Beruflich Dokumente
Kultur Dokumente
MASTER'S THESIS
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
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.
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].
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
Figure 1-2a: Molybdenite sample [17] Figure 1-2b: Molybdenite sample from Aitik.
(From a primary 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)
(2-2)
(2-3)
(2-4)
13
(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
3.8
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.
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].
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].
log MoO4
HMoO
MoO42- + H+
= -6.00 + pH
Z = +3 to +6
2. Mo3+ + 4H2O
E = 0.39 0.1379 pH +
3. Mo3+ + 4H2O
Mo
3+
19
2
4
3+
pH = 6.00
2. Mo3+/HMoO4-
E = 0.300-0.1379pH
3. Mo3+/MoO42-
E = 0.508-0.1576pH
E = -0.072-0.0591pH
Z = +4 to +6
5. MoO2 + H2O
a. E = -1.091-0.0591pH
b. E
= 0.320-0.0591pH
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
20
9. Mo3+ +2H2O
MoO2 + 4H+ + e-
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
MoO42- + 2e-
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.
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).
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-
Mo3O114-
Mo6O216-
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
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.
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
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
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.
4.4
10.3
20.2
41.6
9.8
13.7
+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
35
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
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.
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.
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)
(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.
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
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.
41
5000
80
4500
70
60
3500
50
3000
2500
40
2000
30
1500
20
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
4000
60
3500
3000
50
2500
40
2000
30
1500
20
1000
10
500
0
0
50
100
150
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)
(5-11)
Slow
(5-12)
SO3- + O2 SO5-
Fast
(5-13)
43
Fast
(5-14)
Fast
(5-15)
(5-16)
(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
100
90
Cu recovery %Cu
70
60
50
1.5
40
1
30
20
2.5
80
0.5
10
0
0
0
10
20
30
40
50
60
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.
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
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
<0.1
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
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
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.
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.
Head
Cu
Pb
Fe
Bi
Ca
Cl
%
Hg
Au
g/t
Ag
46
<0.1
0.0016 1.6
g/t
49
0.65
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.
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
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
this may be due to the fact that the duration of leaching was short in this test leading to less
extensive attrition.
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
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.
The use of air as oxidising agent is more reasonable and cost effective and should
be tested also in the pilot scale.
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- + 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
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molybdenum
flotation
concentratesUnited
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Patent
4083921
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[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
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
4612oC
35.6 kJ/mol
251 Jkg-1K-1
Density (20oC)
10.22g/cm3
137 Wm-1K-1
5.7 .cm
o
4.3510-3K-1
324.8 Gpa
Rigidity modulus
125.6 Gpa
Bulk modulus
261.2 Gpa
Poissons ratio
0.293
-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)
(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
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
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
1.04
481.66
4942.14
g
g/ml,
kg/dm3
ml
mgCu/l
2380.44
mg
1322.09
1307.55
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
124.06
137.00
g
g
0.55
%Cu
2007-07-03/05
31334
Aitik Mo-conc
25
Test description:
Performed by:
High
Cyanide
Leaching
Fatai Ikumapayi
Feed:
Tare:
0.000
kg
0.185
kg
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
771.653
mg
1.036
481.662
4,942.140
ml
mg/l
2,380.442
mg
1.322
179.104
1.011
kg
mg/l
234.187
mg
3,386.281
mg
0.137
0.550
kg
%
753.500
mg
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
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
65
74.800
49.183
g
g
Sulphur loss/leach
Sulphur recovery
25.617
65.753
g
%
2.332
1.534
mol
mol
0.019
0.020
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
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
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
Iron
concentration
Conc
(Head)
Iron concentration purified
Conc
Gold
concentration
Conc
(Head)
Gold concentration purified
Conc
66
0.010
0.002
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
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
1.089
675.036
3396.148
g
g/ml,
kg/dm3
ml
mgCu/l
2292.522
mg
748.380
735.668
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
151.906
153.725
g
g
0.470
%Cu
070710/13
31334
Aitik Mo-conc
Fatai Ikumapayi
Feed:
Tare:
0.000
25
kg
68
0.215
kg
1.051
kg
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
1.26562
0.03
0.02
0.12
0.44885
1.41885
0.368
kg
kg
kg
kg
kg
kg
kg
785.16719
mg
1.08872
675.0358219
3396.148
ml
mg/l
2292.5216
mg
0.74838
451.71
1.01728
kg
mg/l
332.30844
mg
3409.9972
mg
0.153725
0.47
kg
%
722.5075
mg
4132.5047
mg
4260
0.06703
127.4953106
mg
mol
mg
69
% Copper leached
3412.990037
Recovery in solution
Recovery in residue
80.04688238
16.96026995
%
%
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
37.4
32.4
74.8
49.8069
g
g
Sulphur loss/leach
Sulphur recovery
24.9931
66.58676471
g
%
2.33239788
1.553068288
mol
mol
0.019
0.02
%
%
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
2.83
2.44
%
%
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
0.00016
0.00004
%
%
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
0.0098
0.0007
%
%
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
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
1256.95
Calc
final
solution
concentration wt.
822.34
1.19
726.49
12478.23
g
g/ml,
kg/dm3
ml
mgCu/l
9065.31
mg
529.11
516.34
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
434.61
391.70
g
g
0.65
%Cu
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
1.315
0.080
0.008
0.160
0.276
1.074
0.168
kg
kg
kg
kg
kg
kg
kg
1.191
726.490
12,478.230
ml
mg/l
9,065.314
mg
0.529
1,426.894
1.025
kg
mg/l
736.757
mg
9,802.070
mg
0.392
0.650
kg
%
2,546.050
mg
12,348.120
mg
13,163.160
0.207
815.040
6.192
9,808.262
mg
mol
mg
%
%
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
%
%
46.000
191.933
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
37.400
37.800
160.820
148.063
g
g
Sulphur loss/leach
Sulphur recovery
12.757
92.067
g
%
5.015
4.617
mol
mol
0.019
0.003
%
%
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
2.830
1.400
%
%
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
0.000
0.000
%
%
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
0.010
0.002
%
%
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
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
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
0.167
kg
1.500
1.667
kg
kg
65
Gross weight
1.667
kg
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
149.3
Temp
(Tare+pulp
weight)
FeSO4
concentration
kg
added
kg/kg
Cu
conc
concentration
77
Cu rec.
% Cu
69.8077
92.0192
84.0865
Appendix V
Atomic absorption spectroscopy, AAS
78
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.
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
80
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.
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
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
Calculated
head
assays
Purified
46
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
Calculated
head
assays
Purified
Ca
%
46
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
Calculated
head
assays
Purified
46
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 -
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
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)
89
90