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A Publication
IN THIS ISSUE
of the Society
• Thermochemistry of the Fe, Ni and Co-NH3-
H2O systems as they relate to the Caron process:
a review for Mining,
• Coarse particle fracture with the ultrafast load cell
• TECHNICAL NOTE: Beneficiation of refractory Metallurgy, and
rock phosphate by calcination and flotation
• Influence of pebble mill operating conditions on
measurements with an in-mill sensor Exploration, Inc.
• Recovery of mercury from spent silver oxide
button cells
• Purification of niobium oxide by dissolution and
solvent extraction
• Leaching characteristics of copper refractory ore
in sulfate media
Volume 28, Number 4

November 2011
M&MP NEWS Vol. 28, No. 4, November 2011
The November 2011 issue of Minerals & Metallurgical Processing is one of the
broadest yet, geographically speaking, with papers coming from Canada, Utah,
Iran, Sweden, Turkey, India and South Africa. The range of subjects is nearly as
broad, as these seven papers explore the processing of mercury, zinc, nickel,
iron, colbalt, phosphate, niobium and copper through different approaches to
leaching, grinding, comminution, flotation, solvent extraction and calcination,
among other key minerals processing techniques.
As many readers are aware, one of M&MP’s strengths are its high-profile
special issues, where specific subtopics of minerals processing are tackled in
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tion (SME) in Seattle, focuses on industrial minerals and will have papers on
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Thermochemistry of the Fe, Ni & Co-NH3-H2O systems 169
as they relate to the Caron process: a review
E. Asselin: University of British Columbia, Vancouver, BC
Coarse particle fracture with the ultrafast load cell 176

E.T. Tuzcu, N. Dhawan and R.K. Rajamani: University of Utah, Salt Lake City, UT
TECHNICAL NOTE: Beneficiation of refractory rock phosphate

by calcination and flotation 187
S. Khoshjavan and B. Rezai: Amirkabir University of Technology, Iran
Influence of pebble mill operating conditions 193

on measurements with an in-mill sensor
J. Alatalo and B.I. Pålsson: Luleå University of Technology, Luleå, Sweden
K. Tano: LKAB, Malmberget, Sweden
Recovery of mercury from spent silver oxide button cells 198

S. Aktas and M.H. Morcali: Istanbul Technical University, Istanbul, Turkey
Purification of niobium oxide by dissolution and solvent extraction 204

K.C. Nathsarma and B.B. Nayak: Institute of Minerals & Materials Technology, Orissa, India
P. Brahmbhatt and S. Pradhan: Institute for Plasma Research, Bhat, Gujarat, India
Leaching characteristics of copper refractory ore in sulfate media 208

R. van der Merwe and H. Kasaini: Tshwane University of Technology, Pretoria, South Africa
Index 215
Volume 28, No. 4

November 2011
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Thermochemistry of the Fe, Ni
and Co-NH3-H2O systems as they
relate to the Caron process: a review
E. Asselin
Assistant professor, University of British Columbia, Vancouver, BC
Abstract
Passivation of Fe-Ni-Co alloys during the Caron leach process is thought to result in low cobalt recoveries in
ammoniacal ammonium carbonate solutions. A brief review of the available thermochemical data for the (Fe,
Ni, Co)-NH3-H2O systems has been undertaken. The stability of the Co(II) and Co(III), Ni(II) and Fe(II) am-
mines was examined through the use of speciation and Pourbaix diagrams at 298 and 333 K and at 6 M total
ammonia. Increasing the temperature reduces the stability fields of the ammines and generally constrains the
thermodynamic window for the leach. The Fe(II) ammines are only thermodynamically stable under reducing
conditions. Polarization experiments show that these ammines are unlikely to form if oxygen is present. Fe-Ni-
Co alloy passivation may be alleviated by careful management of potential.
Minerals & Metallurgical Processing, 2011, Vol. 28, No. 4, pp. 169-175.
An official publication of the Society for Mining, Metallurgy and Exploration, Inc.
Key words: Hydrometallurgy; Thermodynamics; Laterites
Introduction and cobalt are then separated by sulfide precipitation, solvent

There have been several published studies extraction or through the formation of basic nickel carbonate
pertaining to the thermochemistry of the (Fe, Ni, via distillation. While the Caron process has the advantage of
Co)-NH3-H2O systems over the last three decades selective leaching of Ni and Co and of a recyclable leaching
(Osseo-Asare and Asihene, 1979; Osseo-Asare et reagent, there are two significant drawbacks to the process:
al., 1983). These studies have, in large part, been energy requirements for the ore drying and reduction steps
directed toward gaining a better understanding of the are high, and cobalt recovery is low: ~50%. The latter result
stability regions for ammines that play a central role is attributed to a combination of coprecipitation with ferric
in the selective leaching and separation of nickel and hydroxide and passivation of the Fe-Ni-Co alloy formed during
cobalt from both sulfide and laterite ores. After careful the reduction step (Nikoloski and Nicol, 2006; Senanayake et
review of the published equilibrium constant data, it al., 2010). Due to these two significant issues the implementa-
became evident that various gaps existed in our cur- tion of the Caron process has been limited.
rent understanding of ammine stability, particularly While the thermodynamics of this process have generally
for the ferrous ammines. This article aims to present been elucidated, some unresolved issues pertaining to the role
a review of the most current thermochemical data, as and stability of the Fe(II) ammines have not yet been docu-
well as some of the limitations of these data. mented under expected process conditions such as concentration
In the Caron process, limonitic nickel laterites are and temperature. These ammines have, to date, been thought to
dried and then reduced between 750 and 850° C. In play a role in the Caron process by allowing for the dissolution
this temperature range and under the appropriate re- of iron before its subsequent rejection as a hydroxide. This
ducing conditions, only a fraction of the nickel-bearing initial dissolution is thought to enable solubilization of the nickel
goethite (FeOOH) is reduced, while the nickel and and cobalt components of the alloy. This work examines the
cobalt are preferentially reduced to their metallic state. thermochemistry of the iron, cobalt and nickel-ammonia-water
As a result, the main products of this process step are systems with a view to identifying process conditions which
an alloy of Fe-Ni-Co and a largely unreduced gangue could lead to higher cobalt recoveries.
fraction. However, since sulfur-containing fuel oil is
used in the ore reduction process, Fe-Ni-Co sulfides Thermochemical calculations and data
are also a product. After reduction, these products are Speciation and Pourbaix diagrams were calculated for the
oxidatively leached at atmospheric temperatures in a Fe-NH3-H2O, Co-NH3-H2O and Ni-NH3-H2O systems at 298
solution of ammoniacal ammonium carbonate at pH and 333 K. Pourbaix diagrams were constructed based on the
~ 10 to form Ni(II) and Co(II)/(III) ammines. Nickel speciation calculation results, which were performed using an
Paper number MMP-11-006. Original manuscript submitted January 2011. Revised manuscript accepted for publication June
2011. Discussion of this peer-reviewed and approved paper is invited and must be submitted to SME Publications Dept.
prior to May 31, 2012. Copyright 2011, Society for Mining, Metallurgy, and Exploration, Inc.
MINERALS & METALLURGICAL PROCESSING 169 Vol. 28 No. 4 • November 2011

