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2008:012

MASTER'S THESIS

Purification of Molybdenite Concentrates

Ikumapayi Fatai Kolawole

Lule University of Technology


Master Thesis, Continuation Courses
Minerals and Metallurgical Engineering
Department of Chemical Engineering and Geosciences
Division of Process Metallurgy
2008:012 - ISSN: 1653-0187 - ISRN: LTU-PB-EX--08/012--SE

Abstract
A molybdenite flotation concentrate was refined by selective removal of copper impurity with
minimum dissolution of molybdenum in the concentrate. Copper is present in the concentrate
mainly as copper sulphide, chalcopyrite. Investigations were carried out on the removal of the
sulphide by their selective leaching in sodium cyanide, ferric chloride and ferric sulphate
solutions.
Approximately 80 to 100% of the copper concentration was removed under optimum
conditions with sodium cyanide and ferric chloride solutions with little dissolution of
molybdenum while ferric sulphate solution was ineffective due to a number of factors such as
passivation of chalcopyrite, temperature and redox potential.
Leaching with sodium cyanide was carried out with stoichiometric concentration of the salt,
20% solids, at ambient temperature and pH above11 with oxygen as oxidative gas, for 53 and
74 hours. Ferric chloride leaching was carried out at 35% solids with 10% ferric chloride, 1%
cupric chloride, 20% calcium chloride all by weight of solution at an average temperature of
80oC and pH about zero for 4 hours. Ferric sulphate leaching was carried out with
stoichiometric concentration of ferrous sulphate as the starting solution in which ferric
sulphate solution was generated by oxidation with addition of oxygen and sulphur dioxide in
ratio 10:1, 10% solids and pH below 0.5 at 65oC for 5 hours.
The intermediate pregnant solution samples and final leach solutions from the tests were
analyzed for dissolved copper with the aid of atomic absorption spectrophotometer, (AAS)
and the purified concentrate (solid residue) was analyzed for molybdenum, copper and other
important elements with different analytical techniques such as: (i) AAS for molybdenum,
calcium, bismuth and low level copper, iron and lead. (ii) Solution X-ray for high-level
copper, iron and lead. (iii) Fire assay for gold and silver. (iv) Leco-owen for sulphur. (v) Field
ionization mass spectroscopy, (FIMS) instrument for mercury and (vi) Selective electrode for
chloride ion.

Table of content
Abstract ................................................................................................................................2
Acknowledgement ................................................................................................................6
1 Introduction .....................................................................................................................7
1.1 History..........................................................................................................................7
1.2 Characteristics ..............................................................................................................9
1.3 Applications................................................................................................................10
1.3.1 Use as parts and alloys .........................................................................................10
1.3.2 Use as lubricant....................................................................................................10
1.3.3 Use in petrol-chemistry ........................................................................................11
1.3.4 Other uses ............................................................................................................11
1.4 Occurence...................................................................................................................11
2 Recovery of molybdenite .................................................................................................13
3 Molybdenite production in Boliden ................................................................................15
3.1 Background ................................................................................................................15
3.2 Aim ............................................................................................................................16
4 Literature review .............................................................................................................17
4.1 Purification of molybdenite concentrate ......................................................................17
4.1.1 Microorganisms ...................................................................................................17
4.1.3 Sulphuric acid ......................................................................................................17
4.1.4 Sulphuric acid with sodium dichromate solution, Na2Cr2O7..................................18
4.1.5 Leaching with oxygen and halide e.g. CuCl2 ........................................................18
4.1.6 Conventional leaching with chloride salts.............................................................18
4.1.7 Hydrochloric acid and hydrofluoric acid...............................................................19
4.1.8 SO2/O2 as a strong oxidant ...................................................................................19
4.2 Molybdenum-water chemistry ....................................................................................19
4.3 Equilibrium diagram and its interpretation ..................................................................21
4.3.1 Stability of the compounds of trivalent molydenum..............................................25
4.3.2 Stability of the compounds of tetravalent molybdenum ........................................25
4.3.3 Stability of the compounds of pentavalent molybdenum, molybdenum blue.........26
4.3.4 Stability of the compounds of hexavalent molybdenum........................................26
4.4 Cu-CN chemistry........................................................................................................28
4.5 Leaching theory ..........................................................................................................34
4.5.1 Leaching under pressure.......................................................................................34
4.5.2 Leaching theory ...................................................................................................34
5 Experimental ...................................................................................................................35
5.1 Material ......................................................................................................................35
5.2 Reactors......................................................................................................................36
5.3 Methodology ..............................................................................................................37
5.4 Test performance ........................................................................................................37
5.4.1 Cyanide leaching..................................................................................................37
5.4.2 Ferric chloride (FeCl3) leaching ...........................................................................40
5.4.3 Ferric sulphate Fe2(SO4)3 leaching .......................................................................41

6 Results and discussions....................................................................................................45


6.1 Cyanide tests...............................................................................................................45
6.1.1 Mo-losses to solution ...........................................................................................49
6.1.2 Concentrate weight changes .................................................................................49
6.1.3 Oxidising gases ....................................................................................................49
6.2 Ferric chloride (FeCl3) leaching ..................................................................................50
6.3 Ferric sulphate Fe2(SO4)3 leaching ..............................................................................51
7 Conclusion........................................................................................................................55
8 Suggested further work ...................................................................................................56
References...........................................................................................................................57
Appendix.............................................................................................................................60
Appendix I....................................................................................................................60
Properties of molybdenum ....................................................................................60
Appendix II ..................................................................................................................61
Estimation of reagent for cyanide leaching............................................................61
Procedure for cyanide leaching .............................................................................62
Table I-II Protocol and reagent consumption NaCN ..............................................63
Table I-III: Protocol and reagent consumption NaCN............................................64
Table I-IV: Leaching profile and material balance NaCN ......................................64
Table I-V: Profile of residual elemental analysis NaCN.........................................67
Table I-VI: Protocol and reagent consumption NaCN + CaCl2 ...............................67
Table I-VII: Protocol and reagent consumption NaCN + CaCl2 .............................68
Table I-VIII: Leaching profile and material balance...............................................68
Table I-IX: Profile of residual elemental analysis NaCN + CaCl2 ..........................71
Appendix III .................................................................................................................71
Procedure for ferric chloride leaching....................................................................71
Table I-X: Protocol and reagent consumption FeCl3 ..............................................72
Table I-XI: Protocol and reagent consumption FeCl3 .............................................73
Table I-XII: Leaching profile and material balance FeCl3 ......................................73
Table I-XIII: Profile of residual elemental analysis FeCl3 ......................................76
Appendix IV.................................................................................................................76
Procedure for ferric sulphate leaching ...................................................................76
Table I-XIV: Leaching profile and reagent consumption Fe2(SO4)3 ........................77
Table I-XV: Leaching profile and reagent consumption Fe2(SO4)3 .........................77
Table I-XVI: Molybdenum dissolution sodium cyanide leaching ...........................78
Table I-XVII: Molybdenum dissolution sodium cyanide + calcium chloride leaching
.............................................................................................................................78
Appendix V ..................................................................................................................78
Atomic absorption spectroscopy, AAS ..................................................................78
Copper analysis with AAS ....................................................................................79
Procedure for copper analysis with AAS ...............................................................79
Table II-I: Copper concentration in standard solution and corresponding AAS
signals...................................................................................................................80
XRD Equipment ...................................................................................................81
Appendix VI.................................................................................................................82
Composition of commercial molybdenite concentrate brands ................................82
Table II-II Molybdenum Concentrate Brands & Chemical Compositions ..............82
4

Composition of commercial molybdenum oxide brands ........................................83


Table II-III :Technical Grade Molybdenum Oxide.Sadaci .....................................83
Table II-IV :Purified concentrates analysis. ...........................................................83
Table II-V: Cyanide leaching test assays................................................................83
Table II-VI: Cyanide + Chloride leaching test assays.............................................83
Table II-VII: Ferric chloride leaching test assays ...................................................84
Appendix VII................................................................................................................85
SCN formation......................................................................................................85
Appendix VIII ..............................................................................................................87
Mo-CN stability constant ......................................................................................87

Acknowledgement
This research work is completed in partial fulfillment of the requirements for the award of
Masters of Science, Msc in minerals and metallurgical engineering, Lule University of
Technology, (Ltu). Boliden Mineral AB assigned the project and it entails experiments that
involve handling of various materials and equipment such as chemicals, analytical
instruments, laboratory space and other logistics. All experiments and most analysis were
carried out in the mineral-processing laboratory at Boliden Mineral AB. XRD analysis was
carried out at the Department of Chemical Engineering, Ltu.
Hence my profound gratitude goes to the management and staff of Boliden Mineral AB for
providing all logistics and for giving me free access to use all facilities.
My appreciation goes to my supervisors: Prof. ke Sandstrm (Ltu) and Jan-Eric Sundkvist
(Boliden) who has guided me through the research work; they are the brains behind the
success of this project. Many thanks also go to the laboratory staff: Rolf Danielsson, Amang
Saleh, Maria Lagerhielm, Johan Hansson and Mikael Widman who was ever ready to assist
me with all laboratory logistics and Chandra Sekhar Gahan who assisted with XRD analysis
at Ltu. The moral supports of all staff at the mineral processing department in Boliden are
greatly appreciated.
Finally my greatest thanks goes to my family members and particularly my late Dad; Ramon
Ikumapayi, my mother; Fausat Ikumapayi, my brother; Nurudeen Ikumapayi, and Anna
Bauer, all of whom have greatly contributed spiritually, morally and financially towards
successful completion of my study. It would have been impossible without them.

Boliden, August 2007


Fatai Ikumapayi

1 Introduction
1.1 History
Molybdenite, originate from the Greek word molybdos, meaning lead, it is the principal
mineral from which molybdenum metal is now extracted. It was previously known as
molybdena. Molybdena was often confused with and implemented as graphite even after the
two ores were distinguishable; molybdena was still thought to be a lead mineral. In 1754,
Bengt Qvist examined the mineral and determined that it did not contain lead. It was in 1778
that a Swedish chemist named Carl Wilhelm Scheele put a clear light to the identification of
the metal. He discovered that molybdena was neither graphite nor lead. He and other chemists
then correctly assumed that it was the mineral of a distinct new element, named molybdenum
for the mineral in which it was discovered. In 1781 Peter Jacob Hjelm used linseed oil and
carbon to successfully isolate molybdenum [15].
The first major use of molybdenum came during World War I when its addition produced
steel with excellent toughness and strength at high temperatures for use as tank armor and in
aircraft engines. The major source through 19th century was Knaben mine in Norway in which
the molybdenite was concentrated by hand sorting. In 1918 Climax molybdenum company
(Colorado) uses the froth flotation process to concentrate the ore. Although the Climax mine
was shut down after the war due to decreased demand for the metal, it was however reopened
in 1924 when better peacetime applications was developed largely in the automotive industry.
In 1933 molybdenum production as a by-product of copper began when Anaconda Company
developed a method of selective flotation of molybdenite from porphyry copper ores at its
subsidiary Cananea in Mexico. The Kennecott Copper Company mine in Utah, El Teniente
mine in Chile and Anacondas Chuquicamata mine follows suite.
The United States supplied about 90% of the world molybdenum demand during the World
War II, most coming from Climax with balance from Kennecotts Utah mines and Molycorps
Questa mine. Chile, Mexico and Norway remain the largest of the other western -world
producing countries.

Climax Molybdenum Company continues to be the largest western-world producer into the
1980s while production from Mexico and Norway remained small, less expensive by-product
from Chile and United states continue to grow. Endako and other mines in Canada also began
molybdenum production. In 1977 the total world production of molybdenum exceeded 200
million pounds (approx. 90 000t) for the first time.
Late 1970s marks the opening of several molybdenum mines and expansion of many byproducts facilities; this was stimulated due to high price of molybdenum. However price
decline in the early 1980s made the by-products molybdenum a dominant economic force in
the market. The underground mine in Climax was closed by Climax molybdenum company
but the company still remained as a major producer with Henderson mine, and the open pit
mine at Climax Cyprus Minerals. Other major producers at the end of 1980s were Codelcos
Chuquicamata mine in Chile, Placers Endako mine in Canada, the LaCaridad mine in
Mexico, and the Cuajone and Toquepala mines in Peru. The world annual production and
consumption averaged (180-200) million pounds (80 000- 90 000 t) of molybdenum during
the late 1980s [11].
Molybdenum has a value of approximately $65,000 per tonne as of 4 May 2007. It has
maintained a price at or near $10,000 per tonne from 1997 through 2002, and reached a peak
of $103,000 per tonne in June 2005. The world'
s largest producers of molybdenum materials
remained the United States, Canada, Chile, Russia, and China. In 2005, USA remains the top
producer of molybdenum with about 30% world share followed by Chile and China, figure1-1
[15].

Figure1-1: Molybdenum output in 2005 [16]


The figure shows the worlds largest producer of molybdenum in 2005 as a percentage of the
top producer. The green band depicts 100% and corresponds to the United States as the top
producer with annual production of 56,900 tonnes, the yellow band depicts 10%, and the red
band depicts 1% respectively. The yellow bands correspond to Canada, Chile, China, and
other South American producers, while the red bands correspond to Russia, Mexico and other
Asian producer.

1.2 Characteristics
Molybdenum is a transition metal, silvery white in its pure metal form and very hard, it is
somewhat more ductile than tungsten. It has a melting point of 2623C, and only tantalum,
rhenium and tungsten have higher melting points. Molybdenum burns only at temperatures
above 600C. Its expansion during heating is the lowest compared to other commercially used
metals [15].
Molybdenum disulphide, also known as molybdenum sulphide or molybdenum (IV) sulphide,
with the molecular formula MoS2, molar mass 160.07 g/mol, and density 5.06 g/cm3 is a
black crystalline sulphide of molybdenum. It occurs as the mineral molybdenite and it is the
main commercial source of molybdenum. It is insoluble in all solvents and un-reactive toward
dilute acids. Its melting point is 1185C, but it starts oxidizing in air from 315C, limiting the

range of its use as a lubricant in the presence of air between the temperatures of -185 and
+350C; in non-oxidizing environments it is stable up to 1100C [8]. Structurally MoS2 is
trigonal prismatic at Mo, and pyramidal at S. Molybdenum disulphide contains approximately
60% Mo, and 40% S. Detailed properties of molybdenum can be found in appendix I.

1.3 Applications
1.3.1 Use as parts and alloys
Molybdenum can withstand excessive heat at extreme temperatures without softening or
expanding, this unique property makes it very useful in the manufacture of aircraft parts,
filaments, amor tanks, electrical contacts and other applications that involve intence heat.
Molybdenum have very high weldability and it is also highly resistant to corrosion, hence
used in making high strength steel alloys: More than 43 000 tonnes of molybdenum is used
annually as alloying agent in high temperature superalloys stainless steels and tool steels,
although molybdenum contributes only about 8 to 25% composition of the alloys. It is being
implemented in place of tungsten due to its low density. It can be implemented both as an
alloying agent and as a flame-resistant coating for other metals. Molybdenum is better suited
for use in vacuum environments because it oxidises rapidly at temperatures above 760C
although its melting point is 2623C [15].
1.3.2 Use as lubricant
Molybdenum disulphide (MoS2) can form strong films on metal surface, highly resistant to
both extreme temperatures and high pressures; hence it is used as a lubricant and anticorrosion agent [15]. The structure, texture and appearance of molybdenum disulphide are
very similar to that of graphite; it is composed of sandwiched layers of molybdenum atoms
between the layers of sulphur atoms. The interactions between the sulphide atoms sheets are
weak and this is why MoS2 has a lubricating effect. Powdered MoS2 with particle sizes in the
range of 1-100 m is a common dry lubricant. It is also often mixed into various oils and
greases, which keep the lubricated mechanisms running for a while longer, even in cases of
almost complete oil loss this is an important factor that makes it very relevant to aircraft
engines. It is often used also in motorcycle engines, especially in two-stroke engines, which
are otherwise not well lubricated. MoS2 grease is recommended for constant velocity joint
(CV) and universal joints. It is also used as a lubricating additive to special plastics, notably
nylon and teflon. During the Vietnam war, a commercial molybdenum disulphide product,
10

"Dri-Slide", was used for lubricating troops'weapons; the military refused to supply it, as it
was "not in the manual", so it was sent to soldiers by their parents and friends privately.
Another application is for coating bullets, giving them easier passage through the rifle barrel
with less deformation and better ballistic accuracy. Self-lubricating composite coatings for
high temperature applications were developed at the Oak Ridge National laboratory. A
composite coating of molybdenum disulphide and titanium nitride was created on the surface
of parts by chemical vapor deposition.
1.3.3 Use in petrol-chemistry
Artificial MoS2 can also be used as a catalyst in petroleum refineries, specifically for
desulphurization of crude oil e.g. hydrodesulphurization. It has also been discovered that
doping with small amounts of cobalt and alumina can enhance its effectiveness as a catalyst.
This type of catalyst can be generated in-situ by treating molybdate/cobalt-impregnated
alumina with H2S or an equivalent reagent [8].
1.3.4 Other uses
Molybdenum trioxide (MoO3) is used as an adhesive to bind enamels and metals.
Molybdenum powder is also used in agriculture as a fertilizer for some vegetable plants, such
as cauliflower [15].

