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In the name of Allah, the designer, the creator and
the initiator
1
Title:
Investigation of Pre-leaching and particle size’s effects on
copper slag bioleaching
Malek-Ashtar University of Technology 2019-Feb-11
Supervisor:
Dr. Khalilzadeh
Presented by:
Sajad Mohammadi
Advised by:
Dr. Shahrivar
2
1) Introduction
2) Literature Review
3) Methodology
4) Results
5) Suggestion
Content
Title: Investigation of Pre-leaching and particle size’s effects on copper slag bioleaching 3
Title: Investigation of Pre-leaching and particle size’s effects on copper slag bioleaching
Introduction
✓A chemical element with symbol Cu and atomic number 29.
✓ It is a soft, malleable, and ductile metal with very high thermal and electrical conductivity.
Application
43%
19%
19%
12%
7%
Building conestruction Transportation
Electric & electronic Consumer & general
Industrial machinery & equipment
4
How to produce copper?
oCopper in nature
chalcopyrite Bornite enargite chalcocite Covellite
Title: Investigation of Pre-leaching and particle size’s effects on copper slag bioleaching
Introduction
5
Title: Investigation of Pre-leaching and particle size’s effects on copper slag bioleaching
Copper production’s methods
Pyrometallurgy Hydrometallurgy
1 Thermal treatment
2 produce products able to be sold
such as pure metals.(Cu, Zn,Mn,
Ch)
3 The energy is usually provided in
the form of combustion or from
electrical heat.
Introduction
6
Copper slag
•Copper slag is a by-product of copper extraction by smelting.
•Slag from ores that are mechanically concentrated before smelting contain mostly
iron oxides and silicon oxides.
•Copper slag is mainly used for surface blast-cleaning.
•Copper slag can be used in concrete production as a partial replacement for sand.
•It contains 2% - 6% copper.
Introduction
Title: Investigation of Pre-leaching and particle size’s effects on copper slag bioleaching 7
Hydrometallurgy is typically divided into three general areas:
1)Leaching
2)Solution concentration and purification
3)Metal or metal compound recovery
Chemical leaching
Bioleaching
Solvent extraction
Ion exchange
electrowinning
precipitation
Title: Investigation of Pre-leaching and particle size’s effects on copper slag bioleaching 8
Title: Investigation of Pre-leaching and particle size’s effects on copper slag bioleaching
•All kinds of Leaching Introduction
9
o Impressive factors
Impressive factors in bioleaching Variables
Physicochemical parameters of a bioleaching
environment
Temp, pH, redox potential, 𝑐𝑜2, mass transfer,
nutrition, pressure, surface tension, 𝐹𝑒2+
&
𝐹𝑒3+
Microbiological parameters Type of bacteria, population, distribution,
adaptation
Properties of the mineral Type & structure, chemical components,
particle size, prosity
processing Leaching mode, pulp density, flowrate, stirring
rate( tank leaching ), time
Literature review
Title: Investigation of Pre-leaching and particle size’s effects on copper slag bioleaching
10
▪ Adaptation
The microorganism adaptation has been reported as being worthwhile, since it
increases the metabolic capacity and as a consequence the solubilisation of the
metals.
Influence of Bacterial
Adaptation on Copper
Bioleaching
Influence of Bacterial Adaptation on Copper Bioleaching from
Printed Circuit Boards. May 2018. University of São Paulo, Brazil
Literature review
11
Time
Provides more time for the acid and bacteria to react with the ore at the curing humidity, which
allowed for greater solid liquid interaction. This transformed the minerals in the ore, dissolving
mineralogical species and forming new more soluble ones.
Effect of Pretreatment on Leaching Primary Copper
Sulfide in Acid-Chloride Media. December 2017. Chile
Literature review
12
❑ pH
• T. Ferrooxidans, T.Thiooxidans, L.Ferrooxidans are acidophilic which means that these bacteria can
grow and oxidise Iron in a pH range of 1 to 2.5. The strain used by silverman and lundgren in 1959,
Oxidised iron at a pH between 3.0 and 3.6.
• The optimal pH for oxidation and cell growth can vary between strains and is also dependent on
experimental conditions.
• A study on the effect of initial pH ranging from pH 1.0 to 1.7 on the bioleaching of chalcopyrite
concentrate by T. ferrooxidans showed that the dissolution rate of copper and iron increased when
using an initial pH of 1.0.