algorithm developed to determine the free ammonia concentra- species have been left out of this work.
tion as a function of pH. This method was then used to determine
the free metal concentration (Fe, Co or Ni) as a function of pH, Aqueous species. Partial molal properties for many aqueous
which, in turn, was used to calculate the redox reaction lines species at 298 K are available in the NBS Tables (Wagman et
on the Pourbaix diagram. A method similar to the one used for al., 1982). Unfortunately, standard entropy data for complexes
the calculation of the higher-temperature Pourbaix diagrams in such as ammines are often more difficult to find. Most are
this work is described in detail elsewhere (Macdonald, 1972). indirectly available as entropies of complexation, which are
Generally, the standard Gibbs free energy of a given species at listed in Smith and Martell’s tables for stability constants,
temperature T can be calculated according to Eq. (1). while some are available in the literature (Smith and Martell,
1977; Isaev et al., 1990a,b). Sources of data are indicated in
(1) the Appendix.
where and is the standard Gibbs free energy of It should be mentioned here that much of the historically
reported equilibria for Fe(II)-ammines are of an unreliable
formation at 298 K; = standard entropy at 298 K; nature. Generally, these data have come from the Sillen and
= average heat capacity over the temperature interval T – 298 Martell compilation, which lists the stepwise equilibrium
constants for the mono- and diammine Fe(II) species (K1 and
K; θ = T - 298 - T × ln(T/298). From Eq. (1), it can be seen K2) and the cumulative equilibrium constant for tetrammine
that the standard Gibbs free energy at T > 298 K was used in Fe(II), β4 ~ 3.7 (Sillen and Martell, 1964). In all cases, these
this work. This is in contrast to the methods of calculation that data were generated through indirect evidence and/or hypoth-
use the standard Gibbs free energy of formation, , which esis leading to only approximate values (Sillen and Martell,
is zero by convention for H+, Fe0, Co0 and Ni0 or any pure 1964). It is interesting to note that the later compilation of
element in their standard states at any chosen temperature. As Smith and Martell (1977), which is known as “Critical Stabil-
a result, the electrochemical reactions presented here at 333 K ity Constants,” does not include any of these data. Given the
will be referred to the standard hydrogen electrode (SHE) at paucity of published information pertaining to ammino-Fe(II)
298 K. In other words, the free energy change of the hydrogen species, the fact that the estimated equilibrium constants were
electrode was not incorporated into the calculations. small and that ferrous oxidation in even quasi-anoxic neutral
After an extensive literature search, it was decided to use the pH solutions is known to be fast (Park and Dempsey, 2005), it
free energies and entropies listed in the NBS Tables whenever was thought necessary to re-evaluate here the thermodynamic
possible (Wagman et al., 1982). Heat capacities for condensed stability of these species. Fortunately, a more recent investiga-
phases were taken from the thermochemical database compiled tion into the formation of Fe(II) ammines was conducted by
by Roine (2002). Heat capacities for aqueous species were Isaev et al. and data are now available for these species up to
estimated or taken from the literature as discussed below. 328 K in solutions of up to 5 M ammonia (Isaev et al., 1990a).
The various chemical species, together with the necessary As a general observation, it is regrettable that there are
thermodynamic data for use in Eq. (1), are presented in the no studies that we are aware of pertaining to metal ammonia
Appendix. The following paragraphs present a review of the complexation in sulfate or carbonate solutions, which are the
available data. main solutions of interest to the study of hydrometallurgy.
Most measurements have to date been performed in nitrate
Condensed phases. Generally, it can be stated that as solutions. Similarly, metal-ammonia complex equilibrium
temperature is increased, the predominance area for hydroxide data for temperatures greater than ~333 K are rare. A good
species is replaced by that of the equivalent valence oxide. This review on the subject of ammine thermochemical data as it
is due to a dehydration process. Thus, Co(OH)2 and Ni(OH)2 pertains to hydrometallurgy is provided by Mironov (Mironov
are expected to be less stable than CoO and NiO at elevated et al., 1992). The Fe(II) and Co(II) ammine data used here
temperatures. In the case of iron, there are no stable divalent are those of Isaev et al. and, since the equilibrium constants
oxides; rather, Fe(OH)2 is generally replaced by magnetite change according to ammonia concentration, the data chosen
(Fe3O4) as the temperature is increased. Because hydrometal- corresponds to that measured in the most relevant solution: 5
lurgical timescales are usually small, it is common practice to M total ammonia. The data used for the Ni(II) ammines at 298
construct quasi-equilibrium diagrams that present hydroxides K are from the compilation of Mironov (1992) for 2 M total
rather than oxide species. This is particularly relevant for modest ammonia. These data are almost identical to those proposed
temperatures where kinetics are limited. For these reasons, this by Bjerrum (1957).
method of presentation has been retained here at 298 and 333 One common method of estimating the average heat capacity
K. This paper focuses on the Fe, Ni & Co-NH3-H2O system. for ionic species at high temperatures is the Criss-Cobble ionic
It should be noted that the addition of carbonate to the system, entropy correspondence principle (Criss and Cobble, 1964).
as used in the Caron process, would also result in the stability In this work, a variant of the Criss-Cobble method, known as
of siderite (FeCO3) from pH 5 to approximately 8.8 at 298 K the Lewis linearization or, alternatively, as the linear ionic heat
(Osseo-Asare et al., 1983). However, the role of ferrous car- capacity approximation (LIHCA) is employed to estimate the
bonate in the dissolution of iron has been under investigation ionic heat capacities at 333 K (Lewis, 1970). This method is
since the mid-fifties. It has been shown quite conclusively described by the following equation:
that ferrous carbonates do not effectively passivate iron and CP (T) = b iT (2)
that passivation only occurs once magnetite or hematite is
formed. (Pourbaix, 1966; Linter and Burstein, 1999; Davies where ; and where
and Burstein, 1980). The iron dissolution process in the pH e and g depend on the ion type (simple cation, simple anion,
5-8.8 region may occur through a biscarbonato-Fe(II) species oxyanion, etc.) and have the units J.mol-1.K-1 and K-1, respec-
(Linter and Burstein, 1999). Since the inclusion of condensed tively. The number -20.92 represents the absolute entropy of
carbonate phases may lead to the impression that passivation the H+ ion in J.mol-1.K-1 at 298 K.
of iron (or nickel or cobalt) is possible from pH 5 to 8.8, these The Caron leach process is carried out in an ammonia-
November 2011 • Vol. 28 No. 4 170 MINERALS & METALLURGICAL PROCESSING