1.4 Occurence
Molybdenum commonly occurs in nature as the mineral molybdenite, MoS2, and can also be
found as veins in quartz rock [11]. Porphyry copper ores are characterized by sulphide
fractions containing traces of molybdenite which is usually separated as a flotation
concentrate containing up to 90% MoS2. This concentrate is normally characterized by high
rhenium concentration (about 700 ppm Re) and is a major source of this metal. It may also be
a source of uranium [1]. Though molybdenum is also found in such minerals as wulfenite
(PbMoO4) and powellite (CaMoO4), the main commercial source of molybdenum is
molybdenite (MoS2). Molybdenite is mined as a principal ore, and is also recovered as a byproduct of copper and tungsten mining such as in the porphyry copper ore aforementioned.
Molybdenum is the 42nd most abundant element in the universe, and the 25th most abundant
element in Earth'
s oceans, with an average of 10.8 mt/km. The Russian Luna 24 mission
11

discovered a single molybdenum-bearing grain (1 0.6 m) in a pyroxene fragment taken


from Mare Crisium on the Moon [15].

Figure 1-2a: Molybdenite sample [17] Figure 1-2b: Molybdenite sample from Aitik.
(From a primary ore mine)

(From a secondary ore mine)

12

2 Recovery of molybdenite
Molybdenum ore can be mined either by underground or open-pit method as a primary ore
body and can also be produced as a by-product or a co-product of copper or scheelite
production. Typical primary ore body can contain 0.05-0.25% Mo and secondary ore bodies
from a copper porphyry ore with average of 0.3-1.6 % Cu can contain 0.01-0.05% Mo. The
preferred method for concentrating the mineral has been flotation. The flotation process starts
after grinding the ore to liberate the molybdenite singly or in combination with copper
sulphide or other sulphide minerals from the host rock, and then agitating the grounded ore
with water, a collector and other special chemicals to cause preferential wetting, settling
and/or suspension of the host rock particles, while the hydrophobic or un-wetted particles of
molybdenum and copper minerals are carried by air bubbles to the surface where they can be
subsequently recovered by a frothing agent [11].
Molybdenite belongs to the minerals group of easy flotation, which is related to its crystal
structure. Grounded particles of molybdenite present laminar structure that favors natural
hydrophobicity. This elevated hydrophobic capacity allows recovery of molybdenum
successfully from ores with low grades by flotation. The separation of molybdenum-copper
has been practiced for a long time using flotation technique. The predominant process is
normally to depress copper sulphides, capitalizing on the surface property of the easy
floatability of molybdenite. Several reagents have been used as depressant for copper
minerals, for example sodium cyanide, mainly used if copper is present as chalcopyrite. Other
reagents are certain types of sulphides such as sodium sulphide, sodium hydrogen sulphide or
phosphorous pentasulphide when there is a mixture of copper sulphides: bornite, chalcocite,
and chalcopyrite. There are other methods, which are not very common, this include the use
of sodium peroxide or sodium hypochlorite. The depressant agent mostly employed is sodium
hydrogen sulphide (NaHS), which is chosen considering environmental aspects. When the
reagent is added, the potential of copper sulphides is reduced to the point where they are unfloatable (eqns. 2-1 and 2-2).
2CuX(s) + HS- Cu2S + 2X- + H+

(2-1)

2CuFeS2 + HS- S22- + H+ +Cu2S(s) + 2FeS(s)

(2-2)

2HS- + 3/2O2 S2O32- + H2

(2-3)

HS- + 3/2O2 SO32- + H+

(2-4)

13

HS- + 2O2 SO42- + H+

(2-5)

Depression starts at redox potential of -250 mV and when the flotation is stable, the redox
potential is -450 to -500 mV for NaHS. Addition of NaHS allows for obtaining sulphides with
a fresh surface because it desorbs the collector, making its depression easy (eqn. 2-1). With
these conditions, molybdenite is ready for its recovery by flotation. Sometimes, it is useful to
add a little fuel oil, mainly when molybdenite can be associated with certain iron minerals.
It is very important to observe the slurry and try to understand what action is causing the
depression. Oxygen is not desirable in the slurry although with small or big dosages of NaHS,
there is certain amount of oxygen in the slurry, which reduces the sodium hydrogen sulphide
efficiency. The presence of dissolved oxygen in the slurry affect the flotation process because
it leads to an increase in redox potential and formation of sulphoxy species such as
thiosulphate ions (S2O32-), sulphite ions (SO32-), and sulphate ions (SO42-) (eqns. 2-3 to 2-5).
As a result, HS- ions are consumed by oxygen instead of copper sulphide, which give rise to
requirement of additional quantity of NaHS.
In summary, air addition promotes oxidation of sulphide ions to less active compounds. For
this reason nitrogen is commonly employed as flotation gas during rougher and cleaning
flotation stages. An option is to re-cycle used-air, if air is used as a flotation gas because as
the used air is depleted of oxygen, the nitrogen concentration increases. CO2 can be employed
as pH regulator, which forms a weak acid in the slurry; it can also be used to modify froth
texture by the formation of polysulphides in solution (S22-) through dissolution of So from
chalcopyrite surface [7].

14

3 Molybdenite production in Boliden


Boliden is one of the leading mining and smelting companies in Europe with operations in
Sweden, Finland, Norway and Ireland. Bolidens main products are copper, zinc, lead, gold
and silver. Exploration and recycling of metals are also important within the company. The
number of employees is approximately 4500 and the turnover amounts to approximately

3.8

billion annually. Its shares are listed on Stockholmsbrsens Large Cap list and on the
Toronto Stock Exchange in Canada [28].
A molybdenite concentrate has been produced in Boliden Mineral AB in a pilot test as a byproduct from copper concentrate. The copper ore at Boliden Aitik mine contains
approximately 0.004 to 0.008% Mo, initial studies of molybdenum flotation from the copper
concentrate was previously carried out in lab scale during 1981 to 1982, which lead to a grade
of about 30% Mo. However the investigation did not proceed in a pilot scale due to falling
price of molybdenum at that time.
Recent dramatic increase in price of molybdenum during 2004 and 2005 with a peak value of
US$ 103,000 per tonne in June 2005 [15] and to approximately US$ 65,000 per tonne as of 4
May 2007 has motivated renewed interests in the molybdenum production. A long-term price
is hard to estimate, but it is reasonable to forecast a price higher than before. A price of US$
13,000 per tonne has been used in some calculations. The forecast for the nearest coming
years is higher with decreasing level down to US$ 22,000 per tonne in year around 2010 [12].
The price recently is approximately US$ 70,000 per tonne according to Info Mine [13].
Pilot tests with molybdenum recovery in 2006 showed that the process could give good grade
and recovery with reasonable consumption of reagents. A good grade of averagely 53.8% Mo
and 1.65% Cu have been achieved at the pilot plant in Aitik with the use of NaHS as a
depressant agent and air as flotation gas [12].

3.1 Background
In every manufacturing or production set-up, quality of products and services are the most
important factor. When discussing the quality of molybdenum concentrates, the copper
concentration is an undesired impurity and is the most important aspect. Lead, phosphorus
15

and arsenic are also undesirable. There may also be issues concerning potassium, sodium, and
magnesium [12], but concerning the molybdenite concentrate production in Aitik, the most
important impurity is the copper concentration in the concentrate. A flotation circuit to extract
molybdenite from the copper by-products will be built in Aitik. The value of the molybdenite
concentrate will depend to a large degree on the extent of impurities in the molybdenite
concentrate. A number of leaching methods have been applied for the purification of
molybdenite concentrates.

3.2 Aim
This work aim to investigate different alternative leaching methods that can be used for
purification of the molybdenite concentrate from Aitik depending on the type of contaminant
to be leached and to study how well different methods are working on different contaminants
and how molybdenite is affected. The specific aim is to remove the copper concentration in
the molybdenite concentrate to a commercially acceptable minimum using different leaching
methods and selecting the optimum method that effectively reduce the copper concentration
with minimum dissolution of molybdenum. The major copper component of the Aitik
molybdenite concentrate is present as chalcopyrite.
The goal is to find the best leaching method for Aitik molybdenite concentrate that would be
employed in the construction of the plant that will be put into operation approximately in
2010.

16

4 Literature review
4.1 Purification of molybdenite concentrate
Generally, molybdenite concentrates are complex as they contain substantial quantities of
base metal sulphides and numerous quantities of gangue in form of oxides and silicates, but
the specific sulphide to be removed from the molybdenite concentrate considered under this
study is chalcopyrite. A number of attempts have been made to purify molybdenite
concentrates based on the premise that it is possible to selectively dissolve the associated
sulphides, oxides and gangue by leaching. These include leaching with:
1. Microorganisms with ferric sulphate [2]
2. Sulphuric acid [9]
3. Sulphuric acid with sodium dichromate solution [3]
4. Oxygen and halide e.g. CuCl2 [4]
5. Hydrochloric acid [18].
6. Hydrochloric acid with hydrofluoric acid [18].

4.1.1 Microorganisms
Bioleaching tests carried out in an orbital shaker at 150 rpm, 20 g/l pulp density with 5 %
(v/v) Sulfolobus BC extreme thermopile previously adapted to molybdenite at 68oC claimed
100% dissolution of copper after 15 days. Chemical leaching of the same sample with 10 g/l
Fe2(SO4)3 under the same condition indicate 100% dissolution of copper after 15 days but at a
slower rate compared to bioleaching [2]. However assays of the leach solution and solid
residue are not presented; this could have given better insight to whether Mo is affected in
anyway and also the complexity of the leach solution as regards to how it could be treated
and/or disposed afterwards with regard to the environment.

4.1.3 Sulphuric acid


It has also been claimed that more than 98% Cu and most other impurities could be extracted
with less than 0.5% Mo dissolution. In a pulp containing concentrated sulphuric acid (more
than 93%) and molybdenite concentrate in ratio 1:1 in a sulphation reactor at 160-190oC for 210 hours. The hot, acidic pulp discharging from the reactor is water leached, thickened,
filtered and washed to remove the soluble sulphates formed. Based on this claim a 250 kg/day

17

pilot plant was operated continuously for 12 000 hours using several different molybdenite
concentrates with Cu concentrations ranging from 1-9.2 % Cu and less than 0.1% Cu was
consistently achieved in the purified molybdenite concentrate. However operational variables,
reactor designs and material selections are critical to the success of the continuous process.
Two configurations of reactors were developed using glass and teflon linings. Heat transfer
oil jackets provided the necessary heat to maintain the reacting pulp at desired temperature. A
80 t/day commercial plant based on this process was projected [9].

4.1.4 Sulphuric acid with sodium dichromate solution, Na2Cr2O7


Leaching with 0.3 M H2SO4 and 0.12 M Na2Cr2O7 for 90 min at 100oC and 560 rpm claimed
to dissolve 95% copper with little dissolution of molybdenum [3]. The presence of chromium
in the leach solution is critical to environmental requirements.

4.1.5 Leaching with oxygen and halide e.g. CuCl2


A US patent have claimed effective reduction of copper concentration from a molybdenum
concentrate by subjecting the molybdenum concentrate to pressure oxidation in the presence
of oxygen and a feed solution containing copper (e.g. CuSO4) and halide (e.g. CuCl2) to
produce a solution containing copper and a solid residue containing molybdenum. The
solution may be combined with the feed solution to a second pressure oxidation in which a
copper concentrate is treated for the recovery of copper. [4]

4.1.6 Conventional leaching with chloride salts


Another US patent have claimed removal of copper, iron, and lead impurities from
molybdenum flotation concentrates by mixing the feed concentrates with a non-volatile
chloride salt, heating the mixture to a temperature of from about 200o to 350oC for a time
sufficient to activate the lead impurities in the concentrates so that they can be leached during
the subsequent leach step, and leaching copper, iron, and lead impurities from the heat-treated
concentrates with a mildly oxidizing leach solution containing chloride ions and having a pH
of 4 or less. Good homogenization of the chloride salt and the concentrates can be achieved
by thoroughly mixing the feed concentrate with an aqueous solution of the chloride salt. The
patent also stated that, it is advantageous to use an aqueous ferric chloride solution to leach
the heat-treated concentrates as the lead values leached from the concentrates can be
crystallized from the pregnant leach solution and the resulting spent solution can be recycled
without further treatment, by mixing it with the feed concentrates, or it can be treated to
18

oxidize its ferrous constituent to ferric and then recycled for repeated use as regenerated leach
solution [5]. Finally a United States Patent claimed impurity removal from molybdenite
concentrates by leaching the concentrates at a temperature of about 70oC with an aqueous
solution containing an alkali metal or alkaline earth metal chloride and an oxidizing chloride,
for example cupric and ferric chlorides [29].

4.1.7 Hydrochloric acid and hydrofluoric acid


The aforementioned attempts have recorded greater success in removal of sulphide minerals
but only the attempts with hydrochloric acid and hydrofluoric acid administered singly,
sequentially or in mixed mode have proved to remove both the oxides and silicates gangue as
well as the metallic sulphides effectively [18]. However operational variables, reactor designs
and material selections seem to be critical for the success of this process.

4.1.8 SO2/O2 as a strong oxidant


It has also been demonstrated that SO2/O2 can function as a strong oxidant in acidic medium,
which can oxidise Fe2+ to Fe3+. The Fe3+ can be used to leach copper sulphides minerals and
uranium oxides, the Fe3+ and H2SO4 can also be regenerated back as oxidants to leach more
copper sulphides and uranium oxides. [10]. Also SO2/O2 is useful for the oxidative
precipitation of Mn(II) as MnO2, from Co(II) and Ni(II) leach liquors at around pH 3-4 [6].

4.2 Molybdenum-water chemistry


Two dissolved substances

Relative stability of the dissolved substances


Oxidation number, Z = +6
1. HMnO42

log MoO4

HMoO

MoO42- + H+
= -6.00 + pH

Z = +3 to +6
2. Mo3+ + 4H2O

HMoO4- + 7H+ + 3e-

E = 0.39 0.1379 pH +
3. Mo3+ + 4H2O

0.0197 log HMoO 4

Mo

3+

MoO42- + 8H+ + 3e-

19

E = 0.508 0.1576 pH + 0.0197 log MoO


Mo

2
4
3+

Limits of the domains of relative predominance of the dissolved substances


1. HMoO4-/MoO42-

pH = 6.00

2. Mo3+/HMoO4-

E = 0.300-0.1379pH

3. Mo3+/MoO42-

E = 0.508-0.1576pH

Two solid substances

Limits of domains of relative stability of the solid substances


Z = 0 to +4
4. Mo + 2H2O

MoO2 + 4H+ + 4e-

E = -0.072-0.0591pH

Z = +4 to +6
5. MoO2 + H2O

MoO3 + 2H+ + 2e-

a. E = -1.091-0.0591pH
b. E

= 0.320-0.0591pH

One dissolved substance and one solid substance

Solubility of solid substances


Z = +6
6. MoO3 + H2O

HMoO4- + H+

a. log[HMoO4-] = -51.42 + pH
b. log[HMoO4-] = -3.70 + pH

Z = 0 to +3
7. Mo

Mo3+ + 3e-

E = -0.200 + 0.0197log[Mo3+]

Z = 0 to +6
8. Mo + 4H2O

MoO42- + 8H+ + 6e-

E = 0.154 0.0788pH + 0.0098log[MoO42-]


Z= +3 to +4

20

9. Mo3+ +2H2O

MoO2 + 4H+ + e-

E = 0.311 0.2364pH 0.0591log[Mo3+]


Z= +3 to +6
10. Mo3+ + 3H2O

MoO3 + 6H+ + 3e-

a. E = -0.623-0.1182pH - 0.0197log[Mo3+]
b. E = 0.317-0.1182pH - 0.0197log[Mo3+]
Z = +4 to +6
11. MoO2 + 2H2O

HMoO4- + 3H+ + 2e-

E = 0.429 0.0886pH + 0.0295log[HMoO4-]


12. MoO2 + 2H2O

MoO42- + 2e-

E = 0.606 0.1182pH + 0.0295log[MoO42-]

4.3 Equilibrium diagram and its interpretation


The relations above have been used by Pourbaix M et.al to draw the equilibrium diagram in
figure 4-1a which represents the conditions of thermodynamic equilibrium of the system
molybdenum-water at 25oC, in the absence of complexing substances and substances forming
insoluble salts.
Figure 4-2 represents the theoretical conditions of corrosion, immunity and passivation of
molybdenum in the presence of solutions free from substances with which this metal can form
soluble complexes or insoluble salts.
Figures 4-1a and 4-2 depict molybdenum as a base metal, as its domain of stability lies
completely below that of water. It is not found in nature in the native state.
In alkaline solutions, it has tendency to decompose water with the evolution of hydrogen gas,
dissolving in the hexavalent state as molybdate ions MoO42-. In the presence of noncomplexing acid solutions, it tends to dissolve in the trivalent state with the formation of Mo3+

21

ions and also evolution of hydrogen gas. In neutral or slightly acidic or alkaline solutions it
tends to cover itself with tetravalent dioxide MoO2.
In practice molybdenum is noticed to be attacked only slightly by dilute non-complexing acid,
only dilute nitric acid acting as an oxidizing agent attacks it appreciably, while concentrated
nitric acid covers it with a layer of MoO3 which protects the metal from further attack.
In hydrochloric acid the metal is slightly attacked and passivated, it is probable that a film of
insoluble chloride is formed which passivates the metal. Molybdenum in powdered form can
be oxidized by tap water and distilled water (free from CO2). Water turns blue when in
contact with molybdenum.

