Escolar Documentos
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________________________________________________________
An Undergraduate Thesis
College of Engineering
Iligan City
________________________________________________________
In Partial Fulfillment of
May 2010
Mindanao State University
ILIGAN INSTITUTE OF TECHNOLOGY
Iligan City, 9200 Philippines
_____________________________________________________
COLLEGE OF ENGINEERING
APPROVAL SHEET
The undergraduate thesis attach hereto entitled “Bulk Flotation of Complex Copper
Ore From Siocon, Zamboanga del Norte”, prepared and submitted by KHMER LEE P.
LUGOD, in partial fulfillment of the requirements for the degree in Bachelor of Science
in METALLURGICAL ENGINEERING is hereby recommended for approval.
This undergraduate thesis is approved in partial fulfillment of the requirements for the
degree of Bachelor of Science in METALLURGICAL ENGINEERING.
___________________ ___________________
Date Signed
Date Signed
ABSTRACT
Complex ores contain profitable amounts of more than one valuable mineral. One
of the most common of these ores is the copper-zinc sulfide. In the Philippines such type
of ores can be found in the Bicol and Zamboanga peninsula. The separation of zinc and
copper has posed a challenge to a profitable concentration process. The problem is even
more complicated with the presence of arsenic whose content could be greater than the
smelter’s acceptable limit. This study examined the bulk flotation of copper and zinc
utilizing O-isopropyl ethyl thiocarbamate (NASCOL 446) and di-isobutyl
monothiophosphate (NASCOL 201) as collectors. The behavior of the associated arsenic
was also investigated.
One kilogram of ore, at -200 mesh was used as feed to the bulk flotation that was
conducted for 8 minutes. Two collectors, independently added, were used at 3 different
dosages: 20, 30, and 40 g/ton. The copper and zinc contents were determined as well as
their respective recoveries in the bulk concentrate. Arsenic content and recovery were
also calculated. Flotation using NASCOL 446 yielded 14.95% copper with 91.6 %
recovery using 40 g/ton. The best results for zinc was obtain using 40 g/ton NASCOL
446 which yielded 6.85% zinc with recovery 96.18% Zn. Arsenic lowest yield is 0.22%
arsenic with 96.7% recovery using 40 g/ton NASCOL 446.
ACKNOWLEDGEMENT
First and foremost, praise and thanks goes to my savior Jesus Christ for the many
blessing undeservingly bestowed upon me.
It would not have been possible to write this under-graduate thesis without the
help and support of the kind people around me, to only some of whom it is possible to
give particular mention here. Above all, I would like to thank my parents, brother Josef,
sister Lj and Aunt Lorna, who have given me their unequivocal support throughout, as
always, for which my mere expression of thanks likewise does not suffice.
This thesis would not have been possible without the help, support and patience of
my principal supervisor, Prof. Maria Teresa Ignacio, not to mention her advice and
unsurpassed knowledge of flotation studies.
To Prof. Julius Torralba and Engr Vannie Joy Resabal, my panel, thanks for
the truthful comments and suggestions on my papers.
I would like to acknowledge the academic and technical support of TVI Pacific
INC., and its staff, for providing the reagents and the sulphide ore, also in the analysis
of the bulk feed and bulk tails that provided the necessary financial support for this
research. To NASACO INTERNATIONAL and Engr Enrico Nera, for providing the
flotation reagents which is used in the study.
I am most grateful to Engr. Venice Onog and Engr Arnel Ang-og for providing
me the technical knowledge for the flotation study, which have been a valuable and
reliable method in the whole process. I would also like to thank Engr. Hans Enriquez,
for his kindness and generosity during my stay in TVI. To Engr. Edgardo V. Arellano,
for granting the proposal and etc., without his support, this study would not have been
possible.
I would like to thank Mr. Alexes Jann P. Agudera and Mr.Jonas Karl
Liwanag for their kindness, friendship and support, together with. The generosity and
encouragement of Mr. Belrie Dagasuhan, Jr, for his unending support. To Ms. Shelda
Capiral, who has never forgotten and for her generosity. To Ms. Jenny Suerte and
Shehannie Guliman and Richellie Yuson for the resources, kindness and help on the
study. To Ms. Dulce Libby Garay for lending her thesis softcopy is very will
appreciated. To Ate Marivic, Cecil, and Linda thanks for the endless support and
generosity, for the help and encouragement. To Maam Nannete Abatayo, for her
support, patience, and guidance on the use of laboratory equipments and others.
Amongst my fellow undergraduate students in the Department of Metallurgical
Engineering, the effort made by Ms. Patricia Candari, Aileen Insalada, Jane Flores,
and team MESS for organizing the thesis presentation.
