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RECENT TRENDS IN THE BIOLEACHING OF SULFIDIC MINERALS

BY

AKINTOLA MICHAEL OLUWADAMILARE

18/56EF027

A SEMINAR REPORT SUBMITTED TO THE DEPARTMENT OF

INDUSTRIAL CHEMISTRY, FACULTY OF PHYSICAL SCIENCES,

UNIVERSITY OF ILORIN, ILORIN, KWARA STATE, NIGERIA.

IN PARTIAL FULFILMENT OF THE REQUIREMENT FOR THE

AWARD OF BACHELOR OF SCIENCE DEGREE

(B. Sc. HONS) IN INDUSTRIAL CHEMISTRY

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CERTIFICATION

This is to certify that this seminar report has been approved and certified as meeting part

of the requirement for the award of Bachelor of Science Degree (B.Sc. Hons) in the Department

of Industrial Chemistry, Faculty of Physical Sciences, University of Ilorin, Ilorin, Kwara State,

Nigeria.

PROF F.A ADEKOLA DATE

(SEMINAR SUPERVISOR)

Dr. H.K OKORO DATE

(Ag. HEAD OF DEPARTMENT)

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DEDICATION

I dedicate this seminar report first and foremost to Almighty God who has been there

right from the beginning to this very point. I want to specially dedicate this seminar report to my

ever supportive and lovely family, for their relentless support and compassion towards me.

Furthermore, I want to dedicate this seminar report to Professor F.A Adekola for his

continual impact of knowledge. To God be the glory.

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ACKNOWLEDGEMENT

I want to thank the Almighty God, for giving me the wisdom, knowledge, understanding,

strength, support, for the guidance in helping me surpass all the trials that I encountered and for

giving me the determination to pursue my work and to make the completion of this work

possible. I return all praises and adoration to Him.

Foremost, I would like to express my deepest and sincere gratitude to my seminar

supervisor, Professor F.A Adekola, for his patience, sincerity, support, empathy, encouragement

and guidance throughout my work. May God bless you and your family and I want to say I am

extremely grateful.

I also acknowledge and appreciate all my lecturers for their continual impact of

knowledge. Also, the non-academic staff for their efforts during the course of my studies in this

great citadel of learning. May God bless you all.

To my ever loving, caring and supportive parent Mrs Akintola; I want to express my

deepest and sincere gratitude for her relentless moral, financial, emotional, physical, spiritual and

educational support and compassion towards me during the course of my studies. I want to also

say a very big thanks to my dearest siblings, for their love and support. My parent and siblings

are my backbone and I pray God preserve each and every one of them with sound health.

Lastly, I want to appreciate my friends turned family, for their support and love and for

also looking out for me. God bless you all.

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TABLE OF CONTENTS
TITLE PAGE………………………………………………………….. i

CERTIFICATION…………………………………………………….. ii

DEDICATION………………………………………………………… iii

ACKNOWLEDGEMENT…………………………………………….. iv

CHAPTER ONE : INTRODUCTION

1.0 Introduction…………………………………………………… 1-3

1.1 Bioleaching Techniques……………………………………… 4-8

1.2 Mechanism of Bioleaching…………………………………… 9-11

1.3 Pathways of Bioleaching…………………………………….. 12-14

1.4 Factors affecting Bioleaching…………………………………. 15-16

CHAPTER TWO : BIOLEACHING OF SOME COMMON MINERALS

2.1 Bioleaching of copper………………………………………. 17-19

2.2 Bioleaching of cobalt………………………………………… 19

2.3 Bioleaching of Uranium……………………………………… 20

2.4 Bioleaching of Nickel………………………………………... 21-22

2.5 Bioleaching of Zinc………………………………………….. 22

CHAPTER THREE : RECENT TRENDS IN BIOLEACHING

3.1 Pre-mine planning stage: In-situ consideration……………… 23

3.2 Solvents Extraction and Electrowinning…………………….. 24

3.3 Use of Bio-surfactants……………………………………….. 25

3.4 Bioleaching of Electronic Waste…………………………….. 26

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3.5 Pre-treatment of Ore Bodies………………………………… 27

CHAPTER FOUR: SUMMARY AND CONCLUSION

4.1 Summary…………………………………………………….. 28

4.2 Conclusion…………………………………………………... 28

REFERENCES

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CHAPTER ONE
1.0 INTRODUCTION
The technique of bioleaching involves employing microorganisms to recover
metal from ore containing sulfides and/or iron. This particular bio
hydrometallurgical process converts insoluble materials into soluble forms by
the metabolism of microbes or the production of their byproducts, which can
subsequently be collected. Throughout the Bronze and Iron Ages, the
extraction of metal has been a significant sector of the global economy. World
population growth and the development of various countries have boosted
demand for all natural resources, including metals. As technologies advance,
demand for various mineral products has been rising quickly. This finally
results in a decrease in the amount of high-grade ore reserves. As a result,
metal extraction from low-grade ores as well as mining and industrial wastes
has received increased attention. Hydrometallurgical and pyrometallurgical
procedures are advantageous for high-grade ores; however, because to high
process and energy costs, these techniques only recover a small amount of
metal from low-grade ores. These mining methods also seriously pollute the
air, water, and land. By using microorganisms to extract metal from minerals as
well as iron and sulfide ores, biohydrometallurgy may be more
environmentally friendly (fig 1.1) [1] .A cutting-edge method for removing
different metals from their ores is bacterial leaching. Conventional extraction
techniques like roasting and smelting demand a high concentration of elements
in ores and are particularly energy-intensive. Low concentrations are necessary
for bacterial leaching, which also uses little energy. Even though the procedure
results in extraction yields of more than 85% to 90%, it is environmentally
favorable [2]
Due to an increase in global demand for copper, the mining industry
must progressively treat low-grade ores, overburden, and trash from present-
day mining activities. Copper must be economically extracted from low-grade
ores using low-cost processing techniques such in situ, dump, and heap
leaching. An emerging process called bacterially-assisted heap leaching of low-
grade copper sulfides has been successfully used to extract copper from
secondary sulfide minerals like chalcocite at a number of facilities across the
world [3]
Metal sulfide leaching by bacteria has significantly increased over the past few
years. As a result of biotechnology, the use of microorganisms to recover