of aqueous phase stability (for example, the ammines) in favor
of the condensed phases (such as ferrous hydroxide). A lower
concentration of iron would do the opposite. Expected nickel
and cobalt concentrations in the loaded liquor are approximately
10-1 and 10-2 M, respectively, and these values were used in
the thermochemical calculations presented below (Nikoloski
and Nicol, 2010).
Thermodynamics of the Caron process leach

conditions
After reduction, the ore is typically cooled to less than 200°
C (473 K) and then quenched in leach liquor (Matson and
Milian, 1979; Reid, 1983). Reported leach temperatures are
~ 45° C or 318 K (Nikoloski and Nicol, 2006; Nikoloski and
Nicol, 2010). It is expected that the leach temperature should
Figure 1 — Calculated iron speciation at 10-3 M total iron change as the exothermic oxidation process takes place. As a
in 6 M total ammonia at 298 K. “FeAn” represents the result, calculations were performed here at the increments which
ammino-iron(II) species, where “n” is the number of delimit the range from 298 to 333 K. Under these conditions
ammonia ligands in the complex. the speciation of the Fe-NH3-H2O system can be described in
terms of the pH, as shown in Fig. 1 for 298 K.
According to Fig. 1, complete ammonia complexation of
cal ammonium carbonate solution at pH ~ 10, with a total iron is expected to occur between approximately pH 8 and 11.5
ammonia concentration approaching 6 M (90 to 110 g/L). at 298 K. When the temperature is increased to 333 K, there
Expected iron concentration in the loaded leach liquor is very is a more limited range of pH where soluble Fe(II) is fully
low, due to oxidation of ferrous ammine species to ferric hy- complexed—approximately pH 7.3 to 10 (speciation not shown
droxides. Osseo-Asare et al. (1983) have reported a value of here, but the Pourbaix diagram is shown in Fig. 3). While
approximately 3 x 10-5 M for the concentration of total iron the tetrammine-Fe(II) complex is present at 298 K between
in equilibrium with a sintered iron cobalt alloy exposed to an pH 7 and 12, the majority of soluble Fe is in the form of the
aerated ammonium carbonate solution (at 4 M total ammonia). pentammine-Fe(II) complex above pH~8.5. These diagrams
On the other hand, Klocke and Hixson (1972) have reported a also reveal that the number of ammonia ligands associated
ferrous iron solubility in the Fe(OH)2-H2CO3-NH4OH system with Fe(II) will most likely be between 4 and 5 in practical
of 0.5 M in 5.49 M total ammonia and 1.03 M total carbon- leach solutions operating near 318 K.
ate. The Klocke and Hixson results point to the stability of an Figures 2 and 3 demonstrate the stability of the ferrous am-
Fe(II)-hexammine complex, the thermodynamic data for which mines in terms of solution redox potential. At 298 K, pH 10
does not currently exist. Since the present work is concerned and at 333 K, pH 9, one should expect to see the formation of
with both the stability of ammine phases and the potential for ferrous ammines between approximately -0.8 to -0.2 V SHE.
iron passivation (by ferrous or ferric phases) in the presence In the Caron leach process, it is hoped that iron oxidation will
of dissolved oxygen or other oxidants, the concentration of proceed a priori via dissolution as an ammine followed by
10-3 M total iron was chosen for our calculations. A higher subsequent rejection as a hydroxide species. In this respect,
concentration of iron would tend to shrink the Eh-pH regions the leach is selective to nickel and cobalt, which have more
Figure 2 — Quasi-equilibrium Pourbaix diagram for the Figure 3 — Quasi-equilibrium Pourbaix diagram for the
Fe-NH3-H2O system at 298 K. [Fe] = 10-3 and [NH3]T = 6 Fe-NH3-H2O system at 333 K. [Fe] = 10-3 and [NH3]T = 6
M. Lines a, b and c represent, respectively, the hydrogen M. Lines a, b and c represent, respectively, the hydrogen
evolution line, the oxygen reduction line and the ammonia evolution line, the oxygen reduction line and the ammonia
buffer point. “FeAn” represents the ammino-iron(II) species, buffer point. “FeAn” represents the ammino-iron(II) species,
where “n” is the number of ammonia ligands in the complex. where “n” is the number of ammonia ligands in the complex.