I would also like to thank my colleagues and friends in the College of
Engineering, Education, Arts and Sciences, Science and Mathematics. Last, but by no
means least, I thank my friends in Apexmines (Engr. Anarica Palconet and Ruben
Caballero) , A. Boulton of AB Offices LLC -USA, Val Flint of Reinforce- Australia,
Gee Rod of Webmate-UK, and elsewhere for their support and encouragement
throughout, some of whom have already been named.
For any errors or inadequacies that may remain in this work, of course, the
responsibility is entirely my own.
vi
LIST OF CONTENTS
Title Page i
Approval Sheet ii
Free Page iii
Abstract iv
Acknowledgement v
Table of Contents vii
List of Tables ix
List of Figures x
I INTRODUCTION
III METHODOLOGY 17
PAGE
5.1 Conclusion 39
5.2 Recommendations 39
BIBLIOGRAPHY 41
APPENDICES
A Calculations 44
B Tables of Obtained and Calculated 45
Results
C Calculated Recoveries 54
D Statistical Analysis 56
E Equipments, Materials, Procedures and 58
Products
viii
LIST OF TABLES
PAGE
PAGE
INTRODUCTION
TVI Philippines Inc. is mining a complex ore which is being studied for the
recovery of both zinc and copper. A polymetallic ore could possibly produce more than
one mineral concentrate. However, the ore also contains arsenic. It is one of the elements
that is encountered in copper sulfide concentrates, and its removal from associated
sulphide minerals is recommended in order to reduce contamination of the valuable
concentrate and/or to reduce, arsenic emission to the atmosphere (Kantar, 2002).
Complex ores contain profitable amounts of more than one valuable mineral.
Metallic minerals are often found in certain associations within which they may occur as
mixtures of a wide range of particle sizes or as single-phase solid solutions or
compounds. Galena and sphalerite, for example, associate themselves commonly, as do
copper sulphide minerals and sphalerite to a lesser extent. Pyrite (FeS2) is very often
associated with these minerals (Wills, 1997).
According to Bulatovic (2007), the complex sulfide copper ores are considered
easy to treat provided that the main copper mineral is chalcopyrite. In case the ore
contains secondary copper minerals, such as chalcocite, bornite and covellite, depression
of pyrite may be a problem because the pyrite can be activated by copper ions generated
during the grinding operation. Some copper sulfide ores can be partially oxidized, also
influencing the selection of a reagent scheme, with the exception being a hypogene
sulfide copper ore.
2
There are two common options practiced in the treatment of these ores. These are
(1) sequential copper flotation from pyrite and other sulfides, the most common practice
in the treatment of sulfides ores and (2) bulk or semi-bulk flotation followed by copper–
pyrite separation after re-grinding of the bulk concentrate. This method is used in the
case where copper is finely disseminated with pyrite or with ore that contains clay
minerals (of acidic nature), which interferes with copper flotation (Bulatovic, 2007).
The reagent schemes used for the treatment of complex sulfide copper ores are
much more diverse and are designed to cope with specific problems associated with
processing the ore. When treating hypogene sulfide copper ores, the reagent scheme is
relatively simple. It uses xanthate as a collector in alkaline pH (11.0–11.5). In some
cases, dithiophosphate is used as a secondary collector when secondary copper minerals
are present in the ore. In the case of stringer ore and copper ores in which the pyrite is
active, the reagent scheme is more complex and involves different depressant
combinations (Bulatovic, 2007).
The choice of collector also depends on the nature and occurrence of copper and
associated sulfides. In most cases, xanthate collectors are used alone or in combination
with dithiophosphates or thionocarbamates. Dithiophosphates and thionocarbamates are
normally used when secondary copper minerals are present in the ore or when the copper
flotation is carried out at lower pH. A mixture of xanthates (i.e. ethyl-butyl, ethyl-
isopropyl) has been successfully used in a number of Russian operations where both
selectivity and recovery were improved when using a mixture of two xanthates
(Bulatovic, 2007).
The bulk flotation process is essential to pre-clean the mineral of the arsenic
present in its raw stage and prior to sequential flotation of poly-metallic minerals.
3
Flotation is, at the present, the only method that can be used to beneficiate the
complex sulfides such as copper-lead-zinc and copper-zinc. The process involves a
series of flotation known as the differential flotation. In the flotation of copper-zinc
massive sulfide ores, flotation properties of copper and zinc are determined by the nature
and composition of the ore. Copper zinc massive sulfide is even regarded as the most
complex ore and consequently the most difficult to treat. The complexity of the ore leads
to certain ways of treating it by the use of sequential flotation in which copper and zinc
are floated in series of operation that may involve a bulk flotation of copper and zinc
feeding it to another circuit of copper and zinc separation in order to produce both
marketable value of copper and zinc concentrate (Bulatovic, 2007). To optimize a
flotation operation, test works of reagents are conducted.