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heavy metals is now a well-established technique. The term "bioleaching"
refers to the biological oxidation and complexation processes utilized to
liberate metal cations from difficult ores. The main metals that can be
processed using this technology include copper, cobalt, nickel, zinc, and
uranium. In the case of uranium, they are either recovered from oxides or from
sulfides that are insoluble. However, before cyanidation treatment is employed
to recover gold and silver from the ore containing the precious metals, the
activity of leaching bacteria is simply used to remove interfering metal
sulfides. This is due to the fact that the bioleached metals, which are frequently
iron and arsenic, are oxidized. The term "bio oxidation" should be used instead
because the bioleached metals, which are frequently iron and arsenic, are
oxidized in this context [4]
The mineral industry's use of microbial processes, known as
biohydrometallurgy, predates knowledge of the function of microorganisms in
metal extraction, also known as bioleaching. One can trace the recovery of
copper from mine streams to the fifteenth or sixteenth century [5].
Leaching microorganisms have an increasingly complicated biology.
Many new species of leaching bacteria have been described and existing
species have undergone reclassification as a result of growing data on 16S
rDNA gene sequences. Also, whereas mesophilic bacteria were traditionally
the only relevant bacteria, (new) genera of moderately and extremely
thermophilic bacteria have recently gained popularity. Extremely acidophilic
bacteria that can oxidize either inorganic sulfur compounds or iron(II) ions are
the most common microorganisms that can dissolve metal sulfides. The
diversity of the microbial flora in these biotopes was predicted to be incredibly
low due to the limited types of substrates present in mining sites. Yet today we
are aware that mining biotopes exhibit a high level of microbial diversity [4]
Among readily available mining methods, bioleaching occupies a
significant position. Currently, bioleaching is a real moderate choice for
treating specific mineral ores rather than a hopeful breakthrough. Many
underdeveloped countries are the locations of the current bioleaching efforts.
Few poor countries have large mineral reserves, which illustrates this situation,
and bioleaching's advantages, which make it especially practical for
underdeveloped countries due to its simplicity and low cost [6]

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Fig 1.1 Flow sheet of bioleaching of low grade sulfide ores [1]

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1.1 BIOLEACHING TECHNIQUES
Leaching is an effective and simple technology for metals extraction, but
its economics and effectiveness depend on microbial activity and mineralogical
and chemical composition of ores. Leaching techniques can be classified into
many different areas industrially due to several methods.

1.1.1 DUMP BIOLEACHING


Similar to heap leaching, dump leaching involves taking ore straight
from the mine and stacking it on the leach pad without first crushing it; in the
case of gold and silver, however, the dump is irrigated with a weak cyanide
solution that percolates through the ore to dissolve the metals [7]. This method
is the oldest. To encourage microbial development, uncrushed boulders are
piled up to a height of 25 to 400 meters, 100 to 300 meters in breadth, and 100
to 2000 meters in length. These dumps often contain copper concentrations of
0.1-0.5%, which is exceedingly low and difficult to recover using traditional
techniques. The size of the dump varies greatly, and the ore content might be
between hundreds and thousands of tons. Dump is intermittently or
continuously sprayed from the top. Depending on the ore, the lixiviant may be
ordinary water, acidified water, or an acidic ferric sulfate solution acquired
from another leaching operation with similar mining characteristics [1]
Dump bioleaching is a low-cost, naturally occurring microbe-assisted process
that occurs in an environment with access to the atmosphere. Dump leaching is
especially useful when cheaper processing of low-value mineral ores cannot be
accomplished using existing methods. The main mechanism for oxidizing
sulfides is Fe(III), which is (re)generated by the activity of iron-oxidizing
bacteria. Sulfide is oxidized in an acidic environment to form intermediate
sulfur species such sulfate and sulfate, which reduces Fe(III) to Fe (II).
Reoxidation of iron dioxide (Fe(II)) and subsequent oxidation of intermediate
sulfur compounds by oxygen take place slowly in the absence of
microorganisms. Nevertheless, acidophiles, which are autotrophic and can use
iron and sulfur as electron donors while obtaining energy from oxidation, can
accelerate this process [8].The dump bioleaching process is represented in (fig
1.2)

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Fig 1.2. Dump bioleaching process [6]

1.1.2 HEAP BIOLEACHING


Without the need for grinding, heap bioleaching uses microorganisms to
accelerate the decomposition of ore. On top of the liner, the crushed ore is
piled, and the microbial solution permeates the heap from top to bottom.
Valuable metals in sulfide are oxidized by Fe3+, which causes them to enter
the liquid phase as ions. These ions are subsequently recovered in the
subsequent procedure. The main job of microorganisms is to regenerate Fe3+.
With its straightforward criteria, low cost, and suitability for treating low-grade
ore, this technique has many advantages. It was employed in commercial
manufacturing. [9]. Although environmental conditions primarily favor the
development of acidophilic Acidithiobacilli and Leptospirilli, the microbial
population operating in natural leaching processes lacks the characteristics of a
pure culture. Aeration in these procedures might be passive, where air is taken
into the reactor as a result of liquid flow, or active, where air is pushed into the
heap through pipe that has been put towards the bottom. Leach solutions that
contain metal are regularly collected and sent for metal recovery after being
drained from the heap [10]. Heap leaching is more concerned with chemical,
engineering, and biological factors than dump bioleaching. This method is used
for fine-grinded ores that cannot be concentrated by floatation to improve the
lixiviant-mineral interaction and make the base impermeable to prevent