Figure 4-1a: Potential pH equilibrium diagram for the system molybdenum-water, at 25oC by
M.Pourbaix et al.

22

Figure 4-1b: Potential pH equilibrium diagram for the system molybdenum-water, at 25oC
drawn from thermodynamic software, Fact-Sage.

Figure 4-2: Theoretical conditions of corrosion, immunity and passivation of molybdenum, at


25oC
23

Figure 4-3: Influence of pH on the solubility of MoO3, at 25oC


Molybdenum is distinguished by a peculiar behavior with regard to passivation: depending on
the pretreatment of the metal it is either active or passive; chemically passivating reagents are
not only oxidizing agents such as nitric acid concentrated chromic acid and ferric chloride but
also dilute hydrochloric acid and sulphuric acids; the highest degree of passivation is however
obtained by anodic polarization under certain conditions of current density. Activation of the
metal is produced chemically, by KOH or NH3 and reducing agents, or electrochemically by
cathodic polarization in a solution of KOH. This behavior peculiar to molybdenum seems to
be in agreement with the equilibrium diagram, according to which, in alkaline media the
metal is constantly active and dissolves as molybdate ions MoO42- by oxidation, while in acid
media it is liable to dissolve at first as Mo3+ at relatively low electrode potentials and cover
itself with a passivating layer of MoO2 or MoO3 [lines (9) and (10) of Fig.4-1a] at higher
potentials. The passivation of molybdenum in acid media may also be due to the formation of
a film of insoluble salt.
According to fig.4-1a molybdenum can be obtained electrolytically from acid solutions of
molybdenum salts or alkaline solutions of molybdates. In practice, the electrolytic reduction
of the molybdenum chlorides gives a positive result only in non-aqueous solutions, for

24

instance solutions of MoCl2 and anhydrous HCl in absolute alcohol. The usual processes for
the electrolytic separation of molybdenum are however based on the electrolysis of the molten
salts (a mixture of calcium molybdenate and molybdenum carbide in bauxite, or a molten
mixture of sodium and molybdenum chlorides).

4.3.1 Stability of the compounds of trivalent molydenum


The molybdenous ion Mo3+ is stable only in strongly acidic reducing media, on being
oxidized, the Mo3+ ions are slowly converted into a red compound whose composition is
unknown, but according to fig.4-1a the principal oxidation product should be the purplebrown oxide MoO2.
The dehydration of Mo(OH)3 by warming always give rise to oxidation to MoO3, even in a
current of hydrogen, it is most probable that the water contained in the hydroxide acts as an
oxidizing agent at the temperature necessary for the dehydration.

4.3.2 Stability of the compounds of tetravalent molybdenum


Tetravalent molybdenum is known only in solution in the form of complex ions, which are
not considered in figure 4-1a.
By reducing ammonium molybdate solutions with hydrogen at ordinary temperature and
pressure in the presence of colloidal palladium, a brown-black hydroxide Mo(OH)4 (or
MoO2.2H2O) is formed; by drying this hydroxide carefully in the cold the monohydrate
MoO2.H2O [or MoO(OH)2] is obtained; if the hydroxide is dried by warming the brownpurple anhydrous oxide MoO2 is obtained, which, of these three forms of oxide, is the only
one considered in figure 4-1a. This oxide MoO2 can be obtained by other means, for example
by heating molybdenum in air, or in water vapour, by reducing solutions of MoO3 with metals
such as Zn, Cd, Mg, and by the electrolytic reduction of molten MoO3.
From fig.4-1a strong non-oxidising acid should cause MoO2 to split up into molybdenous ions
Mo3+ and the acid molybdate ions HMoO4- [according to the family of lines (9) and (11)] with
the possible formation of molybdenum blue and MoO3. Non-oxidising alkali should cause
MoO2 to split up into molybdate MoO42- and metallic molybdenum [according to the family
of lines (12) and line (4)], which would react with water to form molybdate and hydrogen;
oxidizing alkalis should convert it into molybdate.
In actual fact, MoO2 is oxidized by nitric acid to MoO3, but it is, in general, insoluble in nonoxidizing acids. In the present of aerated water Mo(OH)4 is easily oxidized by forming a
25

solution of molybdenum blue; it is soluble in concentrated acids, forming solutions which


are red to purplish brown and are feebly reducing; it was not clear if the reducing property
was due to the formation of trivalent Mo3+, or to the existence of complexes of tetravalent
molybdenum.

4.3.3 Stability of the compounds of pentavalent molybdenum, molybdenum blue


Pentavalent molybdenum compounds are also known only in solution in form of complexes
just like tetravalent molybdenum. The hydroxide MoO(OH) or pentavalent Mo2O5.3H2O,
molybdenyl hydrate, is obtained as a dark-brown precipitate by treating a solution of
ammonium molybdenum oxychloride (NH4)2 (MoOCl5) with NH3. Due to lack of availability
of thermodynamic data, no derivative of pentavalent molybdenum could be considered
quantitatively in the figure. It was pointed out that Mo2O5.3H2O is easily oxidized by air, and
seems liable to decompose into compounds of tri- and hexavalent molybdenum: when it is
treated with KOH in an atmosphere of hydrogen, it is partially converted into Mo(OH)3 and
the solution contain molybdenum in the hexavalent state.
The dehydration product of MoO(OH)3 is the oxide Mo2O5, which can also be obtained by
reduction of MoO3; it is a purplish-black powder which is very sparingly soluble in acids.
Together with the compounds of pentavalent molybdenum, molybdenum blue can be
considered a compound containing oxygen and molybdenum whose percentages of oxygen
and molybdenum fits approximately the formula Mo3O8, an oxide in which molybdenum
would have valency between +5 and +6; however, it is usually considered to be a molybdenyl
molybdate Mo2O5.xMoO2. It is a blue compound which is very soluble in water and easily
forms colloidal solutions; it is obtained either by reduction of molybdate solutions or by the
oxidation of lower oxide such as MoO2.

4.3.4 Stability of the compounds of hexavalent molybdenum


The compounds of the hexavalent molybdenum are the most important ones; they are
illustrated by molybdenum trioxide or molybdic anhydride MoO3, by its hydrates (molybdic
acids) and by its dissolved forms, principally the molybdate ion MoO42- obtained by the
action of alkalis on MoO3. By varying the relative quantities of MoO3 and alkalis a whole
series of salts can be obtained: the di-, trimolybdates, etc; to these various salts there should
be various condensed ions. Studies on molybdate solutions by diffusion measurements and
26

conductometric titrations have shown that the nature of the ions varies with the pH in such a
way that a domain of stability can be attributed to each of them; for example:
6 < pH < 14

MoO42-

4.5 < pH < 6

Mo3O114-

1.5 < pH 4.5

Mo6O216-

0.9 < pH 1.5

Mo12O4110-

pH = approx. 0.9

Mo24O7812-

This complex range of substances has been symbolized by the ion HMoO4- in establishing the
equilibrium diagram.
The oxide MoO3, prepared by roasting ammonium molybdate, is a white powder; its
solubility in water is about 2 g/l i.e 10-1.85 mole/l, which is in agreement with figure 4-3. It
does not combine directly with water to give hydrates; these are obtained only from
molybdates; there exists two well-defined hydrates MoO3.H2O and MoO3.2H2O.
The fairly close solubility values for MoO3 and its two hydrates show that these three
compounds have stabilities which are practically equal; the domain of stability attributed to
MoO3 in the equilibrium diagram in fig.4-1 can therefore also be attributed to one of its
hydrates. The influence of pH on the solubility of MoO3 is represented in fig.4-3; the
characteristics of the solution obtained by dissolving this oxide in pure water until a saturated
solution is obtained are given in this figure by the coordinates of the point of intersection of
this solubility line with the line showing the values of [(H+)-10-7]; these characteristics are:
pH = 1.85, [HMoO4-] = 10-1.85, i.e. 2 g MoO3/l.
Molybdic solutions treated with hydrogen peroxide give rise to the formation of the so-called
permolybdates, which are yellow-orange in acid media and intense red in alkaline media. On
account of lack of precise data relating to these compounds, in which molybdenum would
have a valency of +7, it is not taken into account in establishing the equilibrium diagram in
which they appear purely as a guide [22].

27

4.4 Cu-CN chemistry


Copper can dissolve in cyanide solution to form different copper-cyanide aqueous complexes,
known as cyanocuprate ions, this includes, Cu(CN)2-, Cu(CN)32- and Cu(CN)43- The
complexes have been confirmed to undergo the following successive equilibrium steps in
reaction with free and un-dissociated hydrocyanic acid:
CuCN

Cu+ + CN-

CuCN + CN-

Cu(CN)2-

Ksp

(4.3-1)

K2

(4.3-2)

Cu(CN) + 2CN-

Cu(CN)2-

(4.3-3)

Cu(CN)2- +CN-

Cu(CN)32-

K3

(4.3-4)

K4

(4.3-5)

Ka

(4.3-6)

Cu(CN)32- + CNHCN

Cu(CN)43-

H+ + CN-

The equilibrium constants for copper cyanide complexes differ among different authors, due
to different methods of measurement and the processing of data [32]. However the calculated
constants listed in table 4-1 have a common agreement.

Table 4-1: Equilibrium constants for copper cyanide system


log Ka

log Ksp

log

25

-9.21

-20

40

-8.84

50
60

Temperature

log K3

log K4

24

5.3

1.5

-19.1

22.98

4.91

1.11

-8.60

-18.33

22.35

4.67

0.86

-8.41

-17.6

21.75

4.45

0.64

oC

Cupric ions react with CN- to form cupric complexes, which are unstable and decompose
rapidly. The distribution and equilibrium potential of copper cyanide species has been found
to depend on the mole ratio of cyanide to copper, total cyanide concentration, pH and
temperature. With increasing CN:Cu mole ratio, the distribution of copper cyanide species
shifts more completely to the highly coordinated complex (Cu(CN)43-). The equilibrium
potential for Cu(I)/Cu decreases with increasing CN:Cu mole ratio. Increasing pH is directly
proportional to increasing the free cyanide concentration. Increasing temperature gave rise to
reduced stability constants. Therefore the distribution of copper cyanide shifts to the lowly
coordinated complexes. The potential measurements have been carried out to confirm the
validity of the calculated results in table 4-1. The potential-pH diagrams shows that the copper
28

complexes, CuCN, Cu(CN)2-, Cu(CN)32- and Cu(CN)43- can predominate in different pH


regions. The free energy data for all species are listed in table 4-2 all the potential-pH
diagrams were calculated based on the data in table 4-2

Table 4-2: Gibbs energy data for copper and cyanide species (J mol-1) [32]

Figure 4-4: CN-H2O potential-pH diagram at all solute species activities of 1 and P(CN)2 = 1
atm and 25oC assuming HCNO and CNO- are stable [32].
Figures 4-4 and 4-5 show the potential-pH diagram for the CN-H2O system assuming that
CN-, CNO-, HCN, HCNO and (CN)2 are stable, although not all of them are stable in
practise. CN- and HCN are oxidised at high potential range and are not stable, they are
however metastable at low potential range shown in figures 4-4 and 4-5 as the potentials for
their oxidation are are much higher (1.0 - 1.2V). Hence they are considered stable in Cu-CNH2O potential-pH diagram.

29

Figure 4-5: CN-H2O potential-pH diagram at all solute species activities of 1 and P(CN)2 = 1
atm and 25oC assuming (CN)2 is stable [32].

30

Figure 4-6: Potential-pH diagrams for Cu-CN-H2O system at 25oC at all solute species
activities of 1, assuming Cu(OH)2 as a stable species, HCNO, CNO- and (CN)2 are not
considered [32].
Figure 4-6 depicts the potential-pH diagram at the activities of all species equal 1, CuCN,
Cu(CN)32-, and Cu(CN)42- are shown to be stable in the three pH regions; -2 to 4.5, 4.5 to 8
and 8 to16 respectively.

Figure.4-7: Potential-pH diagrams for Cu-CN-H2O system at 25oC and all solute species
activities of 10-2, assuming Cu(OH)2 as a stable species, HCNO, CNO- and (CN)2 are not
considered [32].
Figure 4-7 depicts the potential-pH diagram at the activities of all species equal 10-2, CuCN,
Cu(CN)2-, and Cu(CN)32- are shown to be stable in the three pH regions; -2 to 4.5, 4.5 to 6 and
6 to 16 respectively.

31

Figure 4-8: Potential-pH diagrams for Cu-CN-H2O system at 25oC and all solute species
activities of 10-6, assuming Cu(OH)2 as a stable species, HCNO, CNO- and (CN)2 are not
considered [32].
Figure 4-8 depicts the potential-pH diagram at the activities of all species equal 10-6, only
CuCN, and Cu(CN)2-, are shown to be stable in the three pH regions; -2 to 4.5 and 4.5 to 16
respectively.

32

Figure 4-9: Potential pH diagram for Cu-CN-H2O system at 25oC and solute copper species
activities of 0.01 and cyanide species activities of 0.1 considering Cu(OH)2 as a stable
species. HCNO, CNO- and (CN)2 are not considered [32].
Figure 4-9 shows the potential-pH diagram at the activities of copper species equal 0.01 and
activities of cyanide species equal to 0.1 it can be seen that all copper-cyanide species are
stable in their correponding pH regions [32].
Generally copper cyanide species are stable in certain potential and pH regions, with
increasing potential copper cyanide can be oxidised to Cu2+, Cu(OH)2 or CuO and CuO2-.
Cyanide can also be oxidised to cyanate based on thermodynamics data [32].

33

4.5 Leaching theory


4.5.1 Leaching under pressure
The leaching method suitable and commonly adopted for the purification of molybdenite
concentrate is pressure leaching.
Pressure leaching can be broadly divided into two types namely:
(i) In absent of oxygen: In this case the ore is heated with the leaching agent above the boiling
point of the solution to achieve a high reaction rate. Therefore the process must be carried out
in a closed vessel that can withstand the vapor pressure of solution at that temperature. An
example is leaching of bauxite with caustic soda solution
(ii) In present of oxygen: Here the pressure in the autoclave (reactor) is due to the solution
pressure as well as oxygen pressure (or air pressure if air is used instead of oxygen). This
method is used mainly for leaching sulphide ores or uranium oxide ores [1]
The method adopted in this study is a form of pressure leaching in the present of oxygen or air
with some modification with addition of sulphur (iv) oxide, SO2 in some tests.

4.5.2 Leaching theory


Factors influencing the rate of leaching process can be summarized in the following points:
1. Rate of leaching increases with decreasing particle size of the ore since the smaller the
particles the larger is the surface area per unit weight.
2. If a leaching process is diffusion controlled then it will be greatly influenced by the
speed of agitation. On the other hand if it is chemically controlled then it will not be
influenced by agitation, provided that enough agitation is done to prevent the solids
from settling.
3. Leaching rate increases with increasing temperature. However, this increase is much
less remarkable for a diffusion-controlled process than for a chemically controlled
process.
4. Rate of leaching increases with increasing concentration of the leaching agent.
5. Rate of leaching increases with decreasing pulp density, i.e. when a large volume of
leaching agent is added to a small volume of solids.
6. If an insoluble reaction product is formed during leaching, then the rate will depend on
the nature of this product. If it forms a nonporous layer, then the rate of leaching will
greatly decrease. If however, the solid product is porous, it will not affect the
rate[14].
The particle size distribution of the material used in this test is shown in table 5-1.
34

5 Experimental
5.1 Material
The feed material for purification used in the tests is a molybdenite flotation concentrate from
Aitik whose chemical composition is given in table 5-2, particle size analysis in table 5-1 and
can also be viewed in figure 5-1. The mineral phases identified by XRD in the concentrate are
mainly molybdenite (MoS2) and chalcopyrite (CuFeS2) as shown in figure 5-2.

Table 5-1: Particle size distribution of feed ore


wt %

4.4

10.3

20.2

41.6

9.8

13.7

Apparent particle size, m

+90

-90, +63

-63, +45

-45, +20

-20, +10

-10

The particle size distribution of the ore indicated that it was fine enough with 65% below 45
m (350 mesh) and 4% over 90 m (170 mesh). This ensures enough surface area per unit
weight of the ore. The leaching process in this case is chemically controlled and stirrers kept
the material evenly suspended in the pulp as shown in the experimental set-up, figure 5-5.

Table 5-2: Head assays: chemical analysis of the molybdenite concentrate used in this work
Mo
Cu
Pb
Fe
S
Au
Ag
Bi
Hg
Ca
Cl
%
%
%
%
%
g/t
g/t
%
%
%
%
46
2.13
0.019 2.83
37.4
1.6
98
0.011 0.0016 0.11
<0.1

Figure 5-1: Feed molybdenite concentrate to be purified

35

Figure5-2: XRD analysis of the feed molybdenite concentrate


The XRD analysis, figure5-2 shows the main mineral phases present in the feed material. The
high peaks corresponds to molybdenite as the dominant mineral and the low peaks
corresponds to traces of chalcopyrite being the main copper mineral present as impurity in the
concentrate. Details of XRD analysis equipment and procedure are presented in appendix II.