Early removal of arsenic in the bulk flotation will yield better quality of copper
concentrate. With early removal of arsenic, there will be a better feed in the subsequent
flotation system. With a better copper quality in the bulk feed, there is less cost in the
differential separation of copper and zinc. This will result to higher recoveries of copper
after the bulk concentration. It will also result to a more efficient separation since the
gangue mineral has been pre removed and pose fewer problems in the copper and zinc
flotation.
The purpose of bulk flotation is usually to separate one or more minerals from the
other minerals, and the selective adsorption of collector on floatable minerals is a
prerequisite for a successful separation. The selectivity of collector adsorption is often
affected by regulating agents. They can either enhance or prevent the adsorption of
collector on a particular mineral.
The chemical analysis of the sample was done in TVI. Analysis was limited to
base metals, and analysis for gold was not conducted due to financial constraints. The
age of the ore was not considered. Liberation size analysis was not taken and the -200
mesh grinding was assumed to be sufficient based on the physical appearance of the ore.
Analysis of the pulp for the presence of ions was also not conducted.
CHAPTER II
Some minerals are naturally hydrophobic like Sphalerite and Chalcopyrite coal
and molybdenite. However natural hydrophobicity of sulphides minerals is the most
debatable issue in the field of sulphides flotation (Mendiratta, 2000).
and S2O32-, and created relatively fresh surface. Secondly, it sulphadized the mineral
sulphur species (Mendiratta, 2002).
Depending upon pH, excess sulphides ions on the surface may be oxidized to
elemental sulphur or polysulphides, rendering it more hydrophobic. It is proposed that
there is the formation of hydrophobic metal-deficient sulphur layer upon mild oxidation.
On the formation of iron oxide on chalcopyrite, a metal deficient layer (unexposed metal
surface) can be floated without collector (Mendiratta, 2002).
Based on the work of Mendiratta (2002) sulphides minerals are ranked according
to their natural hydrophibicities in the descending order as follows: Chalcopyrite > galena
> Pyrrhotite > Pentlandite > Covellite > Bornite > Chalcocite > Sphalerite > Pyrite >
Arsenopyrite.
According to Bulatovic (2007), sulfide copper ores are considered easy to treat
provided that the main copper mineral is chalcopyrite. In case the ore contains secondary
copper minerals, such as chalcocite, bornite and covellite, depression of pyrite may be a
9
problem because the pyrite can be activated by copper ions generated during the grinding
operation. Some copper sulfide ores can be partially oxidized, also influencing the
selection of a reagent scheme, with the exception being a hypogene sulfide copper ore.
Copper sulfide ores are normally finer grained than porphyry copper ores and require
finer grinding (i.e. 70–80% <200 mesh). He also added that copper sulfide ores are
disseminated and in some cases, would require fine re-grinding of the rougher
concentrate. Fine copper minerals have a low rate of flotation, which may result in losses
in recovery. Unlike porphyry copper ore, where the reagent schemes are similar for most
operations, the reagent schemes used for the treatment of sulfide copper ores are much
more diverse and are designed to cope with specific problems associated with processing
the ore.
Sphalerite is the most important mineral which appears in many lead–zinc and
copper– lead–zinc ores. The composition of sphalerite is highly variable and depends on
the impurities contained in sphalerite. According to Takeuchi and Gondo (1957), the
difference of floatability of zinc ores is due to the difference in kinds or inclusions in it,
such as iron or copper minerals. In zinc fine particles of copper minerals could be found.
Cu++ activates zinc ore, the floatability of zinc ore is controlled by the solubility of
coexisting copper ore, the surface of zinc is activated by Cu++, and then the floatability
of zinc ore increases. These impurities are either replacements of zinc in the crystal
10
Apart from the copper activation of sphalerite, the presence of silver, arsenic or
other ions, which come from sulfosalts, may activate sphalerite and create a problem in
the selective separation of copper and sphalerite. Although literature and textbooks
contain vast references on flotation, activation and de-activation of sphalerite, little to
nothing is known regarding the flotation behavior of sphalerite that contains impurities,
even though it is the mineral that has been studied the most. In actual practice, the
separation of sphalerite from copper can be very difficult on one hand, or flotation of
sphalerite from pyrite and/or pyrrhotite can be relatively easy, on the other hand
(Bulatovic, 2007).
In flotation, several parameters are to be observed such as the pH of the slurry and
its percent solids. In controlling the pH, lime is usually used in plant. The use of a lime
circuit is practically universal in the flotation of copper ores. Lime alkalinity is generally
maintained in the pH range of 9.5 to 11.5. The higher pH serves to depress the iron
sulfide gangue minerals which are commonly present. The pH can also influence the
froth structure and floatability of the copper minerals. These characteristics are adversely
affected below some minimum pH value which varies from ore to ore, especially when
xanthates and dithiophosphates are used. (Cytec Industries Inc., 2002). The presence of
iron ions in solution depends on the oxidation behaviour of the sulphide ore and on the
chemical conditions of the pulp. A common way for activating the surface of pyrite and
arsenopyrite is through the addition of copper ions, which improve their recoveries
(Monte, 2002).