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lixiviant loss and pollution of water bodies [1]. Heap leaching has a low capital
cost for the most part. Precise test work is essential for analyzing and
maintaining successful tasks. Many work-related issues may arise. Externally,
heap leaching appears to be a simple procedure; however, insufficient
preliminary testing has resulted in outrageous issues. A significant amount of
improvement and operation is almost certainly associated with extensive and
flourishing activities. Heap bioleaching microbiology is not well understood.
Numerous factors influence microbiology, including the presence of acid, the
type and amount of sulfide minerals, the availability of oxygen and
supplements, and the temperature [6].Fig1.3 depicts the heap bioleaching
process.

Fig 1.3. Heap bioleaching process. [6]

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1.1.3 IN-SITU BIOLEACHING
In situ leaching (ISL), also known as solution mining or in situ recovery
(ISR), entails leaving the ore in place and recovering the minerals from it by
dissolving it and pumping the pregnant solution to the surface, where the
minerals can be recovered [11]. The efficiency of the interaction between the
leaching solution and the porous media is critical to the success of in-situ
recovery. Instead of using excavation or galleries, in-situ recovery involves
using a leaching solution to extract an ore body where it already is (fig 1.4). It
has been used for more than a century to extract numerous commodities, such
as copper, and in recent years, it has emerged as one of the primary uranium
extraction techniques. Leaching is frequently done in tanks or heaps on the
surface, but it's more intriguing to do it in-situ when the geological conditions
are right. Even though in-situ recovery is still most frequently used to mine
uranium, it has recently attracted interest for a variety of other metals,
including gold, and may lead to a comparable technological advance as it did
for uranium at the beginning of the twenty-first century [12]. A unique method
of extracting metal from running-of-mine ores and unprofitable subterranean
metal deposits is microbial in situ leaching. The potential for this technique to
treat low-grade ore is great. By using a few different techniques for applying
the leach liquor and recovering the pregnant solution, the metal body is drained
in place. Leach liquor may be poured under pressure into bore gaps or allowed
to seep through the surface. It's possible to recover the pregnant solution from
neighboring crevices under the metal body. The porousness of the metal body
is the main aspect influencing the adoption of this tactic. Setting up the
possibility of in-situ filtering with relation to the availability and porousness of
rock [6]. In-Situ leaching often takes place in closed mines. Under pressure,
ores from unmined ore or mining waste inside tunnels trickle or wash out,
drowning galleries. In the ruptured orebody, lixiviant containing
microorganisms is injected into boreholes. Leachate is gathered in deeper
shafts and galleries and pumped into the processing plant [1].

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Fig 1.4 In-situ bioleaching process [6]

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1.2 MECHANISM OF BIOLEACHING
The primary basis for the bioleaching of metal sulfide is the natural
specialization of bacteria that obtain their life-sustaining energy from the
oxidation of ferrous iron and RISCs in an acidic environment.
By moving electrons from the sulfur or/and iron portion of the mineral to the
final electron acceptor oxygen, metal sulfide is bio-oxidized [1]
The mechanisms of bio-leaching is divided into three based on electron
transfer.

1.2.1 DIRECT OR CONTACT MECHANISM


Via a direct method whereby electrons are acquired directly from the
reduced minerals, microorganisms can oxidize metal sulfides. In this situation,
a tight contact is required in order to bind the cells to the mineral surface. In a
matter of minutes or hours, cells adsorb to suspended mineral particles [13]. In
contact leaching, there is a direct interaction between the bacterial cell and the
surface of the mineral sulfide and the sulfate oxidation takes place through
several enzyme catalyzed steps [14]. The direct oxidation of pyrite is given as
follows:

4FeS2 + 14O2 + 4H2O → 4FeSO4 + 4H2SO4…………………………(1)

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

The reaction can be summarized as follows:

4FeS2 + 15O2 + 2H2O→ 2Fe2(SO4)3 + 2H2SO4………………………(3)

Direct oxidation of non-iron sulfide mineral is described as follows:

MS + 2O2 → MSO4…………………………..……………………..(4)

However, the specific mechanism by which microorganisms break the metal


sulfide link in metal sulfides during contact leaching is unknown due to a
lack of experimental data [6]

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1.2.2 INDIRECT OR NON-CONTACT MECHANISM
Physical contact between the solids and the microorganisms is not
necessary in the indirect bioleaching system. Using microscopic organisms
like bacteria and fungus to dissolve metals from intractable materials
requires one of three methods:
• acid secretion, both organic and inorganic
• Redox reactions
• Emission of sophisticated agents to facilitate ligand formation [6]
In indirect mechanism, the ferric (III) ion, which is produced by
microbial oxidation of ferrous iron found in minerals, mediates the oxidation
of reduced metals. Ferrous iron can be reduced to ferric iron, which can then
be oxidized by microorganisms. Ferric iron acts as an oxidant and can
oxidize metal sulfides. Iron serves as an electron carrier in this instance. It
was suggested that iron can oxidize without any direct physical touch [15] .
This ferric ion dissolves metal sulfide and functions as a lixiviant in acidic
solutions [1]

MS + Fe2(SO4) → MSO4 + 2FeSO4 +S0……..……………………..(5)

Sulfur-oxidizing bacteria (At. thiooxidans) simultaneously oxidize the


generated sulfur to H2SO4.