5.2 Reactors
Only one type of experimental set up was used for all the experiments. The experiments were
carried out in round bottom glass reactors of varying capacities (1000-3000 ml) with five
openings and capacity to withstand heating temperature above 100oC. The central opening of
the reactor was used to connect and adjust the shaft of the stirrer, while the other openings
were fitted with a programmable thermometer to automatically regulate the heat supply at the
programmed temperature, a water condenser to prevent and/or reduce evaporation during
heating and leaching, one or two hose(s) as the case may be to supply the appropriate gas(s)
into the pulp. Heat is supplied by an electro-mantle heater, which is automatically regulated
by the programmable thermometer. The stirrer speed was 500 rpm. The experimental set-up is
shown in figure 5-3 below.

36

Figure 5-3: Experimental set-up

5.3 Methodology
Leaching was carried out at both high and low temperatures; the cyanide leaching was carried
out at 25oC, the ferric chloride leaching was carried out at temperature ranging between 70oC
and 100oC, while the optimum temperature for the ferric sulphate leaching tests was 65oC.
The leaching reagent for cyanide leaching was added approximately based on stoichiometric
requirements for the cyanide only test and was in excess of stoichiometric requirement for
the cyanide + calcium chloride test, the pH was constantly maintained above 11 with
addition of sodium hydroxide pellets. The leaching reagent for ferric chloride test was
stoichiometric concentration of ferric chloride with appropriate estimation of copper chloride
and calcium chloride, the pH was kept at about zero with addition of hydrochloric acid. The
leaching reagent for ferric sulphate leaching was stream of Fe3+ produced by SO2/O2
oxidation; the pH was kept below 0.5 initially with addition of sulphuric acid.

5.4 Test performance


5.4.1 Cyanide leaching
Sodium cyanide (NaCN) was used as the leaching agent. Sodium hydroxide (NaOH) was used
as a pH regulator and to eliminate any contamination of the concentrate by gypsum
precipitation. Calcium chloride (CaCl2) was added to one of two set-ups as inhibitor of
molybdenum dissolution, oxygen and air was used separately as oxidizing agents. Copper

37

analysis in leach solution was carried out with the aid of atomic absorption
spectrophotometer, AAS. Detail of AAS and procedure of copper analysis is presented in
appendix II.
Seven experiments were planned to be carried out according to table 5-3 with temperature and
NaOH as variable factors and with leaching time, %solid, NaCN and CaCl2 as constant
factors. It was however reduced based on former experience and logistics reasons.

Table 5-3: Design of cyanide experiment with modde software


Experiment Leaching

Solid

Temperature NaOH

NaCN

CaCl2

No

time

concentration

kg/t

kg/t

kg/t

Hours

%Solids

72

20

20

90

90

150

72

20

80

90

90

150

72

20

20

300

90

150

72

20

80

300

90

150

72

20

50

195

90

150

72

20

50

195

90

150

72

20

50

195

90

150

The design of cyanide leaching conditions was based on Boliden in-house experience with
respect to leachability of chalcopyrite from pyrite by cyanide solution based on the in-house
experience of the 4:1 rule of thumb i.e. four moles of cyanide to one mole of gold; this
normally is for gold leaching but it also works to some extent for copper leaching because the
leaching solution from gold leaching is found to always contain some copper-cyanide
complexes in form of either Cu(CN)2-, Cu(CN)32-, or Cu(CN)43-.
In cyanide leaching of chalcopyrite, possible stoichiometric relations are expressed in
equations 5-1, 5-2 and 5-3 (also in section 4.4) and the overall relation in equation 5-4. The
equations depict cyanide-consuming reactions. However it has been confirmed that formation
of CNO- is very negligible. Hence only (5-2) and (5-3) are valid i.e. one mole of copper
requires three moles of cyanide for dissolution and formation of one mole of Cu(CN)32complex, and also three moles of cyanide is required for the formation of three moles of
thiocyanide complex,(SCN-)[30].

38

2CN- + O2

2CNO-

3CN- +3/8 S8
Cu + 3CN-

(5-1)

3SCN-

(5-2)

Cu(CN)32-

(5-3)

CuFeS2 + 6CN- + H2O + 1/8S8 + O2 + H+

Cu(CN)32- + 3SCN- + Fe(OH)3(s)

(5-4)

The mole and mass ratio of Cu:SCN and CN:Cu was found to vary between 2 and 3 from
analytical results of cyanide leaching tests on Aitik final cleaner tailing, see appendix VII.
Hence the total cyanide requirement for this test was calculated based on the 3 moles
requirement for dissolution of Cu and S as shown in appendix II.
The leaching tests were carried out batch-wise at two different leaching conditions in
oxidative environment. The first experiment was carried out using only NaCN as the leaching
agent, and the other was carried out using NaCN with addition of CaCl2 in order to confirm an
earlier observation that it inhibits the dissolution of Mo [12]. The two experiments were
carried out at ambient temperature 25oC and oxygen was used as oxidative gas. Although the
effect of air as an oxidative gas was previously observed in two preliminary experiments; the
use of air gave rise to flotation in the pulp, this may be as a result of the small volume of the
laboratory reactor, however this effect could be negligible in a pilot or a large scale reactor,
hence air could be a cheaper alternative oxidative gas to oxygen. The duration of the
experiments was 48 for the test with only NaCN and 72 hours for NaCN+CaCl2 test.
The leaching conditions and total amounts of additives are summarized in table 5-4.

Table 5-4: Leaching conditions and additives for cyanide leaching.


Test

Leaching Pulp

solid Temp

time

concentration

Hours

%-Solids

NaCN + 72

NaOH

NaCN

CaCl2

kg/t

kg/t

kg/t

Oxidizing
gas

20

25

100

150

600

O2

20

25

25

100

O2

CaCl2
NaCN

48

The redox potential measured throughout the experiment varied between 0.1V to 0.2V. The
detailed procedure, protocol and material balance can be found in appendix I.

39

5.4.2 Ferric chloride (FeCl3) leaching


Ferric chloride, (FeCl3) and cupric chloride (CuCl2) were used as oxidizing reagents and
calcium chloride (CaCl2) was added in order to elevate the boiling point of the solution as
well as to enhance the extraction rate of copper from the concentrate by complex formation
[29]. Hydrochloric acid was added as a pH regulator, air was supplied for aeration. Copper
analysis in leach solution was carried out with the aid of AAS.
Five experiments were planned to be carried out with only temperature as variable factor
while leaching time, %solid, FeCl3, CuCl2, HCl and CaCl2 were constant factors. It was
however limited to one experiment because the temperature was observed to vary between 70
and 110oC during the experiment, due to the exothermic reactions.
The design of the ferric chloride leaching conditions was based on examples found in the US
patent, No 3674424. The patent claimed removal of sulphide impurities from molybdenite
concentrates with aqueous solution containing an alkaline metal or an alkaline earth metal
chloride and an oxidizing chloride,for example ferric chloride and cupric chloride. A number
of examples in the patent showed that the process was more effective with solution
concentration containing 20% CaCl2 as the alkaline earth metal chloride, 10% FeCl3 and 1%
CuCl2 as oxidizing chlorides [29]. The concentration of the oxidizing metals was estimated in
such a way that it is sufficient for the desired extraction of copper from the molybdenite
concentrate with regard to the stoichiometric concentration as can be observed in equation (57) and (5-8) respectively. The stoichiometric concentration required at least 4 moles of FeCl3
and 3 moles of CuCl2 to leach one of Cu from the chalcopyrite in the concentrate.
CuFeS2 + 4FeCl3

CuCl2 + 5FeCl2 + 2S

(5-7)

CuFeS2 + 3CuCl2

4CuCl + FeCl2 + 2S

(5-8)

Although it was stated that cupric and ferric chloride could be deployed singly, but deploying
them in a mixed mode was observed to have a synergistic effect [29]. Hence the mixed mode
approach was employed in this test. The leaching test was carried out batch-wise oxidative
environment. The experiment was done using, 20% CaCl2, 10% FeCl3 and 1% CuCl2 as
leaching reagent at a temperature between 70 and 110oC and air was also used as oxidative
gas for 4 hours. The leaching conditions and total amounts of additives are summarized in
table 5-5.

40

Table 5-5: Leaching conditions and additives for ferric chloride leaching.
Test

Ferric

Leaching Pulp

solid Temp

time

concentration

Hours

%-Solids

35

FeCl3

CuCl2

CaCl2

kg/t

kg/t

kg/t

Oxidizing
gas

70-110

186

18.6

372.1

Air

chloride
The detailed procedure, protocol and material balance can be found in appendix I.

5.4.3 Ferric sulphate Fe2(SO4)3 leaching


Iron II sulphate hexahydrate (FeSO4.6H2O) was used as initial source of Fe2+. A mixture of
SO2 and O2 gases was used as oxidizing agent to oxidize Fe2+ to Fe3+; the regenerated Fe3+
served as leaching reagent. Fe3+ and Fe-total analysis in the solution was done with the aid of
absorption spectroscopy. Analysis of copper concentration in the leach solution was carried
out with the aid of AAS. The oxygen gas and sulphur dioxide were metered separately with a
5 mm diameter hose as shown in figure 5-3 before feeding directly into the pulp.
Concentrated sulphuric acid was carefully added to maintain the pH below 0.5 during the
tests.
The design of ferric (Fe3+) sulphate leaching tests was based on the claim by [6], [10], and
[21] that Fe3+ can serve as an oxidant to leach some metal sulphides and oxides including
copper sulphides and uranium oxides in acidic medium. The claims demonstrated leaching of
naturally occurring chalcocite and chalcocite concentrates [10], precipitation of manganese
[6] and leaching of uranium [21] with Fe3+ and the regeneration of Fe3+ using SO2/O2.
Preliminary tests were carried out to determine the kinetics of Fe2+ conversion to Fe3+ using
SO2 and O2 combined in a ratio of 1:10, at the temperatures 25, 45, 65 and 80oC as shown in
figure 5-6 and a comparison test using only O2 at the temperature with fastest rate; 65oC
figure 5-7.

41

5000

80

4500

70
60

Fe3+ content in mg/l

3500
50

3000
2500

40

2000

30

1500
20

% of total Fe converted to Fe3+

4000

1000
10

500
0

0
0

20

40

60

80

100

120

140

160

180

200

Time in minutes

Figure 5-6: Rate of Fe2+ conversion to Fe3+ as a function of time at 25oC (), 45oC ( ) 65oC
( ) and 80oC ( ) using a mixture of 10% SO2 and 90% O2 as oxidizing gases and the
percentage of total Fe converted to Fe3+ at 65oC ( ).
The figure shows plots of concentration of Fe3+ generated in solution as a function of reaction
time. It can be seen that the fastest reaction rate was obtained at 65oC.

42

80

4500

70

Fe3+ content in ppm

4000

60

3500
3000

50

2500

40

2000

30

1500

20

1000

10

500
0
0

50

100

150

% of total Fe converted to Fe3+

5000

0
200

Time in min

Fig
ure 5-7: Fe3+ formation as a function of time at 65oC using SO2/O2 ( )and O2 ( )as oxidizing
gases and percentage of total Fe converted to Fe3+ using SO2/O2 ( ).
The figure shows a comparison between the rates of Fe3+ formation using SO2/O2 as well as
O2 separately. It can be seen that the SO2 have strong effect as an oxidizing agent when
combined with O2. It has greatly enhanced the conversion of Fe2+ to Fe3+ as can be seen in
figure 5-7. A kind of autocatalytic phenomenon can also be observed to have taken place after
60 minutes of reaction when about 470 ppm Fe3+ is present in solution with SO2/O2, a rapid
conversion rate can be seen in figure 5-7.
Stoichiometry relations of Fe2+ conversion to Fe3+ based on the mechanism proposed by
Zhang et al are shown in equations 5-9 to 5-16 [10] and leaching of chalcopyrite by Fe3+ in
equation 5-17.
SO2.H2O HSO3- + H+

(5-9)

HSO3- SO32- + H+

(5-10)

Fe3+ + SO32- FeSO3+

(5-11)

FeSO3+ Fe2+ + SO3-

Slow

(5-12)

SO3- + O2 SO5-

Fast

(5-13)

43

Fe2+ + SO5- + H+ Fe3+ + HSO5-

Fast

(5-14)

2Fe2+ + HSO5- + H+ 2Fe3+ + SO42- + H2O

Fast

(5-15)

2HSO5- SO42- + O2 + 2H+

(5-16)

CuFeS2 + 4Fe3+ Cu2+ + 5Fe2+ +2So

(5-17)

It involves the slow initial formation of a ferric sulphite complex and decomposition to
produce sulphite radical SO3-. This is followed by a fast reaction with O2 to form a peroxomonosulphate species SO5-, and subsequently HSO5-which is responsible for the oxidation of
Fe(II) and sulphite species[10]. From (5-17) four moles of Fe3+ is required for dissolution of
one mole of chalcopyrite to produce one mole of Cu2+ five moles of Fe2+ and two moles of
elemental sulphur. Hence it can be concluded that to start up the reaction the mole ratio of Cu
to Fe3+ can be taken as 1:4. The detailed procedure, protocol and material balance can be
found in appendix I.

44

6 Results and discussions


6.1 Cyanide tests
The results obtained from AAS analysis of copper concentration in leach solution was used to
calculate the copper recovery in the solution as well as the amount of copper remaining in the
concentrate, the same concentrates was sent for analysis. The copper recovery, the calculated
residual copper concentration remaining in concentrate and the analyzed copper concentration
were plotted as a function of time as shown in figure 6-1 for the sodium cyanide only test and
in figure 6-3 for the sodium cyanide + calcium chloride test.

100
90

Cu recovery %Cu

70

60
50

1.5

40
1

30
20

Residual Cu grade in conc.%Cu

2.5

80

0.5

10
0

0
0

10

20

30

40

50

60

Leaching time hrs

Figure 6-1: Copper recovery and residual grade in concentrates as a function of time using
sodium cyanide as a leaching reagent at ambient temperature. Cu recovery based on
calculated head ( ). Calculated residual Cu grade in concentrate ( ). Analyzed residual Cu
grade in concentrate ( ).
The recovery curve shows three different zones: first zone between 0 and 10 hours
characterized by very fast kinetics and follows almost a linear relationship, second zone
between 20 and 40 hours characterized by a slower kinetic and follows a separate linear
relationship from first zone and the third zone which is very slow and also follows a

45

relationship. It can be summarized as having a rapid leach rate, which slows down. It can be
observed from the diagram that approximately 91% recovery of copper in the solution was
achieved after 53 hours. The calculated and analyzed copper grade curves are reasonably
inversely proportional to the recovery curve as expected, although there is little deviation
between calculated and analyzed results; probably due to homogenization problems in the
pulp.
Handling of the final pulp was a bit complex in this test; it was difficult to filter the pulp and
to wash the solid residues because the pulp was thick which lead to laminar flow. This may be
due to the fact that the duration of leaching was long which gave rise to too fine particles due
to prolonged attrition. The color of the dry residue seems to be closer to that of commercial
molybdenite as shown in figure 6-2 below.

Figure 6-2: Purified molybdenite concentrate with sodium cyanide


Table 6-1: Head and Purified concentrate assays sodium cyanide leaching

Head

Mo

Cu

Pb

Fe

Bi

Ca

Clx

Hg

Au

Ag

g/t

g/t

49

0.55

0.02

35.9

2.53

0.023 0.16

0.1

0.0014 0.6

46

2.6*

0.019 37.4

2.83

0.011 0.11

<0.1

0.0016 1.6

98

Purified
concentrate

18

In addition to copper notable amounts of gold and silver dissolved in the experiment.
* The copper head assay was calculated from the analyzed copper concentration in the
pregnant solutions and the purified residues. It is a bit higher than the initial head analysis
(2.13%Cu) this could be due to sampling and homogeneity errors.

46

100
90

Cu recovery in solution %

70

60
1.5

50
40

30
20

Cu grade in conc. %Cu

2.5

80

0.5

10
0

0
0

10

20

30

40

50

60

70

80

Leaching time

Figure 6-3: Copper recovery and grade in concentrates as a function of time using sodium
cyanide and calcium chloride as leaching reagents at ambient temperature.
Cu recovery ( ). Calculated Cu grade in concentrate ( ). Analyzed Cu grade in concentrate
( ).
The curve also shows three different zones as the curve in figure 6-1: first zone between 0 and
20 hours which is also characterized by very fast kinetics and following almost a linear
relationship, second zone between 20 and 40 hours characterized by a slower kinetic and
following a separate linear relationship from first zone and the third zone which is very slow.
It can be summarized as having a rapid leach rate, which slows down with time.
It can be observed in the diagram that approximately 86% recovery of copper in the solution
was achieved around 48 hours, after which the recovery starts to decline although the
analyzed copper grade seems not to support this. The decline of recovery after reaching its
peak was also observed in a number of preliminary tests with cyanide. This was confirmed to
have resulted from reduced concentration of NaCN because the recovery normally rises again
after addition of more NaCN. Hence it can be concluded that based on the conditions of this
experiment, maximum recovery of the copper concentration into solution could also be
achieved within 48 hours.

47

Handling of the final pulp from this test was much more complex than that of the sodium
cyanide only test it was difficult to filter the pulp and to wash the solid residues because the
thickened pulp was much more laminar due to too fine particle sizes. The colour of the dry
residue was not similar to commercial molybdenite; it is ash like in colour as can be seen in
figure 6-4 and the particles are too fine; it is actually dusty. This may be due to the fact that
the duration of leaching was longer; 72 hours, which gave, rise to extensive and prolonged
attrition.