11
Arsenic occurs at varying levels in some copper ore bodies, and is a significant
environmental hazard in the copper smelting process when emissions are released into the
atmosphere. The arsenic in the ore is contained in copper-arsenic sulfide minerals, such
as arsenopyrite and tennanite (Smedley and Kinniburgh, 2002). Arsenopyrite is one of
the comparatively little studied sulphide minerals in the flotation technology (O'Connor,
et al, 1990).
Trace elements such as Arsenic, bismuth, cadmium, lead, and etc. may also be
present in varying amounts. Arsenic removal in sulphide flotation has been studied
extensively by Ma and Bruckard, (2009) with various approaches, including pre-
oxidation of flotation pulp, Eh control during flotation and the use of selective
depressants/collectors. Pre-oxidation of flotation pulp using oxidizing agents or aeration
conditioning represents a simple approach in arsenic removal and was found effective in
many cases. Selective flotation of arsenic minerals through Eh control has made
significant advances in recent years with promising results achieved.
In addition, various depressants and collectors have also been studied in arsenic
removal. O'Connor, et al, (1990) suggested the recovery of arsenopyrite from an
arsenopyrite/pyrite ore is desirable for a number of reasons. This can be optimized using
a two stage flotation process in which a dithiophosphate is added at pH=11 in the first
12
stage and copper sulphate and a dithiocarbamate in the second stage. It was found that
better separations were obtained when aged ore was used. It was possible to simulate this
ageing process by heating. The basis of the separation relies on findings that the lower
limiting pulp potential threshold for tennantite is lower than that for chalcopyrite such
that there is a potential window in the reducing region where tennantite is strongly
floatable but chalcopyrite is not. Little or no selectivity between tennantite and
chalcopyrite was found in the oxidizing pulp potential region for the range examined (Ma
and Bruckard, 2009).
From the composite sample tested by Ma and Bruckard (2009), which had a head
grade of 0.11% As and 1.2% Cu, it was possible to produce a low-arsenic high-copper
concentrate containing 52% of the non-tennantite copper and assaying 2600 ppm As.
Computer simulations have shown that for a feed containing a more typical arsenic and
copper level (200 ppm As and 1% Cu) the efficiency of separation should be sufficient to
concentrate about 61% of the copper in a product assaying less than 2000 ppm As. Aside
from flotation studies to remove contaminants like arsenic in the polymetallic minerals by
flotation , studies done by Curreli et. al.( 2008), on alkaline leaching shows an increase
of arsenic extraction which is enhance by the effect of mechanical activation. Arsenic
leaching provides a better separation of gangue minerals by means of alkaline leaching
with mixtures of sodium sulfide and sodium hydroxide. In their study, the influence of
the most significant process variables like specific area of the solid, temperature, pH, and
reagent concentration of the leach solution has been investigated. Leaching selectively
solubilises the arsenic and some gold but does not affect the copper which transform
entirely in the leach residue as a new species. Increasing the surface area of the
concentrates at temperature of 100 degrees improves the efficiency of the whole process.
The theory and practice of sulfide flotation again state that effectiveness of all
classes of flotation agents, to a large extent on the degree of alkalinity or acidity of the
ore pulp. As a result, modifiers that regulate the pH are of great importance. The most
commonly used pH regulators are lime, soda ash and, to a lesser extent, caustic soda. In
sulfide flotation, however, lime is by far the most extensively used. In copper sulfide
13
flotation, which dominates the sulfide flotation industry, or example, lime is used to
maintain pH values over 10.5, more usually above 11.0 and often as high as 12 or 12.5.
In prior art sulfide flotation processes, preadjustment of the pH of the pulp slurry to 11.0
and above is necessary, not only to depress the notorious gangue sulfide minerals of iron,
such as pyrite and pyrrhotite, but also to improve the performance of a majority of the
conventional sulfide collectors, such as xanthates, di-thiophosphates, trithiocarbonates
and thionocarbamates (Nagaraj and Wang, 1986).
Most of operating plants, treating gold bearing sulphide ores, use various types of
xanthate, as primary collector, in combination with dithiophosphate as secondary
collector. Mercaptobenzothiazole is usually employed for the treatment of oxidised
pyrite containing ores, with little or even no xanthate additions to the scavenger flotation
operation. The thiol collector-mineral adsorption reaction strongly affects the floatability
of sulphide minerals. The rate of collector adsorption can be influenced by many factors.
Pre-treatment conditions, such as: the grinding environment, the dissolved oxygen
concentration, the pulp potential and the pH, are the key factors which determine the
extent and kinetics of this reaction (Monte et al, 2002).