Figure 4 — Quasi-equilibrium Pourbaix diagram for the
Ni-NH3-H2O system at 298 K. [Ni] = 10-1 and [NH3]T = 6 Figure 6 — Calculated Co(II) speciation for 10-2 M total
M. Lines a, b and c represent, respectively, the hydrogen cobalt in 6 M total ammonia at 298 K. “CoAn” represents
evolution line, the oxygen reduction line and the ammonia the ammino-cobalt(II) species, where “n” is the number of
buffer point. “NiAn” represents the ammino-nickel(II) ammonia ligands in the complex.
species, where “n” is the number of ammonia ligands in
the complex.
noble ammine stability regions (nickel and cobalt diagrams comparison of Figs. 5 and 8. It is worthwhile to note that the
are presented in Figs. 4 and 5, respectively). The constrained most stable Co(III) ammine appears to be the hexammine
window of ferrous ammine stability indicates that passivation species (Fig. 5). The Co(III) ammines have been shown to
of the Fe-Ni-Co alloy is very likely to occur; particularly as be directly involved in the Caron leach process and appear to
the Caron leach process is oxidative in nature, with a typical act as a redox catalyst during aerated leaching (Nikoloski and
operating Eh between -0.2 and +0.2 V SHE. Leaching of nickel Nicol, 2006; Nikoloski and Nicol, 2010; Senanayake et al.,
and cobalt should then be expected to occur in a mechanism 2010). At 298 K, Co(II) is fully complexed between pH 7.5
akin to de-alloying, where only select metals are extracted and 12.5 (Fig. 6). At 333 K, this range is between pH 6.8 and
from the alloy matrix. As Ni(II) ammines are more thermo- 11. In aqueous ammoniacal systems, pH generally changes
dynamically stable than Co(II) ammines (cf. next paragraph), with temperature in conjunction with the buffer point. This
this mechanism may explain why nickel recoveries are higher means that a pH 10 solution at 298 K should likely rest at a pH
than cobalt recoveries. of ~ 9 at 333 K. At pH of 9 and 333 K, the most stable Co(II)
The effect of temperature on cobalt speciation is similar ammine is the hexammine species representing roughly 50%
to that for the case of iron. There is a general movement of the total dissolved Co(II) in 6 M total ammonia. The effect
of ammine stability to lower pH and the pH range for full of temperature on Ni(II) ammine speciation is also similar, but
complexation decreases with temperature, as is evident upon the hexammine Ni(II) species is considerably more stable: at
333 K, pH 9, it represents over 80% of the total dissolved Ni
in 6 M total ammonia and 0.1 M total nickel (Fig. 7).
The Pourbaix diagrams for Co (hatched lines) and Fe (full
Figure 5 — Quasi-equilibrium Pourbaix diagram for the

Co-NH3-H2O system at 298 K. [Co] = 10-2 and [NH3]T = 6
M. Lines a, b and c represent, respectively, the hydrogen
evolution line, the oxygen reduction line and the ammonia
buffer point. “CoAn” represents the ammino-cobalt(II) Figure 7 — Calculated Ni(II) speciation for 10-1 M total
species where “n” is the number of ammonia ligands nickel in 6 M total ammonia at 333 K. “NiAn” represents
in the complex. “Co(III)A6” represents the hexammine- the ammino-nickel(II) species, where “n” is the number of
cobalt(III) species. ammonia ligands in the complex.

Figure 9 — Potentiodynamic polarization plots for Armco Fe
Figure 8 — Quasi-equilibrium Pourbaix diagram for the in quiescent, naturally aerated ammonium sulfate solution
Fe,Co-NH3-H2O systems at 333 K. [Co] = 10-2, [Fe] = 10-3 at pH 10, 298 K. Total ammonia concentration is 6 M. The
and [NH3]T = 6 M. Lines a and b represent, respectively, anodic nose in case (b) is only apparent due to high cathodic
the hydrogen evolution line and the oxygen reduction line. polarization, indicating that ammine formation can only
“(Fe,Co)An” represents the ammino-iron(II) or cobalt(II) occur under very reducing conditions. Plot (a) indicates
complex, where “n” is the number of ammonia ligands the natural preference of the system. Plot (c) is data from
in the complex. “Co(III)A6” represents the hexammine- Osseo-Asare et al. (1983) obtained in 4 M total ammonia,
cobalt(III) species. 1 M total carbonate at a slower scan rate of 0.1 mV/s.
lines) at 333 K are superimposed in Fig. 8. At pH 9, 333 K iron(II) oxidation reaction. In other words, the exchange current
passivation of iron is likely to occur above -0.2 V. These are density for the Fe/Fe(II)-ammine couple is small. Therefore,
fairly reducing conditions, such that one might expect Fe-Co- case (a) is the scenario most likely to occur in a Caron leach.
Ni alloys to be passivated with little or no anodic precursor. Figure 9 also includes data from the work of Osseo-Asare et al.
Spontaneous passivation has been observed by Nikoloski and (1983), to demonstrate that the kinetics observed in carbonate
Nicol (2006) in electrochemical experiments measuring open solutions are similar to those reported here. The reader will
circuit potentials (OCP) of iron alloys at 45° C (318 K). Simi- note the lower passivation currents observed at high potential
lar findings have been reported by Osseo-Asare et al. (1983), in the Osseo-Asare et al. work, which is consistent with the
even at 298 K when measuring the OCP of Fe in aerated and lower scan rates used.
de-aerated ammoniacal solution at pH 9.8. Polarization mea- These measurements indicate that, even from a kinetic
surements performed for this work on Armco iron (> 99.8% perspective, it is extremely unlikely that anodic dissolution
Fe) at 298 K in 6 M ammoniacal ammonium sulfate solution of iron leading to the formation of ammines should occur in
have also confirmed these findings. These measurements are Caron leaching with oxygen present. This is especially true
shown in Fig. 9, where the following differences in positive when one considers that the Caron leach process is oxidative
sweep potentiodynamic measurement were undertaken: in nature. As a result, leach performance may be improved by
mitigating the iron passivation effect through careful control of
(a) The iron coupon was immersed in quiescent, naturally Eh with a view to maintaining reducing conditions in the initial
aerated solution and immediately polarized from -0.25 stages of dissolution. Subsequent aeration would then result in
V versus OCP. Ni and Co dissolution without limitation from a passive film.
(b) The iron coupon was immersed in quiescent, naturally
aerated solution and immediately polarized from -1 V Conclusions
versus the hydrogen electrode (SHE). Passivation of Fe-Ni-Co alloys during the Caron leach is
thought to result in low Co recoveries. The stability of the
In case (a), the iron coupon was spontaneously passivated Co(II), Co(III) and Fe(II) ammines was examined using the
and in case (b), a clear anodic nose, corresponding to iron most recent and relevant equilibrium constant data, with a
dissolution as a Fe (II) ammine, is visible. This anodic nose view to understanding Co losses during the Caron leach. The
in case (b) is only apparent because of excessive below-OCP most stable Co(II) ammine at 298 K, pH 10 appears to be the
polarization leading to what might be termed “unnatural” hexammine species. Based on the available thermodynamic
conditions. Furthermore, a cathodic loop is visible in case (b), data, Fe(II) ammines are likely associated with only five am-
which indicates that the oxygen reduction reaction is dominant monia ligands. Increased temperature to 333 K reduces the
at moderate anodic overpotentials. Cathodic loops are often stability field for the ammines.
seen on passivating alloys such as stainless steels. It is also The Fe(II) ammines are only thermodynamically stable
interesting to note that the onset of anodic behavior in case (b) under reducing conditions and polarization experiments
occurs at approximately -0.62 V, which is only slightly below show that they are unlikely to form in solutions containing 6
the reversible potential for the hydrogen electrode at pH 10. M ammonia unless high cathodic overpotentials are applied.
This is indicative of a high anodic overvoltage for the iron-to- Maintaining reducing conditions during the initial stages of

