Leaching - Iron & Sulfur

IRON AND SULFUR IN MICROBIAL LEACHING
Introduction:
Bioleaching is a simple and effective technology for metal extraction from low-grade
ores and minerals concentration. Metals recovery from sulfide minerals is based on the activity
of chemolithotrophic bacteria, mainly Thiobacillus ferrooxidans and Thiobacillus thiooxidants,
which convert insoluble metal sulfides into soluble metal sulfides. Non-sulfides ores and
minerals can be treated by heterotrophic bacteria and by fungi. In these cases metal extraction is
due to the production of organic acids and chelating and complexing compounds excreted into
the environment. At present bioleaching is used essentially for the recovery of copper, uranium
and gold, and the main techniques employed are heap, dump and in situ leaching. Tank leaching
is practiced for the treatment of refractory gold ores. Bioleaching has also some potential for
metal recovery and detoxification of industrial waste products, sewage sludges and soil
contaminated with heavy metals.
The most commonly used microorganisms for bioleaching are Thiobacillus

thiooxidans and T.ferrooxidans. The other microorganisms may also be used in bioleaching
viz., Bacillus licheniformis, B. luteus, B. megaterium, B. polymyxa, Leptospirillum ferrooxidans,
Pseudomonas fluorescens, Sulfolobus acidocaldarius, Thermothrix thioparus, Thiobacillus
thermophilica, etc.
Models of Leaching Mechanisms:

Originally, a model with two types of mechanisms which are involved in the microbial
mobilization of metals has been proposed
1. Direct bacterial leaching: Microorganisms can oxidize metal sulfides by a “direct”

mechanism obtaining electrons directly from the reduced minerals. Cells have to be
attached to the mineral surface and a close contact is needed. The adsorption of cells to
suspended mineral particles takes place within minutes or hours. This has been
demonstrated using either radioactively labeled Thiobacillus ferrooxidans cells grown on
NaHCO3 or the oxidative capacity of bacteria attached to the mineral surface. Cells
adhere selectively to mineral surfaces occupying preferentially irregularities of the
surface structure. In addition, a chemotactic behavior to copper, iron, or nickel ions has
been demonstrated for Leptospirillum ferrooxidans. Genes involved in the chemotaxis
were also detected in Thiobacillus ferrooxidans and Thiobacillus thiooxidans.
T. ferrooxidans
2FeS2 + 7O2 + 2H2O 2FeSO4 + 2H2SO4
2. In direct bacterial leaching: The oxidation of reduced metals through the “indirect”
mechanism is mediated by ferric iron (Fe3+) originating from the microbial oxidation of
ferrous iron (Fe2+) compounds present in the minerals. Ferric iron is an oxidizing agent
and can oxidize, e.g., metal sulfides and is (chemically) reduced to ferrous iron which, in
turn, can be microbially oxidized again. In this case, iron has a role as electron carrier. It
was proposed that no direct physical contact is needed for the oxidation of iron.
FeS2 + Fe2 (SO4) 3FeSO4 + 2S°
2S° + 3O2 + 2H2O 2H2SO4
Oxidation of ferrus (Fe2+) to ferric (Fe3+) by T. ferrooxidans at low pH is given below:
T. ferrooxidans
4FeSO4 + 2H2SO4 + O2 2Fe2(SO4)3 + 2H2O
Common Leaching process: There are three commercial methods used in leaching
1. Slope Leaching:
About 10,000 tones of ores are ground first to get fine pieces. It is dumped in large piles
down a mountain side leaching dump. Water containing inoculums of Thiobacillus is
continuously sprinkled over the pile. Water is collected at bottom. It is used to extract metals and
generate bacteria in an oxidation pond.
2. Heap Leaching:
The ore is dumped in large heaps called leach dump. Further steps of treatment are as
described for slope leaching.
3. In situ Leaching:
In this process ores remain in its original position in earth. Surface blasting of rock is
done just to increase permeability of water. Thereafter, water containing Thiobacillus is pumped
through drilled passage to the ores. Acidic water seeps through the rock and collects at bottom.
Again from bottom water is pumped, mineral is extracted and water is reused after generation of
bacteria.
Main factors affecting bioleaching:

• Physicochemical:
Temperature, pH and to keep ferric Oxygen reactions
- affects leaching rate, microbial composition and activity
- needs to be low to obtain the fastest leaching rates and to keep ferric iron and metals in
solution
- Electron acceptor needed in chemical and biological oxidation
• Microbiological:
Microbial diversity cultures - mixed cultures tend to be more robust and efficient than
pure
Population density - high population density tends to increase the leaching rate
Metal tolerance - high metal concentrations may be toxic to metals
• Mineral:
Composition - provides electron donor and trace elements
Particle size - affects the available mineral/liquid contact area
Surface area - leaching proportional to the increase in mineral surface area
Porosity - cracks and pores in the particles give rise to the internal area
Presence of other metal sulfide - mineral having the lowest potential is generally oxidized
first.
Process:
Bioleaching can involve numerous ferrous iron and sulfur oxidizing bacteria,
including Acidithiobacillus ferrooxidans and Acidithiobacillus (also known as Thiobacillus). As
a general principle, Fe3+ ions are used to oxidize the ore. This step is entirely independent of
microbes. The role of the bacteria is the further oxidation of the ore, but also the regeneration of
the chemical oxidant Fe3+ from Fe2+.
For example, bacteria catalyse the breakdown of the mineral pyrite (FeS2) by oxidizing
the sulfur and metal (in this case ferrous iron, (Fe2+)) using oxygen. This yields soluble
products that can be further purified and refined to yield the desired metal.
Pyrite leaching (FeS2):

In the first step, disulfide is spontaneously oxidized to thiosulfate by ferric ion (Fe3+),
which in turn is reduced to give ferrous ion (Fe2+): reaction-1:
FeS2+6Fe3++3H2O 7Fe2++S2O32-+6H+ (Spontaneous)
Reaction-2: The ferrous ion is then oxidized by bacteria using oxygen:
4Fe2+O2+4H+ 4Fe3++2H2O (Iron oxidizers)
Reaction-3: Thiosulfate is also oxidized by bacteria to give sulfate:
S2O32-+2O2+H2O 2SO42-+2H+ (Sulfur oxidizers)
Reaction-4: The ferric ion produced in reaction-2 oxidized more sulfide as in reaction-1, closing
the cycle and given the net reaction:
2FeS2+7O2+2H2O 2Fe2++4SO42-+4H+
The net products of the reaction are soluble ferrous sulfate and sulfuric acid.
The microbial oxidation process occurs at the cell membrane of the bacteria.
The electrons pass into the cells and are used in biochemical processes to produce energy for the
bacteria while reducing oxygen to water. The critical reaction is the oxidation of sulfide by ferric
iron. The main role of the bacterial step is the regeneration of this reactant.
The process for copper is very similar, but the efficiency and kinetics depend on the
copper mineralogy. The most efficient minerals are supergene minerals such as chalcocite, Cu2S
and covellite, CuS. The main copper mineral chalcopyrite (CuFeS2) is not leached very
efficiently, which is why the dominant copper-producing technology remains flotation, followed
by smelting and refining. The leaching of CuFeS2 follows the two stages of being dissolved and
then further oxidized, with Cu2+ ions being left in solution.
Chalcopyrite leaching:
Reaction-1:
CuFeS2+4Fe3+ Cu2++5Fe2++2S0 Spontaneous
Reaction-2:
4Fe2++O2+4H+ 4Fe3++2H2O (Iron oxidizers)
Reaction-3:
2S0+3O2+2H2O 2SO42-+4H+ (Sulfur oxidizers)
Net reaction:
CuFeS2+4O2 Cu2++Fe2++2SO42-
In general, sulfides are first oxidized to elemental sulfur, whereas disulfides are oxidized
to give thiosulfate, and the processes above can be applied to other sulfidic ores. Bioleaching of
non-sulfidic ores such as pitchblende also uses ferric iron as an oxidant (e.g., UO2 + 2 Fe3+ ==>
UO22+ + 2 Fe2+).
In this case, the sole purpose of the bacterial step is the regeneration of Fe3+.
Sulfidic iron ores can be added to speed up the process and provide a source of iron. Bioleaching
of non-sulfidic ores by layering of waste sulfides and elemental sulfur, colonized by
Acidithiobacillus spp., has been accomplished, which provides a strategy for accelerated leaching
of materials that do not contain sulfide minerals.
Further processing
The dissolved copper (Cu2+) ions are removed from the solution by ligand exchange
solvent extraction, which leaves other ions in the solution. The copper is removed by bonding to
a ligand, which is a large molecule consisting of a number of smaller groups, each possessing
a lone electron pair. The ligand-copper complex is extracted from the solution using
an organic solvent such as kerosene:
Cu2+ (aq) + 2LH (organic) → CuL2 (organic) + 2H+ (aq)
The ligand donates electrons to the copper, producing a complex - a central
metal atom (copper) bonded to the ligand. Because this complex has no charge, it is no longer
attracted to polar water molecules and dissolves in the kerosene, which is then easily separated
from the solution. Because the initial reaction is reversible, it is determined by pH. Adding
concentrated acid reverses the equation, and the copper ions go back into an aqueous solution.
Then the copper is passed through an electro-winning process to increase its purity: An
electric current is passed through the resulting solution of copper ions. Because copper ions have
a 2+ charge, they are attracted to the negative cathodes and collect there.
The copper can also be concentrated and separated by displacing the copper with Fe from scrap
iron:
Cu2+ (aq) + Fe(s) → Cu(s) + Fe2+ (aq)
The electrons lost by the iron are taken up by the copper. Copper is the oxidizing agent (it
accepts electrons), and iron is the reducing agent (it loses electrons). Traces of precious metals
such as gold may be left in the original solution. Treating the mixture with sodium cyanide in the
presence of free oxygen dissolves the gold. The gold is removed from the solution
by adsorbing (taking it up on the surface) to charcoal.
Bioleaching with fungi:

Several species of fungi can be used for bioleaching. Fungi can be grown on many
different substrates, such as electronic scrap, catalytic converters, and fly ash from municipal
waste incineration. Experiments have shown that two fungal strains (Aspergillus niger,
Penicillium simplicissimum) were able to mobilize Cu and Sn by 65%, and Al, Ni, Pb, and Zn by
more than 95%. Aspergillus niger can produce some organic acids such as citric acid. This form
of leaching does not rely on microbial oxidation of metal but rather uses microbial metabolism as
source of acids that directly dissolve the metal.
Compared with other extraction techniques:
Extractions involve many expensive steps such as roasting and smelting, which require
sufficient concentrations of elements in ores and are environmentally unfriendly. Low
concentrations are not a problem for bacteria because they simply ignore the waste that
surrounds the metals, attaining extraction yields of over 90% in some cases.
These microorganisms actually gain energy by breaking down minerals into their constituent
elements. The company simply collects the ions out of the solution after the bacteria have
finished. There is a limited amount of ores.
Some advantages associated with bioleaching:

• Economical: bioleaching is in general simpler and, therefore, cheaper to operate and maintain
than traditional processes, since fewer specialists are needed to operate complex chemical plants.
• Environmental: The process is more environmentally friendly than traditional extraction
methods. For the company this can translate into profit, since the necessary limiting of sulfur
dioxide emissions during smelting is expensive. Less landscape damage occurs, since the
bacteria involved grow naturally, and the mine and surrounding area can be left relatively
untouched. As the bacteria breed in the conditions of the mine, they are easily cultivated
and recycled.
• Ore concentration: Bioleaching can extract metals from ores that are too poor for other
technologies. It can be used to partially replace the extensive crushing and grinding that
translates to prohibitive cost and energy consumption in a conventional process.
Some disadvantages associated with bioleaching:

• Economical: The bacterial leaching process is very slow compared to smelting. This brings in
less profit as well as introducing a significant delay in cash flow for new plants.
• Environmental: Toxic chemicals are sometimes produced in the process. Sulfuric acid and
H+ ions that have been formed can leak into the ground and surface water turning it acidic,
causing environmental damage. Heavy ions such as iron, zinc, and arsenic leak during acid mine
drainage. When the pH of this solution rises, as a result of dilution by fresh water, these ions
precipitate, forming "Yellow Boy" pollution. For these reasons, a setup of bioleaching must be
carefully planned, since the process can lead to a biosafety failure.

Leaching - Iron & Sulfur

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IRON AND SULFUR IN MICROBIAL LEACHING

The most commonly used microorganisms for bioleaching are Thiobacillus

Models of Leaching Mechanisms:

1. Direct bacterial leaching: Microorganisms can oxidize metal sulfides by a “direct”

2FeS2 + 7O2 + 2H2O 2FeSO4 + 2H2SO4

2S° + 3O2 + 2H2O 2H2SO4

Oxidation of ferrus (Fe2+) to ferric (Fe3+) by T. ferrooxidans at low pH is given below:

4FeSO4 + 2H2SO4 + O2 2Fe2(SO4)3 + 2H2O

Main factors affecting bioleaching:

Pyrite leaching (FeS2):

Bioleaching with fungi:

Some advantages associated with bioleaching:

Some disadvantages associated with bioleaching:

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