Nakazawa et al. (1998)
Literature review
13
❖ Particle size
a) Ahonen and tuovinen (1995) stated that the leaching rates for metal sulphide ores increased
with a reduction in particle size and this effect was enhanced at lower pH values.
b) The reaction surface is a determinant factor in catalytic reactions.
c) Particle size, affects microbial performance by altering surface area available for bacterial
attachment.
d) The copper and nickel leaching rate approximately doubled when the particle diameter was
decreased from 5, 10 mm to 1.68, 5 mm.
Bioleaching of chalcopyrite. A thesis for the degree of DOCTOR OF
PHILOSOPHY. The university of Birmingham. 2003
Literature review
14
Well controlled column bioleaching of a low-grade
copper ore by a novel equipment. 2015
Literature review
15
➢ What we have done?
Si
K
Ca
Ti
Cr
Mn
Element
13.39
1.08
9.28
0.17
0.21
0.12
%
Cu
Zn
Sb
S
Mg
Al
Element
3.06
4.26
0.19
1.12
1.53
3.02
%
-----
Na
O
Pb
Ba
Fe
Element
-----
0.43
35.46
2.42
0.26
24
%
13.39
Methodology
Title: Investigation of Pre-leaching and particle size’s effects on copper slag bioleaching 16
•Using taguchi method for experimental design(L9)
level pH Particle
size(mm)
Flow rate(
𝒎𝒍
𝒎𝒊𝒏
) %Nitric acid
1 0.8 2-5 1 0
2 1.2 5-11 1.5 33
3 1.5 2-11 2 50
variable
Methodology
Title: Investigation of Pre-leaching and particle size’s effects on copper slag bioleaching 17
Title: Investigation of Pre-leaching and particle size’s effects on copper slag bioleaching
•Shake flask tests
Methodology
ICP analysis
6 Erlenmeyers
Pulp density
20%
pH=0.8&1.5-
sulfuric & nitric acid and
their combination
Shaker incubator:
150rpm & 35 Celsius
Centrifuge
10 mins & 5000
rpm
1
2
3
4
5
6
18
Title: Investigation of Pre-leaching and particle size’s effects on copper slag bioleaching
NO pH Particle size (mm) Flow rate ( ml/min) % Nitric Acid
1 0.8 2-5 1 0
2 0.8 2-11 1.5 33
3 0.8 5-11 2 50
4 1.2 2-5 1.5 50
5 1.2 2-11 2 0
6 1.2 5-11 1 33
7 1.8 2-5 2 33
8 1.8 2-11 1 50
9 1.8 5-11 1.5 0
Methodology
✓ Column test
19
Title: Investigation of Pre-leaching and particle size’s effects on copper slag bioleaching
51.5
64
49.2
10.9
17.2 17.4
0
10
20
30
40
50
60
70
H2SO4 H2SO4/HNO3 1:1 H2SO4/HNO3 2:1
Acid
Consumption
(ml)
pH=0.8 pH=1.5
0%
20%
40%
60%
80%
100%
H2SO4
H2SO4/HNO3 1:1
H2SO4/HNO3 2:1
48%
84%
77%
74%
33%
53%
pH=0.8 pH=1.5
Results
20
Title: Investigation of Pre-leaching and particle size’s effects on copper slag bioleaching
Results
• Column pre-leaching
21
Title: Investigation of Pre-leaching and particle size’s effects on copper slag bioleaching
350
385
420
455
490
525
560
595
630
665
700
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
ORP(mV)
Time(day)
‫تیواکسیدانس‬ ‫تیوباسیلوس‬ ‫اسیدی‬ ‫فرواکسیدانس‬ ‫لپتوسپریلیوم‬ ‫فرواکسیدانس‬ ‫تیوباسیلوس‬ ‫اسیدی‬
• Growth curve Results
22
Title: Investigation of Pre-leaching and particle size’s effects on copper slag bioleaching
Results
• Bioleaching results
0%
10%
20%
30%
40%
50%
60%
C 1 C 2 C 3 C 4 C 5 C 6 C 7 C 8 C 9
Cu
extraction
Column NO
23
Title: Investigation of Pre-leaching and particle size’s effects on copper slag bioleaching
• Taguchi analysis
Results
24
Title: Investigation of Pre-leaching and particle size’s effects on copper slag bioleaching
Results
▪ Effects of pH, particle size
1 .8
1 .2
0.8
60.00%
50.00%
40.00%
30.00%
20.00%
pH
Cu
extraction
Boxplot of Result
25
Title: Investigation of Pre-leaching and particle size’s effects on copper slag bioleaching
▪ Effects of nitric acid & flow rate Results
26
Title: Investigation of Pre-leaching and particle size’s effects on copper slag bioleaching
Results
➢Optimal pH & particle size
27
Title: Investigation of Pre-leaching and particle size’s effects on copper slag bioleaching
28
1) Magnetic field has positive effects on bacterial growth by altering medium’s
surface tension.