dissolution may help reduce the effect of alloy passivation by Mironov, V.E., Pashkov, G.L., and Stupko, T.V., 1992, “Thermodynamics of
enabling Fe dissolution. formation reactions and hydrometallurgical application of metal – ammonia
complexes in aqueous solutions,” Russian Chemical Reviews, Vol. 61, No.
9, p. 944.
Acknowledgments Nikoloski, A.N., and Nicol, M.J., 2006, “The electrochemistry of the leaching
This article has greatly benefited from insightful comments reactions in the Caron process. I. Anodic processes,” ECS Transactions,
Vol. 2, No. 3, p. 197.
by four anonymous reviewers. The author also acknowledges Nikoloski, A.N., and Nicol, M.J., 2010, “The electrochemistry of the leaching
the Natural Sciences and Engineering Research Council of reactions in the caron process. Ii. Cathodic processes,” Hydrometallurgy,
Canada for its financial support. Vol. 105, p. 54.
Osseo-Asare, K., and Asihene, S.W., 1979, “Heterogeneous equilibria in am-
monia/laterite leaching systems,” Proceedings of the International Laterite
References Symposium, New Orleans, LA, February 19-21, New York, NY: AIME.
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P. Haase and Son. extraction in ammoniacal solution: electrochemical effect of metallic iron,”
Criss, C.M., and Cobble, J.W., 1964, “The thermodynamic properties of high Metallurgical Transactions B, 14B, No. 12, p. 571.
temperature aqueous solutions. V. The calculation of ionic heat capacities Park, B., and Dempsey, B.A., 2005, “Heterogeneous oxidation of Fe(II) on Fer-
up to 200°C. Entropies and heat capacities above 200°C,” Journal of the ric Oxide at Neutral pH and a Low Partial Pressure of O2,” Environmental
American Chemical Society, Vol. 86, p. 5390. Science and Technology, Vol. 39, No. 17, p. 6494.
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and passivation of iron,” Corrosion, Vol. 36, p. 416. London: Pergamon Press.
Isaev, I.D., Tverdokhlebov, S.V., Novikov, L.K., Padar, T.G., Pashkov,G.L., and Reid, J.G., 1983, “Some observations of roasting, leaching and washing charac-
Mironov, V.E., 1990a, “The formation of iron(II) ammines in aqueous solution,” teristics of greenvale lateritic ore,” Proceedings of the 3rd International Sym-
Russian Journal of Inorganic Chemistry, Vol. 35, No. 8, p.1162. posium on Hydrometallurgy, Atlanta, GA, March 6-10, Warrendale, PA: AIME.
Isaev, I.D., Tverdokhlebov, S.V., Troyanova, V.G., Drozdov, S.V., Leont’ev, V.M., Roine, A., 2002, Outokumpu HSC Chemistry Thermochemical Database, ver.
Pashkov, G.L., and Mironov, V.E., 1990b, “The influence of temperature on 5.0. Finland: Outokumpu Research Oy.
the formation of cobalt(II) ammines in aqueous solution,” Russian Journal Senanayake, G., Senaputra, A., and Nicol, M.J., 2010, “Effect of thiosulfate,
of Inorganic Chemistry, Vol. 35, No. 12, p. 1789. sulfide, copper(II), cobalt(II)/(III) and iron oxides on the ammoniacal carbonate
Lewis, D., 1970, “Studies of redox equilibria at elevated temperratures,” Arkiv leaching of nickel and ferronickel in the Caron process,” Hydrometallurgy,
For Kemi, Vol. 32, p. 385. Vol. 105, p. 60.
Linter, B.R., and Burstein, G.T., 1999, “Reactions of pipeline steels in carbon Sillen, L.G., and Martell, A.E., 1964, Stability Constants of Metal Ion Complexes,
dioxide solutions,” Corrosion Science, Vol. 41, p. 117. Special Publication No. 17, London: The Chemical Society.
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Temperatures. Part 4: The Nickel-Water System, Atomic Energy of Canada Complexes, New York, NY: Plenum Press. p. 40.
Limited, AECL Publication No. 4139. Wagman, D.D., Evans, W.H., Parker, V.B., Schumm, R.H., Halow, I., Bailey,
Matson, R.F., and Milian, J.M., 1979, “Greenvale nickel project: laboratory and S.M., Churney, K.L., and Nuttall, R.L., 1982, “NBS tables of chemical ther-
pilot plant programs,” Proceedings of the International Laterite Symposium, modynamic properties,” Journal of Physical and Chemical Reference Data,
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Appendix
Thermodynamic data for H2O, NH3, Fe, Ni and Co.a
CP (T) = A + B x 10-3T + C x 105T -2 + D x 10-6T 2