2S0+ 3O2 + 2H2O → 2H2SO4……………………………………..(6)

Microorganisms' production of organic and inorganic acids facilitates


indirect leaching. Two steps of such bioleaching take place: Prior to
bioleaching, the cells are first cultivated in a medium with ideal cultural
conditions for synthesizing active metabolites. Second, the culture-free
medium is used as a mineral-leaching agent when the conditions are
right [16].

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1.2.3 COOPERATIVE BIOLEACHING
This mechanism combines direct and indirect processes that
influence metal dissolution simultaneously. Planktonic cells' need for energy
is met by specific molecules released by the connected cells. The term
"cooperative bioleaching" refers to the dissolution of sulfur intermediates,
sulfur colloids, and other minerals by planktonic cells. These terms are
useful for describing the physical state of the cells that perform bioleaching.
They do not, however, reflect an understanding of the original chemical
mechanism of metal sulfide dissolution. Bioleaching is traditionally
established through the collaboration of chemical and biological oxidation.
The ferrous and ferric iron cycles must be given special consideration [1]

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1.3 PATHWAYS OF BIOLEACHING
Metal sulfide dissolution is controlled by only two different reaction
mechanisms: the thiosulfate and polysulfide pathways. In most cases,
dissolution is accomplished through a combination of proton attack and
oxidation processes. The mineral species determine the reaction pathway. [4].
The crystal structure, such as monosulfide and disulfide, does not regulate
the pathway, but the appropriate principle is metal sulfide reaction with
protons. The electronic configuration of metal sulfide controls this
property [1]

1.3.1 THIOSULPHATE PATHWAYS


Metal sulfides, such as pyrite, tungstenite, and molybdenite,
contain a pair of sulfur atoms that form nonbonding orbitals, whereas the
valence bands are entirely derived from metal atoms and are thus completely
oxidized via ferric iron. Pyrite oxidation has been extensively researched,
and more information can be found elsewhere. Pyrites are oxidized solely by
ferric iron. When ferric attacks pyrite, the sulfur component is oxidized into
soluble sulfur intermediates.
The bond between metal and sulfur does not cleave in such metal sulfides
until six successive one-electron oxidations occur and thiosulfate is
liberated. As a result, this pathway is known as the thiosulfate pathway [1,4].
The thiosulphate pathway can be described as follows:

1
2Fe2+ + 2 O2 +2H+ → 2Fe3+ + H2O.………………….(7)

FeS2 +6Fe3+ +3H2O → S2O32- +7Fe2+ +6H+………….(8)

S2O32- +8Fe3++ 5H2O → 2SO42- + 8Fe2+ +10H+…….(9)

The thiosulphate system is also called the acid insoluble metal sulfides based
on their solvency in acids.

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1.3.2 POLYSULPHIDE PATHWAY
In contrast to pyrite oxidation, the metal-sulfur bond in acid-
soluble metal sulfide can be broken prior to H 2SO4 oxidation. Protons can
dissolve metal sulfides such as orpiment, realgar, chalcopyrite, troilite,
pyrrhotite, hauerite, galena, and sphalerite. Sulfide metals are dissolved by
the collective action of ferric and proton, i.e., proton binding by the sulfide
moiety via valence band electrons. This proton attack breaks the bond
between the metal and the sulfur moiety, and after binding two protons,
hydrogen sulfide is liberated. In the presence of ferric, however, sulfur
oxidizes in a single electron step via proton attack. The sulfur moiety of
metal sulfide is oxidized to elemental sulfur in acidic conditions. Several
reactions have been identified during the dissolution of chalcopyrite, galena,
and pyrrhotite that essentially describe the formation of elemental sulfur via
the polysulfide pathway. The first sulfur compound formed is a sulfide
cation (H2S+) that can spontaneously dimerize to free disulfite (H 2S2) and
then be oxidized to elemental sulfur by polysulfides and polysulfide radicals.
As a result, acid-soluble metal sulfide oxidation is known as the polysulfide
mechanism [1,4].
This can be explained as follows:

MS + Fe3+ + H+ → M2+ + 0.5H2Sn + Fe2+………………….(10)

0.5 H2Sn + Fe3+ →0.125S8 + Fe2+ + H+…………………….(11)

0.125S8 + 1.5O2 +H2O → SO42- + 2H+……………………...(12)

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Fig 1.5. Schematic diagram of the thiosulfate and polysulfide
mechanisms [4]

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1.4 FACTORS AFFECTING BIOLEACHING
Since bioleaching involves microorganisms, biological, environmental,
and physicochemical factors all have an impact on metal extraction yield.
The efficiency of bioleaching is largely determined by the competence of
microorganisms as well as the mineralogical and chemical composition of
ores [1].Below are few variables upon which bioleaching takes place.

1.4.1 pH
The right pH change is a necessary condition for the development of
leaching microscopic organisms and is conclusive for metal solubilization. A
pH range of 2.0-2.5 is optimal for bacterial oxidation of ferrous iron and
sulfide. A. ferrooxidans will be severely restricted at pH levels below 2.0;
however, A. ferrooxidans may be adapted to try lower pH levels through the
expansion of sulfuric acid [6]

1.4.2 Temperature
Microorganisms are classified as mesophiles (30-40 C), moderate
thermophiles (around 50 C), and extreme thermophiles (above 65 C) based
on their optimal growth temperature. Cells become inactive at low
temperatures and die at high temperatures. The bio-oxidation of sulfide
minerals is an exothermic process that generates significant heat in the
stirred tank reactor and heap. The ideal temperature for A. ferrooxidans to
oxidize ferrous and sulfide is 28-30 degrees Celsius. Metal extraction is
reduced at lower temperatures, but at 4 C, two competing factors affect the
process: first, the reaction rate enhancement that is usually carried out by
raising the temperature, and second, the reduction of microbial activity with
temperature rise and the upper tolerance limit of the microorganisms [1].