2) It would have better efficiency, if thermophilic bacteria was used.
3) If there is no problem with operational cost, it is better to use tank bioleaching
to reach high copper recovery rate.
Title: Investigation of Pre-leaching and particle size’s effects on copper slag bioleaching
Suggestions
29
30
References
[1] h. R. Watling, “the bioleaching of sulphide minerals with emphasis on copper sulphides — A review,” vol. 84, pp.
81–108, 2006.
[2] d. Mishra, D. Kim, J. Ahn, and Y. Rhee, “bioleaching : A microbial process of metal recovery ; A review,” vol. 11, no.
3, pp. 249–256, 2005.
[3] r. Ngulube, M. Wanjiya, and K. Nyirenda, “AN OVERVIEW OF SUSTAINABLE COPPER RECOVERY
METHOD,” no. November, pp. 54–59, 2016.
[4] d. M. Urosevic, M. D. Dimitrijevic, and Z. D. Jankovic, “RECOVERY OF COPPER FROM COPPER SLAG AND
COPPER SLAG FLOTATION TAILINGS,” vol. 51, no. 1, 2015.
[5] a. Tahmasbi, S. B. S. A, a. R. Shahverdi, and M. Oliazadeh, “bio-assisted leaching of copper reverberatory furnace
slag,” pp. 4–6, 1994.
[6] h. Zilouei, S. A. Shojaosadati, and R. Khalilzadeh, “bioleaching of copper from low-grade ore using isolated bacteria
and defined mixed cultures,” vol. 1, no. 3, pp. 162–168, 2003.
[7] y. Wang, L. Zhang, C. Zhu, and M. Feng, “effect of particle size on the column bioleaching of tibet yulong copper
ore,” vol. 1130, pp. 375–378, 2015.
Title: Investigation of Pre-leaching and particle size’s effects on copper slag bioleaching 31
[8] n. Jamett and Y. Ghorbani, “effect of pretreatment on leaching primary copper sulfide in acid-chloride media,” no.
1100685, 2017.
[9] w. Jun, H. U. Ming-hao, Z. Hong-bo, and T. A. O. Lang, “well-controlled column bioleaching of a low-grade copper ore
by a novel equipment,” pp. 3318–3325, 2015.
[10] s. M. Mousavi, S. Yaghmaei, M. Vossoughi, R. Roostaazad, and A. Jafari, “the effects of fe ( II ) and fe ( III )
concentration and initial ph on microbial leaching of low-grade sphalerite ore in a column reactor,” vol. 99, pp. 2840–2845, 2008.
[11] j. J. Plumb, R. Muddle, and P. D. Franzmann, “effect of ph on rates of iron and sulfur oxidation by bioleaching
organisms,” vol. 21, pp. 76–82, 2008.
[12] m. Dopson et al., “Silicate mineral dissolution during heap bioleaching,” vol. 99, no. 4, pp. 811–820, 2008.
[13] a. Halinen, N. Rahunen, A. H. Kaksonen, and J. A. Puhakka, “hydrometallurgy heap bioleaching of a complex sul fi de
ore part I : effect of ph on metal extraction and microbial composition in ph controlled columns,” vol. 98, pp. 92–100, 2009.
[14] e. M. Córdoba, J. A. Muñoz, M. L. Blázquez, F. González, and A. Ballester, “hydrometallurgy leaching of chalcopyrite
with ferric ion . part I : general aspects,” vol. 93, pp. 81–87, 2008.