Species
J.[mol.K]-1
kJ.mol-1 J.[mol.K]-1
A B C D
H2O -237.14 186.9 -464.2 -19.6 548.6 69.95
H+ 0 Criss Cobble: = 96.3(333 K) 0
H2 0 22.496 17.044 0.365 11.122 130.68
O2 0 22.06 20.887 1.621 -8.207 205.15
NH3(a) -26.5 507.818 -1522.307 -107.965 1656.854 111.3
NH4 + -79.31 LIHCA: b = 0.40 113.4
Fe 0 31.873 -22.333 -3.519 40.076 27.28
Fe(OH)2 -486.5 95.107 28.477 -5.864 0.001 88
Fe(OH)3 -696.5 162.477 11.916 -43.581 -0.035 106.7
Fe2+ -78.90 LIHCA: b = 0.85 -137.7
Fe(NH3)2+ -115.67 d K Measured up to 328 K (Isaev et al., 1990a) 4.33 d
Fe(NH3)2 2+ -149.10 d K Measured up to 328 K (Isaev et al., 1990a) 109.63 d
Fe(NH3)4 2+ -209.15 d K Measured up to 328 K (Isaev et al., 1990a) 305.23 d
Fe3+ -4.7 LIHCA: b = 1.18 -315.9
Co 0 27.685 -4.386 -2.065 13.710 30.04
Co(OH)2 -454.3 96.914 14.073 -9.877 0.001 79
Co(OH)3 -596.73 f 162.477 11.916 -43.581 -0.035 83.68 f
Co2+ -54.4 LIHCA: b = 0.81 -113
Co(NH3)2+ -94.08 d K Measured up to 398 K (Isaev et al., 1990b) 16.33 d
Co(NH3)4 2+ -196.69 d K Measured up to 398 K (Isaev et al., 1990b) 327.23 d
Co(NH3)6 2+ -249.81 d K Measured up to 398 K (Isaev et al., 1990b) ?
Co(NH3)43+ 19.07 b LIHCA: b = 0.44 131.19 c
Co(NH3)53+ -43.78 b LIHCA: b = 0.14 318.09 f
Co(NH3)63+ -221.1 b LIHCA: b = -0.03 416.79 c
Ni 0 16.27 36.758 0.167 -16.154 29.87
Ni(OH)2 -447.2 92.949 13.372 -13.278 0.006 88
Ni2+ -45.60 LIHCA: b = 0.84 -128.9
Ni(NH3)2+ -88.13 e LIHCA: b = 0.65 -17.30 e
Ni(NH3)22+ -127.59 e LIHCA: b = 0.48 86.70 e
Ni(NH3)32+ -164.20 e LIHCA: b = 0.32 185.00 e
Ni(NH3)4 2+ -197.93 e LIHCA: b = 0.15 288.30 e
Ni(NH3)52+ -228.50 e LIHCA: b = -0.01 386.00 e
Ni(NH3)6 2+ -255.84 e LIHCA: b = -0.16 478.90 e
a Gibbs free energy and entropy data from NBS tables unless otherwise specified (Wagman et al., 1982). Heat capacity Kelly
power functions from the database compiled by Roine unless otherwise specified (Roine, 2002). b Calculated from Log K data
from Smith and Martell. c Calculated from ΔS (Smith and Martell, 1977). d Calculated from Log K or ΔS data (Isaev et al., 1990a,
1990b). e Calculated from Log K or ΔS data (Mironov et al., 1992). f From the database compiled by Roine (2002).

Coarse particle fracture
with the ultrafast load cell
E.T. Tuzcu, N. Dhawan and R.K. Rajamani
Graduate students and professor, respectively
Department of Metallurgical Engineering, University of Utah, Salt Lake City, UT
Abstract
Microscale information about single particle fracture can be incorporated into the macroscale model of the
whole size reduction process in the mill. The ultrafast load cell (UFLC) device provides a substantial amount of
information about fracture characteristics of a particle under impact loading. UFLC captures high-resolution
compressive force signals during particle breakage. The measurement of the compressive force at the instant of
fracture of the particle allows computation of a number of comminution-related particle properties, as well as
the energy absorbed during fracture. In the current study, limestone particles 50 mm in size were fractured to
obtain specific fracture energies. Then, based on the experimental data, two models were proposed to quantify the
fracture process. The specific fracture energy distribution of the particles in the range of 6 to 50 mm was defined
by the well-known Weibull distribution. The other model is a probabilistic fracture model. This model is a link
between energy events occurring in a grinding mill and the breakage rates of particles. The impact energy spectra
or energy events occurring in a grinding mill can be obtained with a discrete element method (DEM) simulation.
One can model the breakage rates of the mill material by combining the energy spectra with the probabilistic
fracture model. This novel approach for the modeling of breakage rates via DEM and UFLC is shown here.
Key words: Comminution; Grinding energy; Particle fracture; Tumbling mill
Introduction model SAG/AG mills, where larger-size particles, up to sev-