It is well established that the adsorption of xanthate occurs via a mixed potential
mechanism, involving the anodic oxidation of xanthate and the cathodic reduction of
oxygen.The adsorption of xanthate results either in the formation of dixanthogen or metal
xanthate. In the first case, the mineral itself does not participate in the reaction except
offering a passage for the transfer of electron. This would be the case for xanthate
adsorption on pyrite, pyrrhotite, and gold (Richardson, 1976).
For the case of xanthate adsorbing on some of the other sulfide minerals (e.g., chalcocite
and galena), the mineral itself is participating in the adsorption process resulting in the
formation of metal xanthates. The mechanism may be viewed as a two-step process
involving an initial electrochemical reaction (E), which is the oxidation of the mineral to
release the metal ions, followed by the chemical reaction (C) between the metal ions and
xanthate to form metal xanthate. In organic electrochemistry, such mechanisms are
referred to as coupled electrochemical and chemical reactions of the EC-type (Dung,
1995).
The beneficial effects of the synergy between two or more reagents were realized
long time ago. The purpose of using a mixture of collectors was to increase both the
recovery and selectivity. Two thiol collectors, isopropyl xanthate (SIPX) and di-isobutyl
dithiophosphinate (DTPI), having different chemical and functional properties, were
used. The adsorption behavior of these collectors from their mixtures was investigated at
various SIPX:DTPI ratios and sequence of addition by cyclic voltammetry and adsorption
experiments at pH 9.2. The results revealed that the maximum synergistic effect of using
mixture of SIPX and DTPI was strongly influenced by the ratio of the collectors in the
mixture and particularly sequence of addition (Bagci, et.al. 2007).
15
Unlike porphyry copper ore, where the reagent schemes are similar for most
operations, the reagent schemes used for the treatment of sulfide copper ores are much
more diverse and are designed to cope with specific problems associated with processing
the ore.
When treating hypogene sulfide copper ores, the reagent scheme is relatively simple.
It uses xanthate as a collector in alkaline pH (11.0–11.5). In some cases, dithiophosphate
is used as a secondary collector when secondary copper minerals are present in the ore.
In the case of stringer ore and copper ores in which the pyrite is active, the reagent
scheme is more complex and involves different depressant combination (Bulatovic,
2007).
The choice of collector also depends on the nature and occurrence of copper and
associated sulfides. In most cases, xanthate collectors are used alone or in combination
with dithiophosphates or thionocarbamates. Dithiophosphates and thionocarbamates are
normally used when secondary copper minerals are present in the ore or when the copper
flotation is carried out at lower pH. Good metallurgical results are obtained with
thionocarbamate during the flotation of clay-containing sulfide copper ore (Bulatovic,
2007).
Ethyl thiocarbamate also exhibits the better flotation results than xanthates and
dithiophosphates in flotation of copper, lead, zinc, antimony and other poly-metallic
sulfides (Flotation Reagents, 2010)
The processes that affected the hydrophobicity of the particles and consequently
affected copper recovery and grade may have been the selective adsorption of the
different collectors on particular sites or changes in the orientation of the alkyl chains
resulting in superior surface coverage (Hangone, et al., 2005). In addition, for a mixture
of xanthate and dithiophosphate there may have been enhanced co-adsorption of
collectors at low collector concentrations. These phenomena may have played a role in
determining the degree of hydrophobicity of the mineral surface and may therefore have
been responsible for the differences in froth properties (Mermillod et. al, 2005)
CHAPTER III
METHODOLOGY
The raw ore was from TVI Phils. Inc, in Siocon, Zamboanga del Norte is a
complex copper-zinc ore obtained from the mine site‘s high sulphide zone. The samples
were crushed to -20 mesh and was ground using a laboratory ball mill. The feed to the
bulk flotation was -200 mesh. A representative sample was taken for chemical analysis.
The density of the ore was obtained using the Volume Displacement Method
using a 100 ml flash and a 32 gram ore sample. The difference in volume of the water
after filling the flask with the ore specimen was used to solve the density of the ore using
this equation:
𝑚
D= 𝑣
A one kilogram ore, passing -200 mesh was fed to the flotation machine for the bulk
flotation of copper and zinc. A 30% solid by weight slurry was used. Collectors were
added separately and independent of each, in the flotation set-up. The collectors are
NASCOL 201 (O-isopropyl ethyl thiocarbamate) and NASCOL 446 (di-isobutyl
monothiophosphate ) , in the three different dosages. NASCOL HEL was used as a
frother. Lime was used to modify pH to 11 after collectors and frothers were added.
Flotation was carried out after 5 minutes of conditioning. Flotation time was 8 minutes.