Title: Investigation of Pre-leaching and particle size’s effects on copper slag bioleaching 32
Copper slag bioleaching

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Copper slag bioleaching

  • 1. In the name of Allah, the designer, the creator and the initiator 1
  • 2. Title: Investigation of Pre-leaching and particle size’s effects on copper slag bioleaching Malek-Ashtar University of Technology 2019-Feb-11 Supervisor: Dr. Khalilzadeh Presented by: Sajad Mohammadi Advised by: Dr. Shahrivar 2
  • 3. 1) Introduction 2) Literature Review 3) Methodology 4) Results 5) Suggestion Content Title: Investigation of Pre-leaching and particle size’s effects on copper slag bioleaching 3
  • 4. Title: Investigation of Pre-leaching and particle size’s effects on copper slag bioleaching Introduction ✓A chemical element with symbol Cu and atomic number 29. ✓ It is a soft, malleable, and ductile metal with very high thermal and electrical conductivity. Application 43% 19% 19% 12% 7% Building conestruction Transportation Electric & electronic Consumer & general Industrial machinery & equipment 4
  • 5. How to produce copper? oCopper in nature chalcopyrite Bornite enargite chalcocite Covellite Title: Investigation of Pre-leaching and particle size’s effects on copper slag bioleaching Introduction 5
  • 6. Title: Investigation of Pre-leaching and particle size’s effects on copper slag bioleaching Copper production’s methods Pyrometallurgy Hydrometallurgy 1 Thermal treatment 2 produce products able to be sold such as pure metals.(Cu, Zn,Mn, Ch) 3 The energy is usually provided in the form of combustion or from electrical heat. Introduction 6
  • 7. Copper slag •Copper slag is a by-product of copper extraction by smelting. •Slag from ores that are mechanically concentrated before smelting contain mostly iron oxides and silicon oxides. •Copper slag is mainly used for surface blast-cleaning. •Copper slag can be used in concrete production as a partial replacement for sand. •It contains 2% - 6% copper. Introduction Title: Investigation of Pre-leaching and particle size’s effects on copper slag bioleaching 7
  • 8. Hydrometallurgy is typically divided into three general areas: 1)Leaching 2)Solution concentration and purification 3)Metal or metal compound recovery Chemical leaching Bioleaching Solvent extraction Ion exchange electrowinning precipitation Title: Investigation of Pre-leaching and particle size’s effects on copper slag bioleaching 8
  • 9. Title: Investigation of Pre-leaching and particle size’s effects on copper slag bioleaching •All kinds of Leaching Introduction 9
  • 10. o Impressive factors Impressive factors in bioleaching Variables Physicochemical parameters of a bioleaching environment Temp, pH, redox potential, 𝑐𝑜2, mass transfer, nutrition, pressure, surface tension, 𝐹𝑒2+ & 𝐹𝑒3+ Microbiological parameters Type of bacteria, population, distribution, adaptation Properties of the mineral Type & structure, chemical components, particle size, prosity processing Leaching mode, pulp density, flowrate, stirring rate( tank leaching ), time Literature review Title: Investigation of Pre-leaching and particle size’s effects on copper slag bioleaching 10
  • 11. ▪ Adaptation The microorganism adaptation has been reported as being worthwhile, since it increases the metabolic capacity and as a consequence the solubilisation of the metals. Influence of Bacterial Adaptation on Copper Bioleaching Influence of Bacterial Adaptation on Copper Bioleaching from Printed Circuit Boards. May 2018. University of São Paulo, Brazil Literature review 11