The process of comminution is made up of several eral hundred millimeters, are ground in the mill (Tavares and
subphenomena. These are simply the mass transport of Carvalho, 2009; Tuzcu, 2010).
the particles to the crushing or stressing zone, stress- In this manuscript, specific fracture energy of the larger-
ing of the particle at the crushing zone, breakage of size particles was measured with a UFLC device. Based on
the particles and, finally, removal of the fragments the specific fracture energy distribution, statistical analysis of
from the crushing zone. The breakage of the particle the experimental data was carried out to quantify the fracture
may be the most difficult phenomenon to understand process.
among these subevents. Many researchers (Schoenert,
1972; Rumpf, 1973; Krogh, 1980; Weichert, 1988; Review: the ultrafast load cell (UFLC) device
Weichert, 1992) have applied the principles of fracture The first UFLC device was developed at the Comminu-
physics to explain the response of the particle in a tion Center of the University of Utah in 1986 (Weichert and
breakage event. After obtaining enough microscale Herbst, 1986). The main reason for developing the UFLC
information by applying these principles, a macroscale device was the limited bandwidth and, hence, low resolution
understanding of the real comminution environment of the conventional load cells of the time. Very high resolution
was achieved. An understanding of the microscale is required when measuring the breakage of a particle, which
breakage events is possible in single-particle breakage happens in the hundred microseconds time range. The UFLC
tests. Such tests have been carried out with impact device has a rod of diameter 50 mm, and is capable of mea-
load cells (Weichert and Herbst, 1986; King and suring the breakage event at a resolution of 2 μs and a force
Bourgeois, 1993; Tavares, 1997; Tavares and King, of 20 N. The UFLC device records the propagation of elastic
2002; Bourgeois and Banini, 2002). waves through a long rod. These waves are created during
It has been more than two decades since the de- the free fall of a steel ball onto the rod. The amplitude of the
velopment of the first UFLC (Weichert and Herbst, waves depends on the pressure exerted by the ball and can be
1986). This device continues to provide substantial measured anywhere on the rod as a function of time. The force
information about the breakage of large-size par- acting on a single particle caught between the ball and the rod
ticles. In the past, the fracture information of small is recorded from the strain gauge signal.
size particles, up to millimeter-scale size, led to the Many detailed studies have been carried out with the UFLC.
development of phenomenological microscale ball Fracture characteristics of the ore particles were analyzed under
mill models (King and Bourgeois, 1993; Tavares impact loading conditions, either on a bed of particles or on
and King, 2002). Now, the UFLC device is used to single particles. The particle size distribution and broken mass
Paper number MMP-10-059. Original manuscript submitted December 2010. Revised manuscript accepted for publication
May 2011. Discussion of this peer-reviewed and approved paper is invited and must be submitted to SME Publications
Dept. prior to May 31, 2012. Copyright 2011, Society for Mining, Metallurgy, and Exploration, Inc.

Nomenclature
Arod = cross sectional area of the UFLC rod (m2) c = material specific parameter
C0 = wave velocity (m/s) e = coefficient of restitution
E = modulus of elasticity of the rod (N/m2) Ek = input energy to the particle by the steel ball (J)
Ek = collision event of energy k (J)
= specific fracture energy (J/kg)
Eu = model scale parameter = applied specific impact energy of collision event of energy
k (J/kg)
= applied specific impact energy of collision event for size class i (J/kg) = median specific fracture energy of size class i (J/kg)
El = energy loss (J) Ep = particle breakage or fracture energy (J)
Er = energy absorbed by the rod (J) Eres = residual energy of the falling sphere (J)
Erod = modulus of elasticity of the UFLC rod (N/m2) fmat = material parameter (kg/m.J)
F = force exerted by the free-falling sphere on UFLC rod (N) F = cumulative functional form of the distribution of the tensile
strength
g = gravitational acceleration (m/s2) i = size class index
j= jth rank of the energy observation k = number of impacts
k = function of sphere, rod geometries and elastic properties of the materials K’ = model constant
m = model shape parameter m = model parameter
m = mass of the falling sphere (kg) N = total number of observations
= cumulative probability of fracture at an energy level = probability of failure of size y particle

S = breakage rate
probability of fracture of the mean size of xi material at the applied
specific impact energy
SiE = energy-based breakage rate for size class i (1/sec) t = time (s)
u = displacement along the axis x of the rod (μm) u1(t) = displacement of the UFLC rod (μm)
u2(t) = displacement of the steel ball (μm) v0 = impact velocity of the falling sphere (m/s)
Vout = output voltage of the Wheatstone bridge circuit (V) Vin = input voltage to the Wheatstone bridge circuit (V)
Wkin = mass specific kinetic energy of the particles before the impact (J/kg) Wmin = minimum energy of the particle to be overcome to achieve
a successful breakage (J/kg)
W = elastic energy stored in the particle at failure (J) Wm = mass-specific elastic energy stored in the particle at failure
(J/kg)
xi = mean size of particular size class (m) y = particle size (m)
z = material specific parameter σ = tensile strength of the material
σo = model parameter α = local relative deformation of the colliding bodies (μm)
ρ = density of the rod (kg/m3) ρrod = density of the UFLC rod (kg/m3)
ε = strain experienced by UFLC λk = number of collisions per second of the collision event of
energy Ek (sec-1)
values of different bed configurations after applying different spectra to arrive at a breakage rate formulation. Finally, with
energy levels were determined in some of these studies. In this breakage rate formulation, the product size distribution of
addition, particle-particle interaction was examined under a lab-scale grinding mill was predicted successfully.
compressive loading. Hofler (1990) determined the optimum A similar device, known as the CSIRO Hopkinson bar, was
impact energies for different loading geometries, i.e., the ef- developed (Fandrich et al., 1998) at the Queensland Centre for
ficiency of breakage was determined for ball-ball and ball-flat Advanced Technologies to measure the fracture of particles up
contacts. Low-impact energy fracture tests were carried out to to 100 mm in size. The force resolution of the device was less
quantify a number of measures (King and Bourgeois, 1993; than 100 N. This device was used to study the fracture force
Tavares and King, 2002). These measures are: force and energy for large-diameter iron ore particles up to 75-90 mm size range.
absorbed at crack initiation, mass specific energy for fracture, Bourgeois and Banini (2002) developed a short-length impact
the breakage function, the distribution of particle breakage load cell to measure the in situ fracture characteristics of the
energy and the distribution of particle strength. A conceptual mineral ores. The novel feature of the 50-mm ultrafast load cell
model for ball mills was also proposed based on these studies. is to show that without loss of resolution, compared to larger-
Tavares and King (1998) analyzed the progressive accumula- size load cells, it is possible to measure the fracture energy.
tion of damage in the particle using the UFLC. After repeated
low-level impacts, a decrease in particle fracture energy was Theoretical background
observed. A recent study (Tuzcu, 2010) carried out fundamen- Hertz theory of impact. Hertz (Goldsmith, 1990) stated
tal work on slightly larger particle sizes for the first time. An that the stresses and deformations should be analyzed near the
impact probability fracture model was proposed based on the contact point as a function of the geometrical and elastic proper-
UFLC tests. These tests were combined with impact energy ties of the contacting bodies. The one-dimensional propagation