18
3.3 Reagents
1000 g Ore
-200 Mesh
Collector A or
Collector B 30% Solid
BULK
CONCENTRATE
3.5 Microscopy
The concentrate produced in the bulk flotation was analyzed by microscopy using
the optical microscope. Representative samples of bulk concentrates and bulk feed were
mounted separately on glass slides. The mineralogy of the ore was determined using
Nikon Optiphot – 100 Metallurgical Microscope. Pictures were taken at 200x
magnification.
20
The recoveries of the concentrate were set up using the material balance. Bulk
feed and bulk tails were weighed after filtration and drying. The weights gathered were
used in the calculation. Results from the chemical analysis (ICP) were used for the
computation of the concentrate‘s assay and percent recoveries using the following
equations:
F=C+T (3.1)
fF = cC + tT (3.2)
fF
where:
F – weight of feed
C – weight of concentrate
T – weight of tails
f – assay of feed
t – assay of tails
c – assay of concentrate
21
COLLECTOR
Dosage A B
Where A and B (NASCOL 201 and NASCOL 446) are collectors used during
bulk flotation with 1, 2, and 3 as dosages. The frother used in the bulk flotation was only
NASCOL HEL.
CHAPTER IV
The minerals present in the ore were bornite, sphalerite, arsenopyrite, and pyrite
as observed by microscopy. XRD analysis by Garay (2010) confirmed the analysis as
major mineral components of the copper ore. Covellite, cubanite, stibnite, bismuthinite,
hematite, magnetite, and quartz are also present Garay (2010). Finely disseminated
pyrite can be observed on the Fig 4.1. The ore was milled up to 100 percent passing 200
mesh to liberate minerals from pyrite. Table 4.1 below provides the chemical analysis of
the bulk feed which confirmed the existence of a copper-zinc polymetallic system.
Table 4.1 Chemical analysis of the bulk feed using Inductive Coupled Plasma (ICP).
As 0.21 Pb 0.07
Bi 71 ppm S 26.61
Cu 9.28 Zn 4.03
Fe 36.51
23
Figure 4.1 Pyrite from bulk feed (a) pyrite at -200, +325 mesh; 500x
magnification (b) Reference picture for pyrite (Chesterton, 2000)
Figure 4.2 From bulk feed,(a) sphalerite (b) arsenopyrite (-200, +140
mesh @ 500x magnification)
24
Figure 4.4 Bornite from bulk feed (a) bornite -200, +200 mesh @ 500x
magnification, (b) Reference picture for bornite (Chesterton, 2000)
25
a b
Fig. 4.7 shows copper flotation. The colour of the froth during copper flotation
was observed to be greyish. It appeared that zinc could have floated with copper during
the bulk flotation.
The Cu grade of the bulk feed was 9.28% Cu. The highest grade of copper in the bulk
concentrate was 14.95% Cu using a 40 g/t NASCOL 446, and 12.85% Cu using 30 g/t
of NASCOL 201. The lowest mean grade was obtained using a 20 g/t of NASCOL 201
at 9.5% Cu.
27
20 11.85 9.5
30 13.1 12.85
40 14.95 11.2
Table 4.4 shows the calculated recoveries of copper for both NASCOL 446 (di-
isobutyl monothiophosphate) and NASCOL 201 (O-isopropyl ethyl thiocarbamate). For
the recovery of copper, the best results were obtained using 30 g/t of NASCOL 446
which is 92.7% as shown on table 4.5. The highest was seen at 30 g/t using NASCOL
446 with 92.70 % recovery as shown in table 4.4. The lowest recovery at 62,22 % Cu
was obtained using a 40 g/t of NASCOL 201.
28
20 89.62 71.91
30 92.7 80.2
40 91.6 62.2
Figures 4.8 shows the copper recoveries and that the lowest recoveries were
obtained with NASCOL 201 (O-isopropyl ethyl thiocarbamate). NASCOL 446 showed
higher recoveries and better copper grades in the concentrate compared with NASCOL
201. The highest mean grade, 14.95% was obtained using NASCOL 446 at 40kg/ton
dosage with a mean recovery of 91.58%. Highest recovery at 92.71% was obtained using
a lower dosage of 30 kg/ton but a lower copper grade of 13.1%. What appeared to be a
better flotation of the copper minerals with NASCOL 446 may be due to the added
hydrophobicity which is provided by the additional alkyl group of di-isobutyl
29
100
90
80
% Recovery of Copper
70
60
50
NASCOL 201
40
NASCOL 446
30
20
10
0
0 20 40 60
Dosage (g/ton)
Statistical analysis showed that the effect of collector was significant on the
recovery of copper, while variation of dosages was insignificant. The lower grade but
high recoveries could be due to the inclusion of pyrites in the float. Pyrite is activated by
copper ions (Monte, 2002). The presence of bornite which releases copper ions activates
pyrite during the grinding operation (Bulatovic, 2007). In most cases according to Wills
(2007), the activated sphalerite and pyrite in the bulk concentrate are covered with a layer
of collector, and are difficult to depress unless extremely large amounts of reagent are
30
16
14
12
% Grade of Copper
10
8
NASCOL 201
6 NASCOL 446
0
0 20 40 60
Dosage (g/ton)
Although the effect of collectors‘ dosage was insignificant grade increased with
increase in concentration up to 40 g/ton, NASCOL 201 exhibited low recovery (62.2%)
and low grade (9.5 %) on the bulk concentrate as shown on table 4.4 and 4.6.