  • 12. Time Provides more time for the acid and bacteria to react with the ore at the curing humidity, which allowed for greater solid liquid interaction. This transformed the minerals in the ore, dissolving mineralogical species and forming new more soluble ones. Effect of Pretreatment on Leaching Primary Copper Sulfide in Acid-Chloride Media. December 2017. Chile Literature review 12
  • 13. ❑ pH • T. Ferrooxidans, T.Thiooxidans, L.Ferrooxidans are acidophilic which means that these bacteria can grow and oxidise Iron in a pH range of 1 to 2.5. The strain used by silverman and lundgren in 1959, Oxidised iron at a pH between 3.0 and 3.6. • The optimal pH for oxidation and cell growth can vary between strains and is also dependent on experimental conditions. • A study on the effect of initial pH ranging from pH 1.0 to 1.7 on the bioleaching of chalcopyrite concentrate by T. ferrooxidans showed that the dissolution rate of copper and iron increased when using an initial pH of 1.0. Nakazawa et al. (1998) Literature review 13
  • 14. ❖ Particle size a) Ahonen and tuovinen (1995) stated that the leaching rates for metal sulphide ores increased with a reduction in particle size and this effect was enhanced at lower pH values. b) The reaction surface is a determinant factor in catalytic reactions. c) Particle size, affects microbial performance by altering surface area available for bacterial attachment. d) The copper and nickel leaching rate approximately doubled when the particle diameter was decreased from 5, 10 mm to 1.68, 5 mm. Bioleaching of chalcopyrite. A thesis for the degree of DOCTOR OF PHILOSOPHY. The university of Birmingham. 2003 Literature review 14
  • 15. Well controlled column bioleaching of a low-grade copper ore by a novel equipment. 2015 Literature review 15
  • 16. ➢ What we have done? Si K Ca Ti Cr Mn Element 13.39 1.08 9.28 0.17 0.21 0.12 % Cu Zn Sb S Mg Al Element 3.06 4.26 0.19 1.12 1.53 3.02 % ----- Na O Pb Ba Fe Element ----- 0.43 35.46 2.42 0.26 24 % 13.39 Methodology Title: Investigation of Pre-leaching and particle size’s effects on copper slag bioleaching 16
  • 17. •Using taguchi method for experimental design(L9) level pH Particle size(mm) Flow rate( 𝒎𝒍 𝒎𝒊𝒏 ) %Nitric acid 1 0.8 2-5 1 0 2 1.2 5-11 1.5 33 3 1.5 2-11 2 50 variable Methodology Title: Investigation of Pre-leaching and particle size’s effects on copper slag bioleaching 17
  • 18. Title: Investigation of Pre-leaching and particle size’s effects on copper slag bioleaching •Shake flask tests Methodology ICP analysis 6 Erlenmeyers Pulp density 20% pH=0.8&1.5- sulfuric & nitric acid and their combination Shaker incubator: 150rpm & 35 Celsius Centrifuge 10 mins & 5000 rpm 1 2 3 4 5 6 18
  • 19. Title: Investigation of Pre-leaching and particle size’s effects on copper slag bioleaching NO pH Particle size (mm) Flow rate ( ml/min) % Nitric Acid 1 0.8 2-5 1 0 2 0.8 2-11 1.5 33 3 0.8 5-11 2 50 4 1.2 2-5 1.5 50 5 1.2 2-11 2 0 6 1.2 5-11 1 33 7 1.8 2-5 2 33 8 1.8 2-11 1 50 9 1.8 5-11 1.5 0 Methodology ✓ Column test 19
  • 20. Title: Investigation of Pre-leaching and particle size’s effects on copper slag bioleaching 51.5 64 49.2 10.9 17.2 17.4 0 10 20 30 40 50 60 70 H2SO4 H2SO4/HNO3 1:1 H2SO4/HNO3 2:1 Acid Consumption (ml) pH=0.8 pH=1.5 0% 20% 40% 60% 80% 100% H2SO4 H2SO4/HNO3 1:1 H2SO4/HNO3 2:1 48% 84% 77% 74% 33% 53% pH=0.8 pH=1.5 Results 20
  • 21. Title: Investigation of Pre-leaching and particle size’s effects on copper slag bioleaching Results • Column pre-leaching 21
  • 22. Title: Investigation of Pre-leaching and particle size’s effects on copper slag bioleaching 350 385 420 455 490 525 560 595 630 665 700 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 ORP(mV) Time(day) ‫تیواکسیدانس‬ ‫تیوباسیلوس‬ ‫اسیدی‬ ‫فرواکسیدانس‬ ‫لپتوسپریلیوم‬ ‫فرواکسیدانس‬ ‫تیوباسیلوس‬ ‫اسیدی‬ • Growth curve Results 22
  • 23. Title: Investigation of Pre-leaching and particle size’s effects on copper slag bioleaching Results • Bioleaching results 0% 10% 20% 30% 40% 50% 60% C 1 C 2 C 3 C 4 C 5 C 6 C 7 C 8 C 9 Cu extraction Column NO 23