1.4.3 Carbondioxide and oxygen


A sufficient supply of oxygen is required for the development and
rapid movement of the leaching microscopic organisms. This can be
accomplished in the lab through air circulation, mixing, and shaking. On a
more specialized scale, adequate oxygen supply may pose a few challenges,
particularly due to heap or dump leaching. Although carbon dioxide is the

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primary carbon source required, there is no requirement for CO 2
expansion [14]

1.4.4 Heavy Metals


Metal sulfide leaching is followed by an increase in metal fixation in
the leachate. Leaching microbes, particularly Thiobacilli, have a high
resistance to heavy metals, and different strains may even tolerate different
metal concentrations. Diverse strains of a few species may exhibit
completely unusual sensitivities to heavy metals. Individual strains can
frequently be changed to higher metal convergences or to specific substrates
by increasing the metal concentration [6]

1.4.5 Nutrients
Microorganisms require nutrients for cellular metabolism, cell
division, and metabolite biosynthesis. Most microorganisms in bioleaching
are chemolithotrophic and require inorganic compounds. Mineral nutrients
are typically obtained from the material being leached. Sulfur and iron
compounds, as well as salts such as ammonium, magnesium, and phosphate,
must be added to the media for optimal microbial growth. Furthermore, the
nutrient supplement must be at the optimal concentration; too low or too
high concentrations may inhibit microbial growth. In the case of
heterotrophs, sucrose was discovered to be the best carbon source for A.
niger citric acid production, followed by glucose and fructose [1]

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CHAPTER TWO
BIOLEACHING OF SOME COMMON MINERALS

2.1 Bio-leaching of Copper

Natural bioleaching has been occurring for almost as long as human


history, but it has only been recognized in the last few decades that bioleaching is
the cause of some mining wastes' acid generation and that this bacterial activity can
be utilized to liberate some metals. The usage of the copper bioleaching reaction
has been tapped into and leveraged to create effective strategies for recovering
copper from copper-containing fluids. Copper heap leaching has been used for
many years, primarily with oxide ores. It's likely that bacteria assisted some of
these oxide activities, although this was never thoroughly investigated [17]Because
of copper bioleaching's benefits, such as its affordability and environmental
friendliness, valuable metals are frequently extracted from waste or low-grade
ores. Nowadays, more than 30% of the cathode copper produced worldwide comes
from copper bioleaching. Contrary to the chemical acid/ammonia leaching method
used in copper oxide and ammonia leaching, coupled and complex circumstances
have an impact on bioleaching with bacteria. Researchers have the possibility to
interfere in and intensify the bioleaching process of copper sulfide heaps since it is
carried out under air exposure and involves numerous industrial processes, multi-
phase media, and multiphysics. [18]The most abundant copper mineral,
chalcopyrite, is extremely resistant to mesophilic biooxidation and is not readily
amenable to it. Chalcopyrite metals are being attempted to be bioleached, with a
focus on using thermophilic living forms. The microorganism that is most
frequently thought of is A. ferrooxidans. In several bioreactor forms,
Leptospirillum ferriphilum frequently outperforms A. ferrooxidans. It has been
shown that L. ferrooxidans and A. thiooxidans worked in highly acidic conditions
in copper bioleach conditions. At increasing temperatures, both extreme and
moderate thermophiles swell enormously (40-80 0C). In a few bioreactor
operations, Acidithiobacillus caldus is the actual sulfur oxidizer. Sulfolobus
species eventually require temperatures greater than 60 0C. Though unpredictable,
microbial consortia in landfills and bioreactors must be properly evaluated.
Chalcopyrite surfaces with sulfur and iron-containing materials undergo surface
passivation, which slows down disintegration rates. To improve biooxidation

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energy, effective sulfur reoxidation and the removal of iron oxidized products and
jarosites are essential. The copper metals' mineralogy also has an effect on
biooxidation. It is important to understand the connection between the
mineralogical solution, as well as reaction and product. Another potential
possibility is processes involving microbiological organisms, but correct leaching
kinetics that affect the activity of thermophiles and mesophiles must be
established [6].

Table 1. Dissociation and oxidation reactions of some copper containing


minerals [3]