The zinc grade of the bulk feed was 4.03% Zn. The amount of zinc in the bulk
concentrate was 6.85 % for the NASCOL 446 and 5.35% for the NASCOL 201. This
31
observation was also verified by calculating the recovery of zinc in the bulk concentrate
shown on table 4.6.
Table 4.6 Recoveries of zinc in the bulk concentrate utilizing NASCOL 446 and
NASCOL 201.
Table 4.7 Mean recoveries of zinc in the bulk concentrate using NASCOL 446 and
NASCOL 201.
20 90.47 86.1
30 96.19 91.6
40 96.18 80.8
Table 4.6 and 4.7 show the calculated recoveries of zinc for both NASCOL 446
(di-isobutyl monothiophosphate) and NASCOL 201 (O-isopropyl ethyl thiocarbamate).
For the recovery of zinc, the best results were obtained using 40 g/t NASCOL 446 with
32
96.19 % recovery (see also tables 4.8 and 4.9 for dosage results). The ANOVA showed
that the effect of the dosages of the collectors were not significant on the recoveries of
zinc. However, collector variation was significant.
20 5.22 5.35
30 5.92 4.98
40 6.85 4.49
The impurities that may be present in the ore such as iron, copper and cadmium
may result to sphalerite activation. The secondary copper minerals that may be present in
the ore could be soluble and during grinding, or in situ, could have released copper ions,
which activated sphalerite. This is common in copper–zinc ores that contain secondary
33
copper minerals with a covellite layer on the sphalerite surface. Figures 4.11 and 4.12,
show O-isopropyl ethyl thiocarbamate had the lowest recovery and zinc content in the
bulk concentrate. Galvanic interaction between sphalerite and chalcopyrite-pyrite
mineral mixtures causes dissolution of copper ions from chalcopyrite and thus activation
of sphalerite and pyrite by these copper ions (Ekmekci,et al.,2004). Soluble cations that
may be present could also activate pyrite minerals, increasing collector consumption and
often activate sphalerite. Ores with strongly activated sphalerite, either by lead cations or
by copper, which comes from the secondary copper minerals such as bornite, digenite
and covellite, may contain iron hydroxides, slimes and clay minerals (Bulatovic, 2007).
Cu++ activates zinc ore, the flotability of zinc ore is controlled by the solubility of
coexisting copper ore, then the flotability of zinc ore increases (Takeuchi, et.al, 1957).
The lowest grade of arsenic was obtained using NASCOL 446 at dosage 40 g/ton
as shown on figure 4.13. The lowest recovery was obtained using 40 g/ton NASCOL 201
as shown on figure 4.11. Arsenic recovery with respect to copper might indicate that
arsenic is in solid solution with copper. The analysis of Garay (2010) showed arsenic at
0.09% As in the run-of-mine ore, and however XRD did not reveal any presence of the
suspected mineral tennantite. Arsenopyrite was also detected on microscopy, but was not
confirmed on XRD analysis. Orpiment (As2S3) was also seen, but XRD only inferred its
presence (Garay, 2010).
Table 4.10, 4.11, 4.12, and 4.13 show the calculated recoveries and grades of
arsenic in copper the bulk concentrate. Arsenic is a penalty element for concentrates
35
which a concentrator wishes to eliminate. Arsenic in the feed was 0.21%, the highest
percentage, 0.36%, was found using NASCOL 446 at 40 g/t. This was below the typical
smelter penalty level of 0.5% As. The best result was obtained using NASCOL 446
which yielded 0.22% Arsenic with recovery of 96.7%.
Table 4.10 Recoveries of arsenic in the bulk concentrate utilizing NASCOL 446
and NASCOL 201.
Table 4.11 Mean recovery of arsenic in the bulk concentrate using NASCOL 446
and NASCOL 201.
20 91.4 86.1
30 95.9 90.4
40 96.7 77.7
36
20 0.28 0.30
30 0.25 0.30
40 0.22 0.36
The Analysis of Variance (ANOVA) showed that the effects of the variation of
collectors were significant on the recovery of arsenic. The effects of the different
dosages of the two collectors were not significant on the recoveries of arsenic.