Figure 6-4: Purified molybdenite concentrate with sodium cyanide and calcium chloride
Table 6-2: Head and Purified concentrate assays sodium cyanide + calcium chloride leaching
Mo

Head

46

Cu

Pb

Fe

Bi

Ca

Clx

Hg

Au

Ag

g/t

g/t

2.13

0.019 37.4 2.83 0.011 0.11

<0.1

0.0016 1.6

98

Purified
concentrate

43
0.47 0.02 32.4 2.44 0.023 5.50 0.47 0.0012 0.4 7.0
In addition to copper, it can also be observed that substantial amount of gold and silver also
dissolved in the experiment.

48

6.1.1 Mo-losses to solution


The dissolution of molybdenum in cyanide leaching tests was negligible as can be seen in
figure 6-5. However, the addition of calcium chloride strongly lowered the dissolution.

Molybdenum recovery in %

0.4
0.35
0.3
0.25
0.2
0.15
0.1
0.05
0
0

20

40

60

80

Leaching time in hours

Figure 6-5: Mo-losses to solution as a function of time. Mo losses in CN test ( ). Mo losses in


CN+Cl test ( ).

6.1.2 Concentrate weight changes


An increase in weight of the concentrate (approximately 7%) was observed in sodium cyanide
+ calcium chloride leaching which also was observed in the preliminary experiments, while
all other leaching experiments gave weight losses. This could be due to precipitation of
compounds like for example gypsum which could have been induced by increased calcium in
residue. Purified concentrates samples was subjected to XRD analysis in order to identify the
precipitated substance but none of the possibly precipitated compound could be found.
Therefore the precipitated compound could be a non-crystalline substance. This may have
contributed to the slow filtration rate observed in the experiment.

6.1.3 Oxidising gases


Oxygen was mainly used in the cyanide leaching experiments; however air was also used in a
number of preliminary tests. The major difference observed between the use of air and pure
oxygen as oxidising agents was that, the pulp was floating after two hours with air as
oxidising agent (which could have lead to incomplete reaction in the pulp because large

49

amounts of material stocked to the wall of the reactor cover. When pure oxygen was used, the
pulp was more stable. The problem with floating is most probably smaller in large scale
reactors. Hence the use of air as oxidising agent could be more reasonable in large scale.

6.2 Ferric chloride (FeCl3) leaching


The results of the copper concentration in leach solution obtained from AAS analysis was
used to calculate the copper recovery in the solution as well as the copper concentration
remaining in the concentrate, the same concentrates was sent for analysis. The copper
recovery, the calculated copper concentration remaining in concentrate and the analyzed
copper concentration were plotted as a function of time as shown in figure 6-5 below.

Figure 6-5: Copper recovery and grade in concentrate as a function of time using ferric
chloride at high temperature above 70oC. Cu recovery ( ). Calculated Cu grade in concentrate
( ). Analyzed Cu grade in concentrate ( ).

50

The curve shows that the leaching rate is fast during the initial two hours and thereafter
becomes slower. It can be observed from the figure that approximately 76% copper recovery
into the solution was achieved after 4 hours leaching time.
Handling of the final pulp from this test was easier than handling the final pulps in the
cyanide test; it was easier to filter the pulp and to wash the dry wet residue, the average
particle size is more granular than the particle sizes of the residues from cyanidation tests and
the dry residue gave a brighter gray color with closer resemblance to normal commercial
molybdenite as shown in figure 6-6; this may be due to the fact that the duration of leaching
was shorter in this test than the cyanidation tests leading to less extensive attrition.

Figure 6-6: Purified molybdenite concentrate after ferric chloride leaching


Table 6-2: Head and Purified concentrate assays ferric chloride leaching
Mo

Head

Cu

Pb

Fe

Bi

Ca

Cl
%

Hg

Au

g/t

Ag

46

3.06* 0.019 37.4 2.83 0.011 0.11

<0.1

0.0016 1.6

g/t

49

0.65

0.003 37.8 1.40 0.004 -

0.0002 3.29 20

98

Purified
concentrate

The copper head assay was calculated from the analyzed copper concentration in the pregnant
solutions and purified residues. It was also found to be higher than the initial head analysis
(2.13% Cu) this is probably due to sampling and homogeneity problems. It can also be
observed that a substantial amount of lead, iron, bismuth, mercury, and silver was leached.

6.3 Ferric sulphate Fe2(SO4)3 leaching


The fastest conversion rate of Fe2+ to Fe3+ using an SO2/O2 ratio at 10% SO2 was obtained at
65oC as shown in figure 5-6.
51

5.0

520

4.5
515

3.5
3.0

510

2.5
2.0

505

1.5
1.0

Redox potential mV

Cu recovery in %

4.0

500

0.5
0.0

495
0

0.5

1.5

2.5

3.5

4.5

leaching time in hours

Figure 6-7: Cu recovery and redox potential as a function of time using a ferric sulphate
solution generated from a ferrous sulphate solution by oxidation with a mixture of sulphur
dioxide and oxygen combined at 10% SO2 and 90% O2 as oxidising gases at 65oC.
Cu recovery ( ). Redox potential ( ).
The leaching result at the optimum conditions for ferric generation is also shown in figure 67. It could however be seen that the result does not look really good but it shows that it works
to some extent with little extraction of copper, which probably could be improved upon based
on explanations by various previous works [23], [24], [33]: The major reason for the
ineffective leaching of copper is probably due to passivation of chalcopyrite at high redox
potential and lower temperature. The extent of copper extraction can however be increased at
elevated temperature and at lower potentials [23] [24]. It has also been demonstrated that
controlling the thermal and redox potential of the medium can counteract the passivation of
chalcopyrite [24]. Lowering the pH is another possibility [25].
The fact that chalcopyrite is the most refractory to leaching, among the copper sulphides,
makes the chemical leaching of chalcopyrite by an acidified solution of ferric sulphate
proceeds at a very slow rate. The rate of this reaction in the temperature range 50110 oC is
also very low and the decrease in the rate is due to the formation of a film (passivation),

52

which builds up on the surface of the mineral and opposes the electron transfer from
chalcopyrite to the ferric medium which is necessary for the redox reaction. Jarosite
(H(Fe)3(SO4)2(OH)6) formation on the surface of chalcopyrite is a possibility as shown in
equation 6-1 and figure 6-8 [33].
H+ + 3Fe3+ + 2SO42- + 7H2O

H3O(Fe)3(SO4)2(OH)6 + 6H+

(6-1)

Passivation
Jarosite
CuFeS2

H3O(Fe)3(SO4)2(OH)6

Figure 6-8: Passivation of chalcopyrite by jarosite


In order to improve the chalcopyrite-leaching rate, much effort has been made and several
catalysts have been proposed, silver ion being the most effective one. It is well known that
low concentrations of silver ions greatly accelerate the chalcopyrite leaching. Therefore, it is
necessary to employ a catalyst such as Ag (I) that kinetically activates the reaction between
chalcopyrite and Fe (III). It has been shown that there is a sharp increase in copper extraction
with addition of 0.2-3.0 mg Ag/g concentrate, further increases of the amount of catalyst have
little effect on the copper extraction [26]. Silver has been effectively recovered from residues
by leaching them with acidic brine medium with 200 g/L of NaCl and 0.5 M sulphuric acid
provided that elemental sulphur had been previously removed. High silver extractions (above
98 wt. %) were obtained in 1 h at 70oC for both concentrates. It is possible to obtain total
recovery of the silver added as a catalyst plus some of the silver originally present in the
concentrate by increasing the temperature to 90oC provided that the acid was not limiting
[26].
Handling of the final pulp from this test was easier; it was easy to filter the pulp and to wash
the dry wet residue, the average particle size was granular and the dry residue gave a gray
color with closer resemblance to the original molybdenite concentrate as shown in figure 6-9;
53

this may be due to the fact that the duration of leaching was short in this test leading to less
extensive attrition.

Figure 6-9: Treated concentrate from ferric sulphate leaching


The treated concentrate was not sent for analysis because the copper concentration in pregnant
solution was not substantial enough.

54

7 Conclusion
91% of the copper concentration in the concentrate was removed with sodium cyanide
in oxidative environment within 53 hours. The molybdenite in the purified concentrate
is about 85% (49% Mo and 36% S) and dissolution of molybdenum was less than
0.4%; however there is concentrate weight loss of about 7%.
74% of the copper was leached with a mixture of sodium cyanide and calcium
chloride solution in oxidative environment within 72 hours. The molybdenite
concentration in the purified concentrate had about 75% (43% Mo and 32% S).and
dissolution of molybdenum was only 0.1%; but there is a concentrate weight increase
of 7% which reduced the molybdenite concentration in the concentrate.
76% of the copper concentration was removed with a solution of ferric, copper and
calcium chloride in oxidative environment within four hours. The molybdenite
concentration in the purified concentrate is about 87% (49% Mo and 38% S) the
molybdenum dissolution has not been analyzed but the concentrate weight loss was
5%. However the kinetics of copper recovery indicated increased copper recovery
with time.
Ferric sulphate solution is not effective with only 4.5% copper removal based on the
pregnant solution analysis. The solid residue was not analyzed.
It is possible to reduce the material loss in pilot scale experiments, because most
losses in the lab scale experiments are due to sticking on the equipment used.

55

8 Suggested further work

Treatment of leach solution; It can be observed from the assays that a substantial
amount of Au and Ag also dissolved during cyanide leaching; hence the solution
can be routed through the gold leaching line and Au and other precious metals can
be recovered. The solution will therefore be treated at the final stage of former
cyanide destruction, hence requiring no separate treatment.

Effect of the concentration of cyanide should be closely studied by taken closely


range samples; this would be more practicable in a pilot scale because the quantity
of concentrate used in this lab scale was small.

The use of air as oxidising agent is more reasonable and cost effective and should
be tested also in the pilot scale.

Detailed reagent consuming reactions (cyanide consuming reaction etc) should be


determined in more detail in order to optimize the process.

Scanning electron microscope, SEM analysis should be carried out on the purified
concentrates in order to verify the precipitated compound, as it may be a noncrystalline compound that could not be detected by XRD analysis.

Recovery of free cyanide with addition of NaHS should be carried out and this
increases the possibility of copper recovery by complex formation and
precipitation of Cu2S.

Cu(CN)2 + NaHS,(S2-) Cu2S + CN-

Cu(CN)2- + HS CuS + S
It could be reasonable to test counter-current method of leaching with possible
bleeding periodically along the cycle in a pilot scale in order to speed up the
leaching rate.

56

References
[1] Fathi Habashi, Text book of Hydrometallurgy, Laval University, Quebec City, Canada,
second Edition
[2] P. Romano, M.L. Blazquez, F.J. Alguacil. J.A. Munoz, A. Ballester, F. Gonzalez (2001)
Comparative study on selective chalcopyrite bioleaching of a molybdenite concentrate with
mesophilic and thermophylic bacterial FEMS Microbiology Letters 196 (1), 71-75 (Volume
196 Issue 1 Page 71 March 2001) doi: 10. 1111/j.1574-6968.2001.tb10543
[3] Ruiz M.C. and Padilla R, Department of Metallurgical Engineering, University of
Concepcin Casilla 53-C, Concepcin, CHILI, Copper removal from molybdenite concentrate
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CODEN HYDRDA, 1998, vol. 48, n 3, pp. 313-325 (13 ref.)
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US2003124040.
[5]

Purifying

molybdenum

flotation

concentratesUnited

States

Patent

4083921

http://www.freepatentsonline.com/4083921.html
[6] W. Zhang, P. Singh and D. Muir., 2001. Oxidative preparation of manganese with
SO2/O2 and separation from cobalt and nickel. Hydrometallurgy 63 (2002) 127-135
[7] http://www.startprospecting.com/html/molybdenum-copper_separation_b.html
[8] Topse, H.; Clausen, B. S.; Massoth, F. E. "Hydrotreating Catalysis, Science and
Technology"; Springer-Verlag: Berlin, 1996.
[9] Continuos Decopperization Process for Molybdenite Concentrates Wilkomirsky, L
Arvena, J Copper 91 (Cobre 91); Ottawa; Ontario; Canada; 18-21 Aug. 1991. 1992
http://md1.csa.com/partners/viewrecord.php?requester=gs&collection=TRD&recid=1993094
40081MD&q=refining+of+molybdenite+concentrate&uid=790088489&setcookie=yes
[10] W. Zhang, .P .Singh, and D .Muir., 2000. SO2/O2 as an oxidant in hydrometallurgy.
Minerals Engineering, Vol. 13. No.13 pp.1319-1328. 2000
[11] Fathi Habashi, Handbook of Extractive Metallurgy, Vol. III, WILEY-VCH, 1997
[12] Pilot tests with Mo recovery in Aitik, Boliden in-house report, process technology,
September 2006.
[13] http://www.infomine.com/investment/metalschart.asp?c=Molybdenum&r=7d

57

[14] Fathi Habashi, Principles of Extractive metallurgy, Volume 2, Hydrometallurgy,


1980,pp. 18-19, Laval University, Quebec City,Canada
[15] http://www.dayah.com/periodic/?lang=en, under Mo
[16]http://upload.wikimedia.org/wikipedia/en/5/54/2005molybdenum_%28mined%29.PNG
[17] http://commons.wikimedia.org/wiki/Image:Molybdenite.jpg
[18] Manoj Kumar, T.R. Mankhand, D.S.R. Murthy, R. Mukhopadhyay, P.M. Prasad. 2006.
Refining of low-grade molybdenite concentrate. ScienceDirect Hydrometallurgy 86 (2007)
56-62.
[19] Website of China Tungsten Online (Xiamen) Manufacturing & Sales Corp.,
http://chinatungsten.com/ctop2.htm
[20] SADACI, websites, http://www.sadaci.be/molybdenum.html
[21] Elizabeth M. Ho, Clifford H. Quan ANSTO Minerals, PMB 1, Menai NSW 2234,
Australia Iron (II) oxidation by SO2/O2 for use in uranium leaching SciencDeirect
Hydrometallurgy 85 (2007) 183192
[22] Marcel Pourbaix, atlas of electrochemical equilibria in aqueous solutions Pergamon
press, (1966) pp 272-279
[23] G. J. Olson J. A. Brierley C. L. Brierley Bioleaching review part B: Progress in
bioleaching: applications of microbial processes by the minerals industries Appl Microbiol
Biotechnol (2003) 63:249257
[24] A.F. Tshilombo, J. Petersen, D.G. Dixon The influence of applied potentials and
temperature on the electrochemical response of chalcopyrite during bacterial leaching
Minerals Engineering 15 (2002) 809813
[25] D.B. Johnson, Importance of microbial ecology in the development of new mineral
technologies. Hydrometallurgy 59_2001.147157
[26] R. Romero, A. Mazuelos, I. Palencia, F. Carranza Copper recovery from chalcopyrite
concentrates by the BRISA process Hydrometallurgy 70 (2003) 205215
[27] cyanide Wikipedia, Wikipedia 2007. Answers.com 25 Jun. 2007
http://www.answers.com/topic/cyanide
[28] www.boliden.com
[29] Process for purifying molybdenite concentrates. United States patent.3673424
http://www.freepatentsonline.com/3674424.pdf
[30] Boliden Internal report.
[31] Atomic absorption spectroscopy. (2007, May 22). In Wikipedia, The Free Encyclopedia
Retrieved 21:55, July 4, 2007, from
58

http://en.wikipedia.org/w/index.php?title=Atomic_absorption_spectroscopy&oldid=13265717
8
[32] Jianming Lu, D.B. Dreisinger, W.C Cooper Thermodynamics of the aqueous coppercyanide system Hydrometallurgy 66 (2002) 23-36
[33] ke Sandstrm, Andrei Shchukarev, Jan Paul XPS characterization of chalcopyrite
chemically and bio-leached at high and low redox potential Minerals Engineering 18 (2004)
505-515

59

Appendix
Appendix I
Properties of molybdenum

Physical properties

Molybdenum is the second member of group 6 of the periodic table, with electronic
configuration [Kr] 4d6 5s1. It may have valency of 2, 3, 4, 5, or 6. It posses typical metallic
properties and lustrous silver-white colour in the massive state, and a dull grey colour in
powdery state. It has a body-centered cubic lattice with ao = 0.31472 nm. Accepted main
physical properties of molybdenum are given in table I-I below.
Table I-I Physical properties of molybdenum
Melting point, mp

2617-2623oC

Boiling point (101.3 kPa),bp

4612oC

Latent heat of fusion at mp

35.6 kJ/mol

Mean specific heat (0-100 C)

251 Jkg-1K-1

Density (20oC)

10.22g/cm3

Thermal conductivity (0-100oC)

137 Wm-1K-1

Electrical resistivity (20oC)

5.7 .cm
o

Temperature coefficient (0-100 C)

4.3510-3K-1

Elastic constants of poly crystalline metal


(20oC)
Youngs modulus

324.8 Gpa

Rigidity modulus

125.6 Gpa

Bulk modulus

261.2 Gpa

Poissons ratio

0.293

Linear coefficient of thermal expansion (0- 5.1 x 10-6K-1


100oC)
Standard electrode potential EoMo3+,Mo

-0.200V

Chemical properties.
The lustre property of molybdenum can be retained indefinitely especially when it has been
drawn into wires. Its oxide, molybdenum trioxide, MoO3 through electrolytic oxidation at
prolonged temperature below 600oC, passivates it. The oxide sublime at 600oC and rapid
oxidation occurs thereafter. The metal also burns in oxygen at 500 to 600oC and it gets
60

oxidised slowly by steam and also attacked by fluorine when it is cold and by chlorine and
bromine when it is hot. It is slightly affected by dilute acids and concentrated hydrochloric
acid. It can be dissolved by moderately concentrated nitric acids but gets passivated in
concentrated nitric acid. A mixture of concentrated nitric and hydrofluoric acid dissolves
molybdenum effectively. Molybdenum is practically unaffected by alkaline solutions and
fused alkali-metal hydroxides, but can be dissolved rapidly by fused oxidising salts such as
sodium peroxide, sodium or potassium nitrate or perchlorate. It can react with carbon, boron,
silicon and nitrogen on heating and it forms many alloys. It finds application in a variety of
catalyst as mentioned earlier (section 1.3.3) especially in combination with cobalt in the
desulphurisation of petroleum. Biologically; molybdenum enhances the performance of
enzymes in the reduction of nitrogen to ammonia and also in the reduction of nitrates [11].