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2.2 Bio-leaching of Cobalt

Magnetic materials and high-temperature alloys are only two examples of


the many industrial products that use cobalt, which is a very significant metal. A
combination of factors, including the depletion or limitation of natural resources,
inadequate reclamation or recovery, geopolitical concerns, and its expanding
significance in a number of emerging electronic and energy technologies, are
driving up demand for cobalt on a global scale. The cobalt supply chain must be
enhanced as a result, and this can be done by improving recovery from wastes,
natural resources, and other materials. In addition to lessening the environmental
impact of conventional mining methods, bioprocessing using microbial systems is
seen as a potentially helpful solution to this issue. In crustal conditions, more than
sixty different cobalt-bearing minerals are found, and among them, Fe, Cu, and Ni
are the main coexisting elements with Cobalt. Among them, laterite ores currently
supply 20% of the Cobalt in the world. Cobalt-containing sulfide ores are also
significant minerals; for instance, the sulfide ores of Bou Azzer, Morocco, supply
8% of the world's cobalt. [19]Cobalt sulfide dissolves as a result of microbial
action. Using A. ferrooxidans, A. thiooxidans, L. ferrooxidans, and thermophilic
acidophiles, cobalt sulfide (CoS) and cobaltite (CoAsS) can be biodissolved. The
first commercial attempt at cobalt bioleaching used cobalt-containing pyrite in
blended reactors. The cobalt is mostly found as pyrite, but there are also trace
amounts in pentlandite [(Ni, Fe, Co) 9S8]-bravoite [(Fe, Ni, Co)S2] and siegenite
[(Co, Ni)3S4]. Cobalt separation and arrival were shown to be connected to pyrite
deterioration. Recovery of the pyrite, bioleaching, iron ejection and solvent
extraction, cobalt generation by electrowinning, as well as the treatment of effluent
and waste transfer, were significant advancements in the plant method [6].

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2.3 Bio-leaching of Uranium

Uranium is a significant natural resource that is employed in the


production of nuclear energy, as a component of anti-corrosive alloys, as a raw
material for the production of uranium oxide (U 3O8), and as a coloring agent for
glass and porcelain. Around 100 million tons of uranium-bearing ore are thought to
exist in South Korea's Daejeon and Okcheon areas. Since the 1960s, uranium has
been extracted commercially from low-grade ores via a process called bioleaching.
The underground uranium mines in the Canadian Elliot Lake district, including the
Stanrock, Milliken, and Denison Mines, are home to the best-known in situ
leaching operations.The traditional method of extracting uranium uses strong acids
as leaching agents. This process frequently results in environmental issues, uses a
lot of energy, and calls for a complicated operational plant [20]. The bioleaching of
uranium can be done in situ, in a vat, a dump, a heap, or a tank. Metal mineralogy
and characteristics, pH, temperature, and microbial culture all affect uranium
bioleaching. Considerations for uranium bioleaching frequently employ enhanced,
pure strains of A. ferrooxidans that oxidize iron and sulfur, or mixed societies of A.
ferrooxidans and A. thiooxidans or A. ferrooxidans and L. ferrooxidans. A.
ferrooxidans or L. ferrooxidans are responsible for producing the oxidant as a
lixiviant in the previous biooxidation response, which pursues the indirect route [6].
Many studies show that bioleaching has the potential to be an economical and cost-
effective way to extract uranium from a variety of sources. The results indicate that
the most widely employed microorganisms for uranium bioleaching are
Acidithiobacillus ferrooxidans and Acidithiobacillus thiooxidans. The efficiency of
the process can be improved by optimizing variables including pH, temperature,
and nutrition [21,22].

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2.4 Bio-leaching of Nickel

Due to the world market for stainless steel, which uses 67% of primary nickel,
nickel demand is rising globally. Due to an increase in demand from China, the
stainless steel market is expanding at a rate of 5.7% per annum and might increase
to nearly 9% per annum. Up until 2006, prices rose sharply due to a disparity
between supply and demand; the more recent price decline in 2007 was caused by
a rise in global stockpiles. A renewed interest in resource exploration to find new
resources and the creation of innovative processing methods for ores with lower
grades or complicated compositions has been sparked by the rise in demand. As
laterite production is expected to greatly outpace that of sulfides in the future,
present and potential laterite projects frequently take center stage when the nickel
industry is reviewed. However, sulfides make up around 30% of the 130 Mt of
contained nickel in estimated land-based nickel deposits. It should be noted that the
use of hydrometallurgy and bioleaching has promise for lowering the capital and
operational expenses for both sulfide and laterite operations [23]. The nickel's
bioheap draining was regarded as the most economical option. A. caldus,
Sulfobacillus spp., and Acidimicrobium were used in a mixed culture to bioleach
nickel sulfide assemblies at higher temperatures up to 55 0C. With A. ferrooxidans
and another unnamed thermophile, a pentlandite focus was bioleached .Nickel
breakdown was greatly aided by the appended A. ferrooxidans, while ferrous
particles were oxidized by free bacterial cells. Significant outcomes of several
forms of investigative research on the bioleaching of pentlandite minerals are
included here:

Following an adjustment period of 18 weeks, ferrooxidans used to Ni-Cu-Fe


sulfide concentrates could separate about 55% nickel.

• In a bioreactor, selective bioleaching of pentlandite-chalcopyrite aggregates


produced a unique nickel extraction (55%).

• About 87% and 91% nickel recovery could be achieved from nickel-rich
pyrrhotite concentrates in close proximity to unadapted and modified strains of A.
ferrooxidans.

21
• After a month, a pentlandite-pyrrhotite-chalcopyrite was bioleached, yielding a
60% nickel extraction.

• Thermophiles, such as Acidimicrobium, Sulfobacillus, and A. caldus, have been


found to be more effective at extracting nickel at temperatures between 50 and 80 0
C. [6]