37
Dosage vs Recovery of As
120
100
80
% Recovery
60
NASCOL 201
40 NASCOL 446
20
0
0 1 2 3 4
Dosage
5.1 Conclusions
1. The effect of the collector variation was significant on both recoveries and grades of
copper and zinc. Using 40 g/ton of NASCOL 446, the highest copper percentage in
the bulk concentrate was 14.95% Cu, with a recovery of 91.6 %; while for zinc; best
grade was 6.85% Zn, and a recovery of 96.18 %. For arsenic, lowest grade was at
0.22% As using NASCOL 221.
2. Variation of dosage for both collectors had no significant effects on copper, zinc, and
arsenic recovery in the bulk concentrate, however, the highest was observed at 40
kg/ton of NASCOL 446 with 91.6 % % for copper, 96.18% for zinc. The lowest
recovery, 96.7% for arsenic was at 40 g/ton kg/ton dosage using NASCOL 446.
3. Bulk feed was made of chalcopyrite, bornite, pyrite and sphalerite, and other
associated mineral.
40
5.2 Recommendations
BIBLIOGRAPHY
Curreli, L., Garbarino, C., Ghiani, M., Orru, G. 2009. Arsenic leaching from a gold
bearing enargite flotation concentrate. Hydrometallurgy, 96(3):258-263
Hangone, G., et al,2005. Flotation of a copper sulphide ore from Okiep using thiol
collectors and their mixtures. Journal of the South African Institute of Mining and
Metallurgy, 105(3):200-206
42
Mendiratta, N., 2000. Kinetic Studies of Sulfide Mineral Oxidation and Xanthate
adsorption. PhD Thesis. Virginia Polytechnic Institute and State University, Virginia,
USA. pp 13-17
Mermillod R., Kongolo, M., de Donato, P., Benzaazoua, M., Barrès, O., Bussière, B.,
Aubertin, M., 2005. Pyrite flotation with xanthate under alkaline conditions –
application to environmental desulfurization. Centenary of Flotation Symposium.
Brisbane, QLD, Australia
Ma, X. and Bruckard W.J., 2009. Rejection of arsenic minerals in sulfide flotation —
A literature review. CSIRO Minerals, Box 312, Clayton, Victoria, Australia,
ScienceDirect - International Journal of Mineral, 93(2):89-94
<http://tinyurl.com/28nzp2q> (Accessed: May, 10 2010).
Makita, M., Esperon M., Pereyra, M., López, A., Orrantia, E., 2004. Reduction of
arsenic content in a complex galena concentrate by Acidithiobacillus, BioMed
Central | Full text | Reduction of arsenic content in a complex galena concentrate by
Acidithiobacillus ferrooxidans, <www.biomedcentral.com/1472-6750/4/22>
(Accessed :May 7, 2000) .
Monte, MB. Lins, FF., Dutra, AJ., Albuquerque, CR., Tondo, LA., 2002. The
Influence of the oxidation state of pyrite and arsenopyrite on the flotation of an
auriferous sulphide ore. Minerals Engineering, 15(12):1113-1120
Smedley PL & Kinniburgh DG, 2002. A review of the source, behavior and
distribution of arsenic in natural water. Appl Geochem 17:517-568
43
Takeuchi, T.,Gondo, K., 1957. Studies on the treatment of Complex Sulphide Ores
from Yonaihata Mine, Fukushima Prefecture. The Research Institute of Mineral
Dressing and Metallurgy. pp 451-452
Yoon, R.H., 1989. The Effect of Bubble Size on Fine Particle Flotation, Mineral
Processing and Extractive Metallurgy Review, 1(4):101-122
44
APPENDIX A
CALCULATIONS
A. Recovery Formula
Mass balances and material balances were set up to calculate for recoveries.
F=C+T A.1
fF = cC + tT A.2
C=F–T
C = 1000 g – 340.6
C = 659.4 g
fF = cC + tT
c = (fF – tT)/ C
% Recovery = cC x 100
Ff
45
APPENDIX B
Copper Grade
Dosage
NASCOL 201
1 2 3
Copper Grade
Dosage
NASCOL 446
1 2 3
Zinc Grade
Dosage
NASCOL 201
1 2 3
Zinc Grade
Dosage
NASCOL 446
1 2 3
Arsenic Grade
Dosage
NASCOL 201
1 2 3
Arsenic Grade
Dosage
NASCOL 446
1 2 3
Element Assay, %
Ag 57.8 ppm
As 0.21
Bi 71 ppm
Cd 303.22 ppm
Cu 9.28
Fe 36.51
Hg 17.94 ppm
Pb 0.07
S 26.61
Sb 165 ppm
Zn 4.03
54
APPENDIX C
CALCULATED RECOVERIES
% Recovery of Copper
% Recovery of Zinc
% Recovery of Arsenic
APPENDIX D
STATISTICAL ANALYSIS
90
Estimated Marginal Means
80
Reagent Type
nascol 201
70 nascol 446
Dosage 1 Dosage 2 Dosage 3
Dosage
APPENDIX E
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Educational Background