Appendix II
Estimation of reagent for cyanide leaching

Total cyanide requirement for the test was calculated based on the 3 moles requirement for
dissolution of Cu and S as stated in equations (II-I) and (II-II) below:
MCu(CN)3- = nCN/Cu nCu MNaCN

(II-I)

MSCN = nSCN/Cu nCu MNaCN

(II-II)

MCu(CN)3- = Quantity of cyanide required for dissolution of Cu and formation of Cu(CN)32complex in gram.
MSCN = Quantity of cyanide required for formation of SCN- complex in gram.
nCN/Cu = mole ratio of CN: Cu
nSCN/Cu = mole ratio of SCN : Cu
nCu = number of mole of Copper in the concentrate in mol
MNaCN = molar mass of sodium cyanide in g per mole
Hence the total sodium cyanide requirement for the reaction, MCN is
MCN = MCu(CN)3- + MSCN
61

MCN was calculated to be approximately 20 g for this experiment.


This was calculated thus; nCN/Cu = 3 and nSCN/Cu = 3
The copper concentration in the concentrate is 2.13% Cu i.e. 4.26 g of Cu in 200 g
concentrate. Hence nCu = 4.26 g/63.55 gmol-1 = 0.0670 mol
MNaCN = 23 + 14 + 12 = 49 gmol-1
Therefore, MCu(CN)3- = 3 0.0670 mol 49 gmol-1 = 9.85 g
Also MSCN = 3 0.0670 mol 49 gmol-1 = 9.85 g
Hence MCN = MCu(CN)3- + MSCN = 19.71 g ~ 20 g NaCN required for complete dissolution of
Cu with formation of Cu(CN)32- and formation of SCN- complexes.
Procedure for cyanide leaching

The experimental set-up was as shown in figure 5-3, the concentrate and distilled water was
initially placed in the reactor and conditioned by heating the set-up to the specified
temperature, 25oC. The pulp solid concentration was initially 20%. Thereafter estimated
quantity of NaOH pellets (also CaCl2 in the second set-up) and NaCN were added along with
the supply of oxidative gas. The pH was constantly maintained above 11 throughout the
experiment by addition of NaOH pellets when required.
Pulp samples (pregnant solution) were taken periodically with the aid of a pipette; the sample
weight is always about 20 to 25 g (and it is assumed to be a true representative pulp sample).
The pulp sample is filtered to separate the solution from the solid residue. The density of the
solution is determined immediately after filtration (The weight of 5 ml of the solution was
measured and the density is calculated). The solution samples were analyzed for dissolved
copper concentration at Boliden Bioleaching Lab., with the aid of atomic absorption
spectrophotometer, AAS. The wet solid residues are oven-dried at about 70oC for about 72
hours. The dry weight of residue was measured accordingly and it was sent for analysis at
Rnskrs central laboratory.
At the end of the experiment, the final pulp was weighted filtered and washed respectively.
The density of the final solution was determined (also by measuring the weight of 5 ml of the
solution). The weight and density of wash water was also measured. The wet residue was also
oven-dried at about 70oC for about 72 hours. The dry weight of residue was measured
afterwards and it was sent for analysis.

62

Table I-II Protocol and reagent consumption NaCN


Leaching of Aititk Molybdenite concentrate to remove copper concentration by means of sodium cyanide
Protocol and reagent consumption
Date of Experiment
Reference number
sample
Material
Grinding time
Screen analysis, k80

of

2007-07-03/05
31334
Aitik Mo-conc

Test description
Test temperature

High
Cyanide
Leaching
25

Tare

0.00

kg

Copper concentration
Weight of material
Weight of solution
weight of pulp
%solid
Gross weight

2.60
0.20
0.80
1.00
19.51
1.00

%Cu
kg
kg
kg
%
kg

Solid density
solution density
Volume of pulp
Pulp density

4.30
1.03
0.8232
1.2148

kg/dm3
kg/dm3
litre
kg/dm3

Reactor+Pulp wt
Empty reactor wt
Final pulp weight

1085.80
450.01
635.79

g
g
g

Calc
final
solution
concentration wt.

511.73

dosage

Density of final filtrate


Volume of final filtrate
Cu conc. in filtrate
Cu concentration. in
filtrate

1.04
481.66
4942.14

g
g/ml,
kg/dm3
ml
mgCu/l

2380.44

mg

Weight of wash water


Volume of wash water

1322.09
1307.55

Density of wash water


Cu cont. in wash water
Cu concentration in wash
water

1.01
179.10

g
ml
g/ml,
kg/dm3
mgCu/l

234.19

mg

Ini.wt.diswater+bot
Fin.wt.diswater+bot
Water added

578.00
362.57
215.43

g
g
g

C
Wt.
of
Copper

assumed

4.192

5.2
6.5
852
0.52

g Cu
g/l

g/ml

measured

63

Calc dry cake wt.


Dry cake wt
Cu concentration in dry
cake

124.06
137.00

g
g

0.55

%Cu

Table I-III: Protocol and reagent consumption NaCN

Table I-IV: Leaching profile and material balance NaCN


Leaching profile and material balance
Date:
Reference number:
Material:
Grinding time:
Leaching temperature:
Screen analysis:

2007-07-03/05
31334
Aitik Mo-conc
25

Test description:
Performed by:

High
Cyanide
Leaching
Fatai Ikumapayi

Feed:
Tare:

0.000

kg

Final weight of material:

0.185

kg

Final weight of solution


Final weight of pulp:

0.726
0.912

kg
kg

%solid:
Gross weight

20.334
0.912

%
kg

Solid density:
Solution density:
Volume of pulp:
Pulp density
Cu concentration
Inventory
of
solution
concentration
Total final pulp weight
Total weight of NaCN added
Total weight of NaOH added
Total weight of CaCl2 added
Water addition
Total weights in
Total water losses

4.300
1.035
0.745
1.224
2.600

kg/dm3
kg/dm3
liter
kg/dm3
%Cu

0.912
0.020
0.005
0.000
0.215
1.040
0.314

dosage

Weight
in
Weight
in
Solid
losses

0.200

kg

0.800

kg

0.015
7.315

kg
%

assumed

kg
kg
kg
kg
kg
kg
kg

64

Cu cont. In all soln. Samples

771.653

mg

specific gravity of filtrate


Volume of filtrate
Copper conc. in filtrate
Copper concentration in separated
filtrate

1.036
481.662
4,942.140

ml
mg/l

2,380.442

mg

Weight of wash water


Copper conc. in wash water
Specific gravity of wash water
Copper concentration in wash
water

1.322
179.104
1.011

kg
mg/l

234.187

mg

3,386.281

mg

Weight of final leach residue


Copper conc. in leach residue
Copper concentration in leach
residue

0.137
0.550

kg
%

753.500

mg

Total weight of copper found

4,139.781

mg

5,200.000
0.082
1,060.219
20.389

mg
mol
mg
%

% Copper leached

85.510

Recovery in solution
Recovery in residue
Molybdenum
concentration
Conc. (HEAD)
Molybdenum
concentration
purified conc.

65.121
14.490

%
%

46.000

49.000

Mo weight in conc. (Head)


Mo weight in purified conc.

92.000
67.130

g
g

Molybdenum loss/leached
Molybdenum recovery

24.870
72.967

g
%

Mo-mol in Head
Mo-mol in purified conc

0.959
0.700

mol
mol

37.400

35.900

Total copper concentration in


solution

Copper concentration in the


material
Cu mol in material
Copper concentration loss

Sulphur concentration Conc


(Head)
Sulphur
concentration
purified Conc

65

S weight in conc. (Head)


S weight in purified conc.

74.800
49.183

g
g

Sulphur loss/leach
Sulphur recovery

25.617
65.753

g
%

S-mol in Head = 2*Mo-mol


S-mol in purif.con = 2*Mo-mol

2.332
1.534

mol
mol

0.019

0.020

Pb weight in conc. (Head)


Pb weight in purified conc.

0.038
0.027

g
g

Lead loss/leach
Lead recovery

0.011
72.105

g
%

Pb-mol in Head
Pb-mol in purif.con

0.000
0.000

mol
mol

2.830

2.530

Fe weight in conc. (Head)


Fe weight in purified conc.

5.660
3.466

g
g

Iron loss/leach
Iron recovery

2.194
61.239

g
%

Fe-mol in Head
Fe-mol in purif.con

0.101
0.062

mol
mol

0.000

0.000

Au weight in conc. (Head)


Au weight in purified conc.

0.000
0.000

g
g

Gold loss/leach
Gold recovery

0.000
25.69

g
%

Au-mol in Head
Au-mol in purif.con

0.000
0.000

mol
mol

Lead concentration Conc


(Head)
Lead concentration purified
Conc

Iron
concentration
Conc
(Head)
Iron concentration purified
Conc

Gold
concentration
Conc
(Head)
Gold concentration purified
Conc

66

Silver concentration Conc


(Head)
Silver concentration purified
Conc

0.010

0.002

Ag weight in conc. (Head)


Ag weight in purified conc.

0.020
0.002

g
g

Silver loss/leach
Silver recovery

0.017
12.582

g
%

Ag-mol in Head
Ag-mol in purif.con

0.000
0.000

mol
mol

Table I-V: Profile of residual elemental analysis NaCN


Purified analysis
Leach
time
Mo
Cu
Pb
S
Fe
Bi
Ca
Clx
Hg
Au
Ag
hrs
%
%
%
%
%
%
%
%
%
g/t
g/t
1
46
1.82 0.02
36.9 2.66 0.019
0.20
<0.1 0.0015 1.1
60
2
45
1.61 0.02
37.1 2.67 0.019
0.20
<0.1 0.0015 1.3
55
6
45
1.30 0.02
36.4 2.59 0.019
0.20
<0.1 0.0015 1.1
44
24
48
0.85 0.02
35.9 2.54 0.019
0.19
<0.1 0.0015 1.1
46
26
47
0.89 0.02
35.9 2.72 0.019
0.20
<0.1 0.0016 1.0
45
30
48
0.84 0.04
35.8 2.68 0.018
0.19
<0.1 0.0016 1.0
36
48
48
0.67 0.02
35.8 2.55 0.019
0.20
<0.1 0.0015 1.0
33
51
47
0.74 0.02
35.7 2.70 0.023
0.20
<0.1 0.0016 1.0
35
53
49
0.55 0.02
35.9 2.53 0.023
0.16
0.1
0.0014 0.6
18
Table I-VI: Protocol and reagent consumption NaCN + CaCl2
Leaching of Aititk Molybdenite concentrate to remove copper concentration by means of sodium cyanide
Protocol and reagent consumption
Date of Experiment
Reference number of
sample
Material
Grinding time
Screen analysis, k80

070710/13
31334
Aitik Mo-conc

Test description
Test temperature

High Cyanide
Leaching
25

dosage

Tare

0.00

kg

Copper concentration
Weight of material
Weight of solution
weight of pulp
%solid
Gross weight

2.13
0.20
0.80
1.00
17.09
1.17

%Cu
kg
kg
kg
%
kg

Solid density
solution density
Volume of pulp
Pulp density

4.30
1.03
0.8232
1.2148

kg/dm3
kg/dm3
litre
kg/dm3

Weight
Copper

assumed

4.192

of

4.26
5.325
705.3969953
0.426

g Cu
g Cu/l

g/ml

measured

67

Reactor+Pulp wt
Empty reactor wt
Final pulp weight

1337
448.35
888.65

g
g
g

Calc
final
solution
concentration wt.

736.744

Density of final filtrate


Volume of final filtrate
Cu conc. in filtrate
Cu concentration. in
filtrate

1.089
675.036
3396.148

g
g/ml,
kg/dm3
ml
mgCu/l

2292.522

mg

Weight of wash water


Volume of wash water

748.380
735.668

Density of wash water


Cu conc. in wash water
Cu concentration in wash
water

1.017
451.710

g
ml
g/ml,
kg/dm3
mgCu/l

332.308

mg

Ini.wt.diswater+bot
Fin.wt.diswater+bot
Water added

566.17
117.32
448.85

g
g
g

Calc dry cake wt.


Dry cake wt
Cu concentration in dry
cake

151.906
153.725

g
g

0.470

%Cu

Table I-VII: Protocol and reagent consumption NaCN + CaCl2

Table I-VIII: Leaching profile and material balance


Leaching profile and material balance
Date:
Reference number:
Material:
Grinding time:
Leaching temperature:
Screen analysis:
Test description:
Performed by:

070710/13
31334
Aitik Mo-conc

Fatai Ikumapayi

Feed:
Tare:

0.000

25

kg

68

Final weight of material:

0.215

kg

Final weight of solution

1.051

kg

Final weight of pulp:

1.266

kg

%solid:
Gross weight

16.986
1.266

%
kg

Solid density:
Solution density:
Volume of pulp:
Pulp density
Cu concentration

4.300
1.088
1.015
1.247
2.13

kg/dm3
kg/dm3
liter
kg/dm3
%Cu

Inventory
of
concentration

Weight
in
Weight
in
Solid
losses

0.2

kg

0.8

kg

-0.015
7.48888

kg
%

assumed

solution

Total final pulp weight


Total weight of NaCN added
Total weight of NaOH added
Total weight of CaCl2 added
Water addition
Total weights in
Total water losses

1.26562
0.03
0.02
0.12
0.44885
1.41885
0.368

kg
kg
kg
kg
kg
kg
kg

Copper concentration in all soln.


samples

785.16719

mg

specific gravity of filtrate


Volume of filtrate
Copper conc. in filtrate
Copper concentration in separated
filtrate

1.08872
675.0358219
3396.148

ml
mg/l

2292.5216

mg

Weight of wash water


Copper conc. in wash water
Specific gravity of wash water
Copper concentration in wash
water

0.74838
451.71
1.01728

kg
mg/l

332.30844

mg

3409.9972

mg

Weight of final leach residue


Copper conc. in leach residue
Copper concentration in leach
residue

0.153725
0.47

kg
%

722.5075

mg

Total weight of copper found

4132.5047

mg

Copper concentration in the


material
Cu mol in material
Copper concentration loss

4260
0.06703
127.4953106

mg
mol
mg

Total copper concentration in


solution

69

% Copper leached

3412.990037

Recovery in solution
Recovery in residue

80.04688238
16.96026995

%
%

Mo weight in conc. (Head)


Mo weight in purified conc.

92
66.10175

g
g

Molybdenum loss/leached
Molybdenum recovery

25.89825
71.84972826

g
%

Mo-mol in Head
Mo-mol in purified conc

0.95893
0.688990515

mol
mol

Sulphur concentration Conc (Head)


Sulphur concentration purified
Conc

37.4

32.4

S weight in conc. (Head)


S weight in purified conc.

74.8
49.8069

g
g

Sulphur loss/leach
Sulphur recovery

24.9931
66.58676471

g
%

S-mol in Head = 2*Mo-mol


S-mol in purif.con = 2*Mo-mol

2.33239788
1.553068288

mol
mol

Lead concentration Conc (Head)


Lead concentration purified Conc

0.019
0.02

%
%

Pb weight in conc. (Head)


Pb weight in purified conc.

0.038
0.030745

g
g

Lead loss/leach
Lead recovery

0.007255
80.90789474

g
%

Pb-mol in Head
Pb-mol in purif.con

0.000183398
0.000148383

mol
mol

Iron concentration Conc (Head)


Iron concentration purified Conc

2.83
2.44

%
%

Fe weight in conc. (Head)


Fe weight in purified conc.

5.66
3.75089

g
g

Iron loss/leach
Iron recovery

1.90911
66.27014134

g
%

Fe-mol in Head
Fe-mol in purif.con

0.101342883
0.067160072

mol
mol

70

Gold concentration Conc (Head)


Gold concentration purified Conc

0.00016
0.00004

%
%

Au weight in conc. (Head)


Au weight in purified conc.

0.00032
0.00006149

g
g

Gold loss/leach
Gold recovery

0.00025851
19.215625

g
%

Au-mol in Head
Au-mol in purif.con

1.62461E-06
3.1218E-07

mol
mol

Silver concentration Conc (Head)


Silver concentration purified Conc

0.0098
0.0007

%
%

Ag weight in conc. (Head)


Ag weight in purified conc.