2.5 Bio-leaching of Zinc

The annual production of zinc is around 7 million tons, and since 2005,
demand has grown dramatically. The zinc industry switched from conventional
pyrometallurgy to hydrometallurgy over the past 25–30 years. Currently, roast-
leach-electrowinning (RLE) and pressure hydrometallurgy are used to extract zinc
from sphalerite, which accounts for roughly 90% of the world's total zinc
production [24]. One of the most significant sources of Zn-bearing sulfide minerals
is sphalerite (ZnS), from which Zn is extracted. Currently, traditional processes
like roast-leach-electrowinning and pressure hydrometallurgy are used to create
90% of the world's total Zn from sphalerite. The particle size, pulp density, and
temperature combinations that produced the maximum Zn extraction from
sphalerite by bioleaching were 38-150 m, 4% wt/vol, and 33 °C, respectively. High
grade Zn-Pb bearing ore was the subject of an experiment utilizing a variety of
moderately thermophilic microorganisms. The results showed that a pulp density
of 50 (g/L) was used for 25 days to achieve the greatest zinc recovery, which was
98.5%. Bioleaching can be used to treat zinc sulfide ores in either a direct or
indirect manner. The sulfur-oxidizing bacteria (SOB) Acidithiobacillus
ferrooxidans and Acidithiobacillus thiooxidans catalyze the direct oxidation of
insoluble zinc sulfide to soluble zinc sulfate in the direct bioleaching mechanism.
Indirect bioleaching mostly uses a method based on iron, in which ferric ions are
created through the bio-oxidation of ferrous ions and act as an oxidizing agent to
aid Zn dissolution from its sulfide material [25]. Combining A. ferrooxidans and A.
thiooxidans results in a faster rate of zinc disintegration from zinc sulfide minerals

22
than either A. ferrooxidans or A. thiooxidans alone. Zinc disintegration benefits
from the addition of a suitable quantity of ferric iron; greater ferric concentrations
slow zinc disintegration because jarosite formation occurs [6].

CHAPTER THREE
3.0 RECENT TRENDS IN BIOLEACHING

In recent years, bioleaching has gained attention as a sustainable and


environmentally friendly alternative to traditional mineral extraction methods. This
seminar report will discuss the recent trends in bioleaching of sulfidic minerals,
including the use of new microorganisms, bioreactor designs, and emerging
technologies. The trends are discussed below.

3.1 Pre-mine planning stage: In-situ consideration

The caving method, such as the block caving method, used during underground
mining from porphyry copper deposits is comparable to open-pit mining in terms
of both production capacity and costs. As a result, it can be used for low-grade
ores, particularly once the practical and economical depth limit for open-pit mining
is reached. The orebody has been left in place by 25–30% using innovative block
caving techniques. During pre-mine planning phases, in situ bioleaching for the
abandoned ores to be used during block caving has not yet been addressed. When
developing large-scale mining operations, taking into account in situ bioleaching
processing can increase the value of mining technology and resource efficiency.
Block caving mining was used in the underground mine in Chuquicamata, Chile,
which was put into operation in 2018 and produce 350,000 t of copper yearly. As a
result, cave mining was predicted to leave behind 30% of the ore, meaning that the
abandoned ores still contained around 105,000 tons of copper annually. Moreover,
50,000 tons of copper recovery per year was said to be achieved by using a
conventional in situ post-bioleaching extraction for copper (50%) from dump or
stockpile bioleaching. Bioleaching is the greatest alternative method to utilize
concentrates that are difficult to process by conventional methods due to pollutant
chemicals like bismuth and arsenic and their unfavorable polymetallic structures or
high transportation costs [1].

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3.2 Solvent extraction and Electrowinning

Large US mining operations constructed flooded percolation leaching in vats,


especially at Chuquicamata (1915) and Potrerillos, throughout the early years of
this century. These advances were the basis for the leaching processes utilized in
Chile into the 1970s (1928). In both instances, direct electrowinning was used to
recover copper. Although the copper cathode wasn't always of consistent quality
and wouldn't meet today's standards, the procedure generated cathodes of
acceptable quality for the standards of the time. Copper recovery was ensured
through precipitation in additional vat operations built later, such as Mantos
Blancos (1961) and Sagasca (1972), using SO 2 in the first instance and scrap iron
in the second [26].The successive use of bioleaching and electrowinning to
selectively extract copper is proven in [27] concept of closed-loop recycling of
copper from PCBs. The challenge of the ever-growing environmental buildup of
electronic garbage, or "e-waste," is addressed in part by this strategy. The most
prevalent metal in e-waste, copper, which can account for up to 20% of the weight
of printed circuit boards, is the focus of this effort (PCBs). The acidophilic
bacterium Acidithiobacillus ferrooxidans was successfully employed in the first
step of bioleaching to extract various metals from PCBs at different pulp densities
(0.25–1.00% w/v). The method's second stage concentrated on electrowinning
copper out of the bioleachate. By using energy dispersive X-ray analysis and
inductively coupled plasma optical emission spectrometry, metallic copper foils
were created, and the results showed that 75.8% of the copper present in PCBs had
been recovered as a high quality, 99+% pure copper foil. This copper extraction
model offers a closed-loop recycling technique that exemplifies the use of
bioleaching in the circular economy. It combines electrowinning and bioleaching.
For the purpose of creating intricate printed circuit boards for the electronics
manufacturing sector, the copper foils have the potential to be recycled to create
new, high-value copper clad laminate.

