bioleaching of Cr from Tannery Sludge: The Effects of Initial Acid Addition and
Recycling of Acidified Bioleached Sludge
Environmental Technology
Volume 26, Issue 3, 2005, Pages 277 - 284
Authors: L. X. Zhou; D. Fang; S. M. Wang; J. W. C. Wong; D. Z. Wang
DOI: 10.1080/09593332608618558
Abstract
Abstract
This paper reviews analysis and modeling for the bioleaching of pyrite in stirred tank
reactors operated in a variety of modes: batch, repeated-batch and continuous flow. In
a batch reactor, rate data were consistent with a kinetic model assuming that the
growth rate of adsorbed bacteria on the mineral surface is proportional to the product
of the concentration of adsorbed cells and the fraction of adsorption sites unoccupied
by cells. In this modeling, the adsorbed cell concentration was related to the free cell
concentration in liquid medium through the Langmuir adsorption isotherm. The
reactor model for batch operation is used to investigate the effect of solution
replacement on bioleaching rate in repeated-batch reactor. Moreover, the batch
model is extended to analyze and model the bioleaching in a continuous-flow tank
reactor.
The use of recyclable forms of sulfur will exclude the risk of sediment reacidification
and reduce the cost of bioleaching process. Three different forms of sulfur (namely
sulfur powder, prills and pieces) were used to examine the utilization and recycle of
sulfur, used as energy substrate for sulfur-oxidizing bacteria (SOB) in the bioleaching of
heavy metal-contaminated sediments. The results showed that despite their relatively
smaller surface areas, the efficiency of metal bioleaching with sulfur prills and pieces
were comparable to that with sulfur powder. After 13 days of bioleaching, 71-74% of
Zn, 58-62% of Cu, and 22-31% of Cr could be leached from the sediments, respectively.
During bioleaching, most of the oxidizable and reducible forms of metals were
transformed to acid soluble, posing a favorable condition for final metals removal.
Sulfur recycling experiments showed that the recovered sulfur prills and pieces were as
the same effective in pH reduction as fresh sulfur, revealing the feasibility of eventual
reuse of the recycled sulfur in the bioleaching process. Further studies are required to
testify the performance of these recyclable forms of sulfur in future large-scale
bioleaching reactor.
Abstract
The aim of the present study was to examine Cr removal from tannery sludge by
bioleaching method using indigenous sulfur-oxidizing bacteria with special emphasis
on the influence of bioleaching process on sludge settleability. Chemical leaching with
sulfuric acid was designed as the control. The results showed that the inoculation of
sulfur-oxidizing bacteria and the addition of elemental sulfur were effective in
removing Cr from tannery sludge. After 144 hours of bioleaching, 98% of Cr could be
leached. Although it took only 8 hours to reduce the sludge pH from 7.8 to about 2.0
by chemical leaching as compared to 144 hours for bioleaching treatment, chemical
leaching removed only 91% of the total Cr. Regardless of bioleaching and chemical
leaching treatments, sludge settleability improved considerably with a decrease in
sludge pH. Bioleaching treatment performed better than chemical leaching in terms of
the percentage of settled sludge and the effluent suspended solids (ESS) content in
sludge supernatant. Nevertheless, further work should be carried out to investigate
the precise mechanisms leading to such enhanced sludge settleability during sludge
bioleaching process.
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En los procesos pirometalúrgicos, parte del cobre se pierde en la escoria que se genera
como residuo del proceso, pudiendo estar presente en ella, en concentraciones muy
superiores a las de muchas menas. El cobre se encuentra formando parte de pequeñas
partículas de mata, metal blanco y blister, ocluidas en fase de fayalita. En este trabajo se
ha probado la viabilidad técnica del proceso BRISA, que está basado en la
biolixiviación indirecta, para el tratamiento de este residuo. Se ha caracterizado una
escoria con un 2 % en cobre, desde los planos químico, granulométrico y metalográfico.
Este material se ha lixiviado con disoluciones de sulfato férrico en reactores agitados,
estudiándose el efecto de diversas variables. A partir de los resultados obtenidos, e
incluyendo un estudio económico, con resultados muy atractivos, se han seleccionado
las mejores condiciones de operación y se ha diseñado la etapa de lixiviación para una
planta de 30 t/h de capacidad. En esta planta sería posible alcanzar extracciones de
cobre superiores al 70 % con un tiempo de residencia de sólo 5 h. La etapa de
biooxidación suministraría el férrico necesario pese a haber presente Cu(II) en el
circuito en concentraciones de hasta 30 g/l.
The main source of copper loss from a smelter is copper in discard slag. Slag can
contain Cu in concentrations very much higher than those of many ores. Cu is present in
slag entrained in very small drops of matte, white metal and blister copper occluded in
fayalitic phase. In this work, the technical viability of the BRISA process, that is based
on the indirect bioleaching, for this residue has been proved. A sample of slag,
containing 2 % of copper, has been chemical, granulometrical and metallographic
characterized and it has been leached with ferric sulphate solutions in agitated reactors.
The influence of several variables have been investigated. Once the best operating
conditions had been selecting and an economic estimation had been done (with very
really attractive results), the leaching stage has been designed for a plant of 30 tonnes
per hour capacity. Cu extractions higher than 70% can be achieved with a residence
time of only five hours. Despite of Cu(II) concentration in fed is as high as 30 g/l,
biooxidation stage can supply Fe(III) demanded by ferric leaching stage.
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