0.0196
0.001076075

g
g

Silver loss/leach
Silver recovery

0.018523925
5.490178571

g
%

Ag-mol in Head
Ag-mol in purif.con

0.0001817
9.97567E-06

mol
mol

Table I-IX: Profile of residual elemental analysis NaCN + CaCl2


Purified analysis
Leach
time
Mo Cu
Pb
S
Fe
Bi
Ca
Clx
hrs
%
%
%
%
%
%
%
%
1
42
1.67 0.02
31.6 2.6
0.019
4.52 1.59
3
42
1.42 0.02
31.1 2.58 0.019
4.72 1.88
5
42
1.18 0.02
32.2 2.52 0.019
4.65 1.86
7
42
1.09 0.02
31.8 2.52 0.019
4.89 2.06
24
42
0.90 <0.02 30.9 2.55 0.023
5.50 2.42
27
42
0.85 0.02
31.4 2.47 0.019
5.00 2.31
48
41
0.72 0.02
31.2 2.42 0.022
5.10 2.79
52
40
0.73 0.02
30.7 2.52 0.019
5.40 2.86
55
38
0.69 0.02
29.2 2.50 0.019
7.00 2.94
72
40
0.59 <0.02 29.4 2.25 0.023
5.40 3.47
74
43
0.47 0.02
32.4 2.44 0.023
5.50 0.47

Hg
%
0.0013
0.0012
0.0011
0.0014
0.0014
0.0014
0.0014
0.0014
0.0012
0.0011
0.0012

Au
g/t
1.3
1.3
1.1
1.1
1.0
0.9
1.2
1.0
1.0
0.8
0.4

Ag
g/t
68
49
43
41
42
37
28
34
41
41
7

Appendix III
Procedure for ferric chloride leaching

The experimental set-up was as shown in figure 5-3, the concentrate and distilled water was
initially placed in the reactor. The concentrate was conditioned by heating the set-up to the
specified temperature about 90oC. The pulp solid concentration was initially 35%. Thereafter
estimated quantity of FeCl3, CuCl2 and were added along with the air supply. The pH was
71

constantly maintained about zero throughout the experiment by addition of aqueous solution
of HCl when required.
Pulp sample of about 58 g was taken after 2 hours of leaching with the aid of a pipette. The
pulp sample was filtered to separate the solution from the solid residue. The density of the
solution was determined immediately after filtration. The sample solution was analyzed for
dissolved copper concentration with the aid of AAS. The wet solid residues are oven-dried at
about 70oC for about 72 hours. The dry weight of residue was measured accordingly and it
was sent for analysis.
At the end of the experiment, the final pulp was weighted filtered and washed respectively.
The density of the final solution was determined. The weight and density of wash water was
also measured. The wet residue was oven dried at 70oC for about 72 hours. The dry weight of
residue was measured and was subsequently sent for analysis.
Table I-X: Protocol and reagent consumption FeCl3
Leaching of Aititk Molybdenite concentrate to remove copper concentration by means of Ferric chloride
and other ligands
Protocol and reagent consumption
Date of Experiment
Reference number
sample
Material
Grinding time
Screen analysis, k80

of

7/3/2007
31334
Aitik Mo-conc

Test description
Test temperature

Ferric
leaching
110

Tare

0.00

kg

Copper concentration
Weight of material
Weight of solution
weight of pulp
%solid
Gross weight

3.06
0.43
0.55
0.98
34.58
0.98

%Cu
kg
kg
kg
%
kg

Solid density

4.30

kg/dm3

solution density

1.03

kg/dm3

Volume of pulp
Pulp density

0.6340
1.5458

litre
kg/dm3

Reactor+Pulp wt
Empty reactor wt

1707.00
450.05

Chloride
C

Maximum

Weight
Copper

assumed

4.192

of

13.16316
23.93302
0
0.61224

g Cu
g/l

g/ml

measured

g
g

72

Final pulp weight

1256.95

Calc
final
solution
concentration wt.

822.34

Density of final filtrate


Volume of final filtrate
Cu conc. in filtrate
Cu
concentration.
in
filtrate

1.19
726.49
12478.23

g
g/ml,
kg/dm3
ml
mgCu/l

9065.31

mg

Weight of wash water


Volume of wash water

529.11
516.34

Density of wash water


Cu cont. in wash water
Cu concentration in wash
water

1.02
1426.89

g
ml
g/ml,
kg/dm3
mgCu/l

736.76

mg

Ini.wt.diswater+bot
Fin.wt.diswater+bot
Water added

576.78
300.59
276.19

g
g
g

Calc dry cake wt.


Dry cake wt
Cu concentration in dry
cake

434.61
391.70

g
g

0.65

%Cu

Table I-XI: Protocol and reagent consumption FeCl3

Table I-XII: Leaching profile and material balance FeCl3


Leaching profile and material balance
Date:
Reference number:
Material:
Grinding time:
Leaching temperature:
Screen analysis:

7/3/2007
31334
Aitik Mo-conc
70-110

Test description:
Performed by:

Ferric
Chloride
leaching
Fatai Ikumapayi

Feed:
Tare:

0.000

kg

73

Final
weight
of
material:
Final
weight
of
solution
Final weight of pulp:

0.408

kg

0.906
1.315

kg
kg

%solid:
Gross weight

31.052
1.315

%
kg

Solid density:
Solution density:
Volume of pulp:
Pulp density
Cu concentration

4.300
1.190
0.856
1.535
3.061

kg/dm3
kg/dm3
liter
kg/dm3
%Cu

Inventory
of
concentration

solution

Total final pulp weight


Total weight of FeCl3 added
Total weight of CuCl2 added
Total weight of CaCl2 added
Water addition
Total weights in
Total water losses

1.315
0.080
0.008
0.160
0.276
1.074
0.168

kg
kg
kg
kg
kg
kg
kg

specific gravity of filtrate


Volume of filtrate
Copper conc. in filtrate
Copper concentration in separated
filtrate

1.191
726.490
12,478.230

ml
mg/l

9,065.314

mg

Weight of wash water


Copper conc. in wash water
Specific gravity of wash water
Copper concentration in wash
water

0.529
1,426.894
1.025

kg
mg/l

736.757

mg

9,802.070

mg

Weight of final leach residue


Copper conc. in leach residue
Copper concentration in leach
residue

0.392
0.650

kg
%

2,546.050

mg

Total weight of copper found

12,348.120

mg

13,163.160
0.207
815.040
6.192
9,808.262

mg
mol
mg
%
%

Total copper concentration in


solution

Copper concentration in the


material
Cu mol in material
Copper concentration loss
% Copper leached

Weight
in
Weight
in
Solid
losses

0.430

kg

0.550

kg

0.022
5.070

kg
%

assumed

74

Recovery in solution
Recovery in residue

74.466
19.342

%
%

Molybdenum concentration Conc.


(HEAD)
Molybdenum
concentration
purified conc.

46.000

191.933

Mo weight in conc. (Head)


Mo weight in purified conc.

197.800
751.802

g
g

Molybdenum loss/leached
Molybdenum recovery

-554.002
380.082

g
%

Mo-mol in Head
Mo-mol in purified conc

2.062
7.836

mol
mol

Sulphur concentration Conc (Head)


Sulphur concentration purified
Conc

37.400

37.800

S weight in conc. (Head)


S weight in purified conc.

160.820
148.063

g
g

Sulphur loss/leach
Sulphur recovery

12.757
92.067

g
%

S-mol in Head = 2*Mo-mol


S-mol in purif.con = 2*Mo-mol

5.015
4.617

mol
mol

Lead concentration Conc (Head)


Lead concentration purified Conc

0.019
0.003

%
%

Pb weight in conc. (Head)


Pb weight in purified conc.

0.082
0.012

g
g

Lead loss/leach
Lead recovery

0.070
14.383

g
%

Pb-mol in Head
Pb-mol in purif.con

0.000
0.000

mol
mol

Iron concentration Conc (Head)


Iron concentration purified Conc

2.830
1.400

%
%

Fe weight in conc. (Head)


Fe weight in purified conc.
Iron loss/leach
Iron recovery

12.169
5.484
6.685
45.064

g
g
g
%

75

Fe-mol in Head
Fe-mol in purif.con

0.218
0.098

mol
mol

Gold concentration Conc (Head)


Gold concentration purified Conc

0.000
0.000

%
%

Au weight in conc. (Head)


Au weight in purified conc.

0.001
0.001

g
g

Gold loss/leach
Gold recovery

-0.001
187.310

g
%

Au-mol in Head
Au-mol in purif.con

0.000
0.000

mol
mol

Silver concentration Conc (Head)


Silver concentration purified Conc

0.010
0.002

%
%

Ag weight in conc. (Head)


Ag weight in purified conc.

0.042
0.008

g
g

Silver loss/leach
Silver recovery

0.034
18.590

g
%

Ag-mol in Head
Ag-mol in purif.con

0.000
0.000

mol
mol

Table I-XIII: Profile of residual elemental analysis FeCl3


Purified analysis
Leach time Mo
Cu
Pb
S
Fe
hrs
%
%
%
%
%
0
*3.0612
2
45
1.11
0.004
34.4
1.91
4
49
0.65
0.003
37.8
1.40

Bi
%

Hg
%

Au
g/t

Ag
g/t

0.004
0.004

0.0004
0.0002

3.22
3.29

27
20

Appendix IV
Procedure for ferric sulphate leaching

The experimental set-up was as shown in figure 5-3, 1.5 kg of 0.1 M solution of FeSO4.6H2O
was placed in the reactor, and the set-up was heated to the fastest generating temperature,
65oC. SO2/O2 was subsequently supplied to the solution for minimum of one hour (when
sufficient Fe3+ has been formed to start up the leaching). The concentrate was added to the
solution to make up 10% solid concentration of the pulp. The pH was constantly maintained
below 1.00 throughout the experiment by addition of aqueous solution of H2SO4 when
required. The experiments lasted for 3 to 5 hours.

76

Pulp samples were taken at every one-hour and the solution concentration of the intermediate
samples and the final pulp was analyzed for dissolved copper concentration with the aid of
AAS. The wet solid residue was oven dried at about 70oC for about 72 hours. The dry weight
of residue was measured accordingly and kept for analysis.
Table I-XIV: Leaching profile and reagent consumption Fe2(SO4)3

leaching of Aitik Moly-conc to separate Copper through Ferric sulphate


leaching
date of experiment
Provnr (sample number)
Tare
Cu-halt (Cu-concentration)

5/22/2007

0.004683

kg Cu in 250g conc

0
2.81

kg
%

7.37E-05

Antag (% solid)
Godsmngd(amount or quantity of
material)
Lsningsvolym start(initial solution
volume)
Pulp weight

10

0.016464

Kmol Cu in 250g conc


kg Fe3+ required stoich.
To leach Cu in conc.

0.167

kg

1.500
1.667

kg
kg

65

Gross weight

1.667

kg

Total Fe3+ requred stoichiometrically to


leach Cu concentration in Conc.

0.016

40.5

4.68333

0.099
Final pulp+reator
Reactor empty
Final pulp weight

2838.7
941.6
1897.1

g
g
g

wwbini
final
water addition

563.48
183.28
380.2

g
g
g

wash water+bottleini
wash wate+bottle final
washwater

573.16
50.98
522.18

g
g
g

Weight of dry purified


residue

149.3

Temp

(Tare+pulp
weight)
FeSO4
concentration
kg
added
kg/kg
Cu
conc
concentration

Table I-XV: Leaching profile and reagent consumption Fe2(SO4)3

77

Table I-XVI: Molybdenum dissolution sodium cyanide leaching


Mo
concentration
Cu
in
leach concentration
in solution
Leaching time solution
Cal. Cu grade Mo rec.
hrs
mgMo/l
mgCu/l
%Cu
% Mo
30
210
4400
0.84
0.18832
51
420
5800
0.36
0.37663
53
390
5300
0.56
0.34973

Cu rec.
% Cu
69.8077
92.0192
84.0865

Table I-XVII: Molybdenum dissolution sodium cyanide + calcium chloride leaching


Mo
concentration
Cu
in
leach concentration
Leaching time solution
in solution
Cal. Cu grade Mo rec.
Cu rec.
hrs
mgMo/l
mgCu/l
%Cu
% Mo
% Cu
27
47
3200
0.7
0.04955435
72.8638498
48
85
4000
0.31
0.08961957
91.0798122
74
95
3600
0.48
0.10016304
81.971831

Appendix V
Atomic absorption spectroscopy, AAS

Atomic absorption spectroscopy, AAS is an analytical technique for determining the


concentration of a particular metal element in a sample. Atomic absorption spectroscopy can
be used to analyze the concentration of over 62 different metals concentration in different
solutions. The technique normally makes use of flame to atomize the sample and turning the
sample into an atomic gas. Three basic steps are involved in achieving the atomization:
1. Desolvation the liquid solvent is evaporated, and the dry sample remains
2. Vaporisation the solid sample vaporises to a gas
3. Volatilisation the compounds making up the sample are broken into free atoms
The flame is arranged such that it is laterally long (usually 10 cm) and not deep. Controlling
the flow of the fuel mixture must also control the height of the flame. A beam of light is
focused through this flame at its longest axis (the lateral axis) onto a detector past the flame.
A hollow cathode lamp produces the light that is focused into the flame. The lamp contains an
anode and a cylindrical metal cathode that holds the metal for excitation. When a high voltage
is applied across the anode and cathode, the metal atoms in the cathode are excited into
producing light with a certain emission spectra. The type of hollow cathode tube depends on
the metal being analyzed. For analyzing the concentration of copper in an ore, a copper
cathode tube would be used, and likewise for any other metal being analyzed. The electrons of
the atoms in the flame can be promoted to higher orbitals for instant by absorbing a set of

78

quantum energy. The amount of energy is specific to a particular electron transition in a


particular element. As the quantity of energy put into the flame is known, and the quantity
remaining at the other side (of the detector) can be measured, it is possible to calculate how
many of these transitions took place, and thus get a signal that is proportional to the
concentration of the element being measured [31].
Copper analysis with AAS

The copper analysis in leach solution was carried out on fresh pregnant leach solution in the
Boliden Bioleach-Cyanide Lab., with the aid of Atomic Absorption Spectrometer, AAS
model PU 9100X made by Phillips, using acetylene as burner gas.

Procedure for copper analysis with AAS

A copper-in-cyanide standard solution was prepared by diluting 1.41 g CuCN and 4 g NaCN
to make 1liter of solution.
Standard solutions containing 1 ppm, 3 ppm, 5 ppm, 10 ppm and 20 ppm respectively was
prepared from the copper-in-cyanide standard solution.
1ppm standard was prepared by diluting 100 l 100 times in a 100 ml standard volumetric
reagent bottle, 3 ppm by diluting 300 microns 100 times, 5 ppm by diluting 500 microns 100
times, 10 ppm by 1 ml 100 times and 20 ppm by diluting 2 ml 100 times. The figure shows
the linear curve as ppm as a function of AAS signals in each of the standard solutions. A line
of best fit was plotted such that the R2 value is 0.9-1.0. The copper quantity in solution is
calculated using the equation of the curve and the appropriate signals. The value of signals
obtained from experimental samples must lie within the range of signals obtained from the
standard samples therefore appropriate dilution of the experimental samples must be done in
order to achieve this. An example is shown in figure II-I.

79

Cu analysis
120
y = 4.7019x + 1.5251

AAS signals

100

R = 0.9999

80
60
40
20
0
0

10

15

20

25

Cu contents in ppm

Figure II-I
The figure shows the plots of AAS signals as a function of copper concentration of the
corresponding standard solution in table II-I.
Table II-I: Copper concentration in standard solution and corresponding AAS signals
Cu
concentration AAS
in ppm
signals
1
6
3
15.5
5
25.5
10
48.5
20
95.5

If 200 m of a leach solution is diluted to 100 ml i.e. 500 times and the AAS signals from this
solution is 37.7. The copper concentration in the solution can be calculated using the equation
of the curve since the signal lies within the standard solutions signals and the R2 of the curve
is 0.999: y = 4.7019 + 1.5251
x=

y 1.5251
500
4.7019

= 3825.57 ppm Cu i.e. the copper concentration in the solution.

80

Figure II-I: Atomic Absorption Spectrometer


The AAS equipment used in this study is shown in figure II-I.
XRD Equipment

The material was placed in sample holders and pressed manually with a glass slide to achieve
a flat surface. The equipment utilized was a Siemens D5000 X-ray diffractometer, figure II-II,
using copper K radiation with accelerating voltage of 20 kV. XRD patterns were recorded
from 30 to 50 and 30 to 45. The phase identification was made by reference patterns in an
evaluating program known as EVA.