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3.3 Use of Bio-surfactants

In order to meet rising demand for commercially significant metals, secondary


resources and low-grade ores are being sought after due to the increase in global
demand for these metals and the depletion of easily accessible ores. Innovative
biobased industry technologies, such microbial biosurfactants, could be used to
increase the sustainability of conventional hydrometallurgy processes. This study
studies the leaching of metals (especially Cu and Zn) from a variety of mine
tailings, metallurgical sludges, and automobile shredder residues using newly
developed microbial biosurfactants (acidic- and bolaform glycolipids). The best
results for Cu leaching were seen from a fayalite slag (27%) and a copper sulfide
mine tailing (53%), and acidic sophorolipids were often the most effective.
Subsequent analysis of the fayalite material that had been leached revealed that
leaching was occurring from small metallic Cu droplets in this material via a
corrosion-based process and/or from CuPb sulfides, which were selective against
the predominant Fe-silicate matrix [28]A study looked into the viability of using
alternate cycles of treatment with rhamnolipid biosurfactants and bioleaching with
a mixed bacterial culture of Acidithiobacillus thiooxidans and Acidithiobacillus
ferrooxidans to improve the removal of metal ions from mineral
waste/contaminated soils. 50% Zn and 19% Fe were removed solely by
bioleaching. 11% Fe and 25% Zn were eliminated when rhamnolipids were
utilized at low concentrations (0.4 mg/mL), whereas 19% Fe and 52% Zn were
removed at 1 mg/mL. Metal removal when adopting a cyclic treatment that
combines bioleaching and biosurfactants was up to 36% for Fe and 63%–70% for
Zn [29]. Metal extraction from bacteria that require iron for their metabolism is
already practiced on a large scale commercially. Today, research is concentrated
on bio-floatation, a method that has not yet been fully understood in which active
molecules can change the surface of minerals without the use of living microbes.
They could be biomolecules, metabolic products, or components of the cell.
Studying the interaction between a mineral surface and a specific molecule will be
the next goal after the proper bacteria have been reported and the bio-surfactants
have been extracted. Biofloatation can eventually be incorporated into

25
conventional procedures. These bioactive compounds can also naturally deteriorate
in the environment. To make these chemicals technologically and commercially
feasible, more research must be done on how they behave inside the process. [1].

3.4 Bioleaching of Electronic Waste( E-waste)

The amount of solid trash has drastically expanded along with industrialization and
the growth of society and economy. Electronic waste (E-waste), in particular, has
become the fastest-growing category of solid waste globally as a result of the
enormous number of abandoned electronic items. E-waste is a natural result of the
technology revolution, particularly at the period of rapid technological
advancement. E-waste covers a wide range of abandoned electronic devices, parts,
and accessories, including refrigerators, laptops, and cell phones. E-waste
production was expected to reach 50 million metric tonnes worldwide in 2018. The
majority of the thousands of distinct compounds found in e-waste are harmful,
including arsenic, brominated flame retardants, copper, lead, chromium, mercury,
and lead [30].Using mesophillic Acidithiobacillus thiooxidans, copper-rich
electronic waste material was bioleached. Three different techniques were used to
study the leaching behavior of copper: abiotic chemical leaching using inorganic
sulfuric acid, indirect leaching using sulfuric acid produced by bacteria, and direct
leaching using acidophilic bacteria. The output of bacterially produced sulfuric
acid employed for both indirect and direct leaching was 14.9 g/dm 3 and was
cultivated for 14 days at 300C in a medium containing 25 g/dm 3 of elemental sulfur
and basalt salts. For the leaching tests, this acid was diluted to obtain different pHs.
The variables evaluated included pulp density, solution pH, temperature, time, and
copper concentration in the trash. The findings showed that passivation and
galvanic coupling, both of which decreased the copper yield and caused slower
leaching, have an impact on copper dissolving. Higher yields and improved copper
selectivity were encouraged by increasing the acid content, copper concentration in
the waste, temperature, and length of the leaching process. The usage of pulp
density (10 g/dm3) had no impact on direct bioleaching due to the toxicity of e-
waste. Yet the partially oxidized sulfide compounds in the growing medium
encouraged copper surface passivation, resulting in decreased Cu recovery (60%)
compared to abiotic leaching (98%) [31].

26
3.5 Pre-treatment of Ore Bodies

Pretreatment methods have been explored as a means of improving the efficiency


of bioleaching by increasing the surface area and accessibility of the mineral to
microorganisms. One such method is microwave-assisted grinding, which has been
shown to increase the rate and extent of copper bioleaching. By generating grain
boundary fracture, microwave and ultrasonic treatment of ores can increase the
effectiveness of bioleaching. As a result of particle weakening and high exposure
to or release of valuable grains, this technique may have advantages in the
subsequent comminution stage of the recovery process, such as energy
conservation. This type of treatment improves metal recovery since the kinetics
and degree of bioleaching rely on how accessible the grain is to the lixiviant.
Because microwave treatment causes internal fissures in the zinc sulfide ores,
improved metal recovery has been recorded [1].

27
CHAPTER FOUR
SUMMARY AND CONCLUSION

4.1 SUMMARY

Bioleaching is a process that involves the use of microorganisms to extract metals


from sulfidic minerals. There are three main bioleaching techniques which are;
dump, heap and In-situ bioleaching. There are three ways bacteria interact with the
sulfide ore and they are; direct , indirect and cooperative mechanism. Cooperative
mechanism consists of both the direct and indirect mechanism. There are two
pathways of metal dissolution and they are; thiosulfate and polysulfide pathways.
The factors affecting or influencing bioleaching includes; pH, temperature,
carbondioxide and oxygen, heavy metals, nutrients, etc. The Recent trends in
bioleaching have focused on improving the efficiency and sustainability of the
process.

4.2 CONCLUSION

The Recent trends in bioleaching have focused on improving the efficiency and
sustainability of the process. One major trend is the In-situ consideration during
pre-mine planning stage in order to increase the value of mining technology and
resource efficiency. Another is the use of solvent extraction and electrowinning for
the extraction of metals like copper. The use of bio-surfactants is another trend in
bio-leaching in order to improve the removal of metals. Bioleaching of electronic
waste for the extraction of metals like; arsenic, chromium, copper ,lead, and
mercury is also discussed. Together with the pre-treatment of ore bodies in order to
improve the efficiency of bioleaching. Overall, the recent trends in bioleaching of
28
sulfidic minerals are focused on improving efficiency, sustainability, and
environmental impact.

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