  • 24. Title: Investigation of Pre-leaching and particle size’s effects on copper slag bioleaching • Taguchi analysis Results 24
  • 25. Title: Investigation of Pre-leaching and particle size’s effects on copper slag bioleaching Results ▪ Effects of pH, particle size 1 .8 1 .2 0.8 60.00% 50.00% 40.00% 30.00% 20.00% pH Cu extraction Boxplot of Result 25
  • 26. Title: Investigation of Pre-leaching and particle size’s effects on copper slag bioleaching ▪ Effects of nitric acid & flow rate Results 26
  • 27. Title: Investigation of Pre-leaching and particle size’s effects on copper slag bioleaching Results ➢Optimal pH & particle size 27
  • 28. Title: Investigation of Pre-leaching and particle size’s effects on copper slag bioleaching 28
  • 29. 1) Magnetic field has positive effects on bacterial growth by altering medium’s surface tension. 2) It would have better efficiency, if thermophilic bacteria was used. 3) If there is no problem with operational cost, it is better to use tank bioleaching to reach high copper recovery rate. Title: Investigation of Pre-leaching and particle size’s effects on copper slag bioleaching Suggestions 29
  • 30. 30
  • 31. References [1] h. R. Watling, “the bioleaching of sulphide minerals with emphasis on copper sulphides — A review,” vol. 84, pp. 81–108, 2006. [2] d. Mishra, D. Kim, J. Ahn, and Y. Rhee, “bioleaching : A microbial process of metal recovery ; A review,” vol. 11, no. 3, pp. 249–256, 2005. [3] r. Ngulube, M. Wanjiya, and K. Nyirenda, “AN OVERVIEW OF SUSTAINABLE COPPER RECOVERY METHOD,” no. November, pp. 54–59, 2016. [4] d. M. Urosevic, M. D. Dimitrijevic, and Z. D. Jankovic, “RECOVERY OF COPPER FROM COPPER SLAG AND COPPER SLAG FLOTATION TAILINGS,” vol. 51, no. 1, 2015. [5] a. Tahmasbi, S. B. S. A, a. R. Shahverdi, and M. Oliazadeh, “bio-assisted leaching of copper reverberatory furnace slag,” pp. 4–6, 1994. [6] h. Zilouei, S. A. Shojaosadati, and R. Khalilzadeh, “bioleaching of copper from low-grade ore using isolated bacteria and defined mixed cultures,” vol. 1, no. 3, pp. 162–168, 2003. [7] y. Wang, L. Zhang, C. Zhu, and M. Feng, “effect of particle size on the column bioleaching of tibet yulong copper ore,” vol. 1130, pp. 375–378, 2015. Title: Investigation of Pre-leaching and particle size’s effects on copper slag bioleaching 31
  • 32. [8] n. Jamett and Y. Ghorbani, “effect of pretreatment on leaching primary copper sulfide in acid-chloride media,” no. 1100685, 2017. [9] w. Jun, H. U. Ming-hao, Z. Hong-bo, and T. A. O. Lang, “well-controlled column bioleaching of a low-grade copper ore by a novel equipment,” pp. 3318–3325, 2015. [10] s. M. Mousavi, S. Yaghmaei, M. Vossoughi, R. Roostaazad, and A. Jafari, “the effects of fe ( II ) and fe ( III ) concentration and initial ph on microbial leaching of low-grade sphalerite ore in a column reactor,” vol. 99, pp. 2840–2845, 2008. [11] j. J. Plumb, R. Muddle, and P. D. Franzmann, “effect of ph on rates of iron and sulfur oxidation by bioleaching organisms,” vol. 21, pp. 76–82, 2008. [12] m. Dopson et al., “Silicate mineral dissolution during heap bioleaching,” vol. 99, no. 4, pp. 811–820, 2008. [13] a. Halinen, N. Rahunen, A. H. Kaksonen, and J. A. Puhakka, “hydrometallurgy heap bioleaching of a complex sul fi de ore part I : effect of ph on metal extraction and microbial composition in ph controlled columns,” vol. 98, pp. 92–100, 2009. [14] e. M. Córdoba, J. A. Muñoz, M. L. Blázquez, F. González, and A. Ballester, “hydrometallurgy leaching of chalcopyrite with ferric ion . part I : general aspects,” vol. 93, pp. 81–87, 2008. Title: Investigation of Pre-leaching and particle size’s effects on copper slag bioleaching 32