Figure II-II: X-ray diffractometer

81

Appendix VI
Composition of commercial molybdenite concentrate brands
Table II-II Molybdenum Concentrate Brands & Chemical Compositions

Chemical compositions

Brand

Mo
%

SiO2

As

Sn

Cu

Pb

CaO

WO3

Bi

53

6.5

0.01

0.01

0.01

0.015

0.15

1.50

0.05

0.05

53

5.0

0.05

0.05

0.02

0.20

0.30

2.00

0.25

0.10

51

8.0

0.02

0.02

0.02

0.20

0.18

1.80

0.06

0.06

51

5.5

0.10

0.06

0.03

0.40

0.40

2.00

0.30

0.15

49

9.0

0.03

0.03

0.03

0.22

0.20

2.20

--

--

49

6.5

0.15

0.06

0.04

0.60

0.60

2.00

--

--

47

11.0

0.04

0.04

0.04

0.25

0.25

2.70

--

--

47

7.5

0.20

0.07

0.05

0.80

0.65

2.40

--

--

45

13.0

0.05

0.05

0.05

0.20

0.30

3.00

--

--

45

8.5

0.22

0.07

0.07

1.20

0.07

2.60

--

--

min
Kmo53A
Kmo53B
Kmo51A
Kmo51B
Kmo49A
Kmo49B
Kmo47A
Kmo47B
Kmo45A
Kmo45B

Impurities, %, Max

[19]

82

Composition of commercial molybdenum oxide brands


Table II-III :Technical Grade Molybdenum Oxide.Sadaci

Mo

57.00%

min.

Cu

0.50%

max.

0.10%

max.

0.10%

max.

0.05%

max.

Pb

0.05%

max.

[20]
Table II-IV :Purified concentrates analysis.
Test
Mo
Cu
Pb
S
Fe
%
%
%
%
%
CN
49
0.55
0.02
35.9
2.53
CN+Cl 43
0.47
0.02
32.4
2.44
FeCl3
49
0.65
0.003 37.8
1.40
Mo
%

Head 46

Cu
%

2.13

Pb
%

S
%

0.019 37.4

Fe
%

2.83

Table II-V: Cyanide leaching test assays


Mo
Cu
Pb
S
%
%
%
%

Calculated
head
assays
Purified

46

2.6* 0.019 37.4

49

0.55 0.02

Bi
%
0.023
0.023
0.004

Ca
%
0.16
5.50
-

Clx
%
0.1
0.47
-

Hg
%
0.0014
0.0012
0.0002

Bi
%

Ca
%

Clx
%

Hg
%

0.011 0.11

<0.1

Fe
%

Bi
%

2.53

0.023 0.16

2.83

Ca
%

0.011 0.11

Au
g/t
0.6
0.4
3.29

Ag
g/t
18
7
20

Au
g/t

Ag
g/t

0.0016 1.6

98

Clx
%

Hg
%

Au
g/t

Ag
g/t

0.1

0.0014 0.6

18

Clx
%

Hg
%

Ag
g/t

0.47

0.0012 0.4

<0.1

0.0016 1.6

98

concentrate
assays

35.9

Table II-VI: Cyanide + Chloride leaching test assays


Mo
Cu
Pb
S
Fe
Bi
%
%
%
%
%
%

Calculated
head
assays
Purified

Ca
%

46

2.13 0.019 37.4

2.83

0.011 0.11

43

0.47 0.02

2.44

0.023 5.50

<0.1

Au
g/t

0.0016 1.6

98

concentrate
assays

32.4

83

Table II-VII: Ferric chloride leaching test assays


Mo
Cu
Pb
S
Fe
%
%
%
%
%

Calculated
head
assays
Purified

46

3.06* 0.019 37.4

2.83

49

0.65

1.40

Bi
%

Ca
%

0.011 0.11

Clx
%

Hg
%

0.0002 3.29 20

<0.1

Au
g/t

0.0016 1.6

Ag
g/t

98

concentrate
assays

0.003 37.8

0.004 -

* Assays calculated from analyzed solutions and residues

84

Appendix VII
SCN formation

The major cyanide consuming reactions in the cyanidation tests is the formation of Cu(CN)3-,
SCN complexes and negligible CNO complex formation.
Table III-I: SCN formation from previous study
Time in hours
48
48
48
48

Cu mg/l
124
127
819
860

CNS mg/l
370
290
1300
1310

mg/mg
ratio
2.983871
2.283465
1.587302
1.523256
2.094473

mol/mol
ratio
3.268882
2.501575
1.738916
1.668753
2.294532

Average

~3

~3

The table shows SCN formation as a ratio of copper complex formation from previous
experiments on cyanide leaching of Lakefield chalcopyrite. It gives estimation of cyanide
consumed by both sulphur and copper in a typical reaction containing chalcopyrite and other
metal sulphides. It can be seen that both the mass: mass and mol: mol ratio can be rounded up
to 3 [30]. This shows an indication of cyanide consuming species in the reaction involving
cyanide and metal sulphides, especially chalcopyrite. It can be seen that sulphur is always
consuming as much mole of cyanide as copper is consuming. It was also observed in the
study that CNO is also formed during such reaction, but the quantity is negligible compared to
CNS formation. Therefore the major consumption of cyanide is the formation of copper
complex and sulphur thiocyanite.
Table III-II: SCN formation this study NaCN
Time in hours
1
6
24
30
51

SCN mg/l
2085
3987.5
6460
7210
8830

Cu mg/l
1300.2
2503.1
3900
4270
5420.67

mg/mg
1.603599
1.593025
1.65641
1.688525
1.62895

mol/mol
1.757047
1.745461
1.814912
1.850099
1.784824

Average

1.634102

1.790468

Still approximately 1:1 but as 2 mol: 2 mol unlike the observation from the previous study
which is 3 mol: 3 mol.
The previous higher formation rate of SCN versus Cu dissolution seems to have come from
the high pyrite concentration or pyrrotite. However it seems not to have any significant

85

contribution of sulphur from MoS2 to the SCN formation in this case. Hence there seems to be
better utilization of CN in this test. Although it can be observed that the SCN formation rate is
increasing with time; this may be due to increased concentration of sulphur in the solution,
which seem to increase the formation rate of the complex.
Table III-III: SCN formation this study NaCN + CaCl2
Time in hours
1
5
27
48
74

SCN mg/l
2002
3506
5905
6659
6030

Cu mg/l
1175.095
2011.236
3009.314
3756.239
3396.148

mg/mg
1.703692
1.743207
1.962241
1.772784
1.775541

mol/mol
1.866718
1.910014
2.150007
1.942421
1.945442

Average

1.79149

1.96292

The formation rate of SCN is much reduced in the test with addition of CaCl2 as can be seen
in the table III-III, the formation is actually still approximately 1:1 i.e. mg/mg is ~2 with more
reduced mol/mol ~2 indicating that sulphur is not consuming much of the cyanide and a better
cyanide utilization.

86

Appendix VIII

Mo-CN stability constant

START Experiments recorded for Boliden Mineral AB, Boliden, Sweden


from SC-Database on Monday, 20 July, 7-02 at 08:51:38
Software version = 5.4 Data version = 4.51
Experiment list contains 26 experiments for
4 ligands : Cyanide, Cyanate, Thiocyanate, Selenocyanate
5 metals: Mo(0), Mo(III), Mo(IV), Mo(V), Mo(VI)
(no references specified)
(no experimental details specified)
***************************************************************************
**
CNHL Cyanide
CAS 74-90-8 (230)
Cyanide;
----------------------------------------------------------------------------Metal
Mtd Medium Temp Conc Cal Flags Lg K values
Reference ExptNo
----------------------------------------------------------------------------Mo(IV) nmr KNO3 25C 0.10M C
1994RLa (2705) 1
*K(MoO(CN)4(H2O)=-9.88
Method: N.M.R.
----------------------------------------------------------------------------Mo(IV) con oth/un 25C dil U M
1974FIb (2706) 2
K(K+Mo(CN)8)=1.8
K(Me4N+Mo(CN)8)=2.5
K(Et4N+Mo(CN)8)=2.3
----------------------------------------------------------------------------Mo(IV) gl none 25C 0.0 U T H
1973BKa (2707) 3
K(MoOOH(CN)4+H)=8.81
K=8.86(30 C). K=8.90(35 C). K=8.97(40 C). K=9.04(45 C). K=9.13(50 C).
DH=23.4 kJ mol-1
----------------------------------------------------------------------------Mo(IV) sp NaClO4 25C var U
1973MHa (2708) 4
K(Fe+Mo(CN)8)=2.6
----------------------------------------------------------------------------Mo(IV) sp NaClO4 25C var U M
1971JSb (2709) 5
K(Fe+Mo(CN)8)=2.6
----------------------------------------------------------------------------Mo(IV) sp oth/un 25C var U M
1969KBc (2710) 6
K(UO2+Mo(CN)4(OH)3(H2O))=3.71
----------------------------------------------------------------------------Mo(IV) sp oth/un 25C var U M
1968DBb (2711) 7
K(VO+MoL4(OH)3H2O)=4.86
----------------------------------------------------------------------------Mo (IV) gl oth/un 25C 0.0 U
1968PNb (2712) 8
K (H+MoO2L4) =12.62
K (H+MoOOHL4) =9.98
----------------------------------------------------------------------------Mo(IV) con oth/un 25?C dil U M
1958SEa (2713) 9
Ks(KAg2Y(s))=-13.96

87

Ks(Ag3Y(s))=-13.83
Ks(Mn3Y2(s))=-12.35
Ks(Fe3Y2(s))=-16.28
Y=MoSOHL4 (H2O)2---. Ks(Co3Y2)=-13.92; Ks(Ni3Y2)=-18.23; Ks(Cu3Y2)=-18.46;
Ks(Zn3Y2)=-13.62; Ks(Cd3L2)=-18.32; Ks(Hg3Y2)=-18.73; Ks(Pb3Y2)=-18.52
***************************************************************************
**
SCNHL Thiocyanate
CAS 463-56-9 (106)
Thiocyanate;
----------------------------------------------------------------------------Metal
Mtd Medium Temp Conc Cal Flags Lg K values
Reference ExptNo
----------------------------------------------------------------------------Mo(III) kin oth/un 25C 2.00M U
1997NCa (14850) 10
K(Mo4S4(H2O)12+L)=3.11
K(Mo7S8(H2O)18+L)=2.94
Medium: Li-p-toluenesulfonate.
----------------------------------------------------------------------------Mo(III) kin oth/un 25C 2.00M U
1993HLa (14851) 11
K(Mo4S4+L)=3.11
Medium: Li toluene-p-sulfonic acid. For Mo(IV), K=3.72; for mixed Mo(III)/
Mo(IV) (Mo4S4+++++), K=3.48.
----------------------------------------------------------------------------Mo(III) kin oth/un 25C 1.0M U
K1=5.0
1974SSd (14852) 12
medium:lithium p-toluenesulfonate
----------------------------------------------------------------------------Mo(III) sp oth/un ? 1.0M U
K1=0.6
1972KTa (14853) 13
Medium: p-toluenesulfonic acid
----------------------------------------------------------------------------Mo(IV) kin NaClO4 25C 2.00M U
1993LMb (14854) 14
K(Mo3Se4+NCS)=3.38
K(Mo3OSe3+NCS)=3.23
K(Mo3O2Se2+NCS)=3.66
K(Mo3O3Se+NCS)=3.18
K(Mo3O4+NCS)=2.99. Medium: 2.0 M HClO4.
----------------------------------------------------------------------------Mo(IV) kin NaClO4 25C 2.00M U
1993VSa (14855) 15
K(Mo3S4(H2O)9+L)=3.36
K(Mo2WS4(H2O)9+L)=3.48
K(MoW2S4(H2O)9+L)=3.68
Medium: 2.0 M HClO4. For mixed Mo/W species data refer to L binding to Mo.
Metals are Mo(IV) and W(IV).
----------------------------------------------------------------------------Mo(IV) kin oth/un 25C 2.0M U T
K1=2.54
1976OSa (14856) 16
Medium: LiClO4/HClO4, metal: MoO++. K1=2.89 (10 C); 2.73 (15 C); 2.61 (20 C)
----------------------------------------------------------------------------Mo(V)
sp mixed 20C ? C
1986CZa (14857) 17
B(CuH-2L)=-7.88
B(CuH-3L)=-15.12
Medium: DMSO/acetone
-----------------------------------------------------------------------------

88

Mo(V)

kin NaClO4 25C 1.00M U M


1976CSa (14858) 18
K(Mo2O4(C2O4)2+L)=0.74
By spectrophotometry: K=0.63
----------------------------------------------------------------------------Mo(V)
kin NaClO4 25C 2.00M U
T
1975STa (14859) 19
K(Mo2O4+L=Mo2O4L)=2.38
Medium: LiClO4
----------------------------------------------------------------------------Mo(V)
sp non-aq ? 100% U
K1=2.88
1970BRb (14860) 20
Medium: (EtO)2PSSEt + EtOH(4:1)
----------------------------------------------------------------------------Mo(V)
nmr NaClO4 23C 2.0M U M
1968MDf (14861) 21
K(MoOL4+A=MoOL3A+L)=-1.64
K(MoOL4+2A=MoOL2A2+2L)=-3.24
K(MoOL4+3A=MoOLA3+3L)=-6.19
Medium: HClO4. A=(NH2)2CS
----------------------------------------------------------------------------Mo(V)
sp non-aq ? 100% U I K1=5.0 B2=9.40 1965ULa (14862) 22
K3=4.0
K4=3.4
Medium: Me2CO, Mo as MoCl5. In MeOH: K1=3.85
----------------------------------------------------------------------------Mo(V)
sp oth/un ? 3.25M U I
1959NAb (14863) 23
K6?=1.35
Medium: H2SO4. In 3.1 M (NH4)2SO4 K3*K4*K5?=2.25
----------------------------------------------------------------------------Mo(V)
sp mixed ? 60% U
K1=3.2 B2=6.2 1958PEb (14864) 24
K3=ca.2
K4=-1.6
Medium: 60% w/w acetone/H2O
----------------------------------------------------------------------------Mo(V)
sp mixed 20C 60% U
K1=3.2 B2=6.2 1958PEb (14865) 25
K3=1.85
Meedium: 60% w/w acetone/H2O, 1 M HCl. Also by electrical migration
----------------------------------------------------------------------------Mo(VI) nmr oth/un ? var U M
1969MDb (14866) 26
K(MoOL4+A=MoOL3A+L)=-1.5
K(MoOL4+2A=MoOL2A2+2L)=-3.1
K(MoOL4+3A=MoOLA3+3L)-5.1
K(MoOL4+4A=MoOA4+4L)=-7.6
A=Br-. Other ternary complexes also reported. Method: esr
----------------------------------------------------------------------------REFERENCES
1997NCa M Sokolov,N Coichev,H Moya,A Sykes et al; J.Chem.Soc.,Dalton Trans.,1863
(1997)
1994RLa A Roodt,J Leipoldt,L Helm et al; Inorg.Chem.,33,140 (1994)
1993HLa M Hong,Y Li,J Lu,M Nasreldin et al; J.Chem.Soc.,Dalton Trans.,2613 (1993)
1993LMb G Lamprecht,M Martinez,M Nasreldin; J.Chem.Soc.,Dalton Trans.,747 (1993)

89

1993VSa J Varey,A Sykes; J.Chem.Soc.,Dalton Trans.,3293 (1993)


1986CZa Chen Lianshan,Zhao G L,He,Z L,Zhao H G; Acta Chimica Sinica,520 (1986)
1976CSa G Cayley,A Sykes; Inorg.Chem.,15,2882 (1976)
1976OSa J Ojo,Y Sasaki,R Taylor et al; Inorg.Chem.,15,1006 (1976)
1975STa Y Sasaki,R Taylor,A Sykes; J.Chem.Soc.,Dalton Trans.396 (1975)
1974FIb F Ferranti,A Indelli; J.Solution Chem.,3,619 (1974)
1974SSd Y Sasaki,A Sykes; J.Less Common Metals,36,125 (1974)
1973BKa M Beg,Kabir-ud-Din et al; Australian J.Chem.,26,671 (1973)
1973MHa G McKnight,G Haight; Inorg.Chem.,12,1934 (1973)
1972KTa K Kustin,D Toppen; Inorg.Chem.,11,2851 (1972)
1971JSb D Joshi,K Sharma; Z.Phys.Chem.,246,281 (1971)
1970BRb A Busev,T Rodionova; Anal.Lett.,3,325 (1970)
1969KBc Kabir-ud-Din,M Beg; J.Indian Chem.Soc.,46,503 (1969)
1969MDb I Marov,Y Dubrov,A Ermakov,G Martynova; Zh.Neorg.Khim.,14,438(E:224)
(1969)
1968DBb Kabir-ud-Din,M Beg; J.Indian Chem.Soc.,45,455 (1968)
1968MDf I Marov,Y Dubrov,A Ermakov,G Martynova; Zh.Neorg.Khim.,13,3247 (1968)
1968PNb J van de Poel,H Neumann; Inorg.Chem.,7,2086 (1968)
1965ULa N Ulko; Ukr.Khim.Zh.,31,887 (1965)
1959NAb B Nabivanets; Zh.Neorg.Khim.,4,1797 (1959)
1958PEb D Perrin; J.Am.Chem.Soc.,80,3540 (1958)
1958SEa A Sergeeva; Nauk Zapiski L'
vov Inst.,50,22 (1958)
EXPLANATORY NOTES
DATA Flags are :T Data at other TEMPERATURES
I Data with various BACKGROUNDS
H Data for THERMOCHEMICAL quantities
M Data for TERNARY Complexes
EVALUATION Flags are :T or IUP=T signifies EVALUATION RATING = Tentative by IUPAC
----------------------------------------------------------------------------END Experiments recorded for Boliden Mineral AB, Boliden, Sweden
from SC-Database on Monday, 20 July, 7-02 at 08:51:38

90