obtained by an iterative numerical technique. Presuming the
elastic properties of the materials and diameter of the falling
sphere, the force on the upper end of the UFLC rod is given by
Eq. (3). More details about the deformation and force evolution
are given in Tavares (1997).
Statistical approach for the particle fracture. The inter-

nal composition of flaws inside a particle is, at best, random,
varying from particle to particle. The energy required to break
the particle directly depends on the composition and structure
of these flaws within the particle. Therefore, when the fracture
energy is measured with a sensitive device such as the UFLC,
one gets a spectrum of energy values even for a narrow par-
ticle size range. The spectrum exhibits the characteristics of
a probability distribution. Hence, this function describes the
breakage probability of a particle of a particular energy level.
For this reason, evaluation of the experimental data generated
by UFLC experiments is based on statistical models rather than
deterministic models.
In particular, data generated from the fracture of the single
particle by UFLC are suitable for analysis with order statistics.
The experimental specific energy results for a single particle
size are sorted from the lowest value to highest value. The
statistical description of the rank is called order statistics. The
kth order statistic of a sample is equal to its kth smallest value.
Figure 1 — Deformations occurring in the UFLC rod and Thus, the cumulative probability of fracture at an energy level
the falling sphere. is given by
(4)
of an elastic wave in a long circular rod of constant diameter
is described by the linear wave equation: where j is the jth rank of the fracture energy observation and
is the specific fracture energy for the jth observation and
(1) N is the total number of observations. Next, an appropriate
statistical distribution, Weibull, log-logistic or log-normal,
is fitted to the experimental data ( , P( )). In this work,
where u is the displacement along the axis x of the rod, t is the analysis of the specific fracture energy data was carried out
time and C0 is the wave velocity. Wave velocity is related to using the Weibull distribution.
modulus of elasticity, E, and density, ρ, of the rod material in The Weibull distribution, given in Eq. (5), is based on the
accordance with the following equation: weakest link failure criterion and assumes that the most severely
stressed flaw will lead to failure of the sample. The cumulative
(2) functional form of the distribution is given by
In the UFLC device shown in Fig. 1, a steel ball falls on a (5)

particle situated at the upper end of the rod. The deformation of
the particle, force and energy consumed for comminution during where ϭ is the tensile strength of the material and ϭ0 and m are
an impact event can be calculated with the impact velocity of model parameters that refer to the scale and shape, respectively.
the falling mass. In this analysis, the inelastic deformation of A variant of Weibull statistics was proposed by Weichert
the rod and the elastic and inelastic deformation of the falling (1988,1992) in a study of breakage and fragment size distri-
sphere during the impact event are negligibly small compared bution of 4-mm glass spheres. In Weichert’s formulation,
to particle deformation. The solution of Eq. (1) yields force- shown in Eq. (6), W is the elastic energy stored in the particle
time history during fracture. The deformation process in the at failure, m is the mass of the particle and Wm = W/m is the
UFLC rod and falling sphere starts when the sphere touches mass-specific fracture energy at failure. The probability of
the rod and ends when the sphere leaves or rebounds from the breakage is given as
rod. As shown in Fig. 1, the displacement at the center of the (6)
rod is denoted as u1 and that of the sphere is denoted as u2. The
force exerted by the free falling sphere on UFLC is calculated where y is the particle size and c and z are material-specific
by force deformation law thus: parameters.
In more recent studies, Vogel and Peukert (2003) and Peukert
(3)
(2004) derived, in a fundamental way, the breakage probability
where α = u2 - u1 is the local relative deformation of the col- or the fraction of particles that are broken as a function of the
liding bodies, and k is a function of sphere and rod geometries applied energy. The importance of the material properties
and elastic properties of the materials. being processed was introduced and they defined a material
The local relative deformation, α, of the colliding bodies is parameter term fmat. The material parameter is the response of

Figure 2 — Schematic drawing of a UFLC (Tuzcu and Rajamani, 2010).
the particles to the stress exerted by the environment. In this of the Wheatstone bridge. The digital oscilloscope is capable
formulation the breakage rate, S, is given as, of storing sample in the range of 0.5 to 2 μs. The data input
is triggered by a laser-photodiode couple. Whenever a falling
(7) ball cuts the laser light, the triggering unit sends a signal to
the oscilloscope, which then starts to record a number of data
where Wkin is the mass-specific kinetic energy of the impacting points. The stored data is transmitted to a computer for the
particles for repeated single impacts, x is the particle diameter, computation of force and applied energy.
k is the number of impacts, fmat is the material parameter and
Wmin is the minimum energy of the particle to be overcome to Determination of the fracture force. One must first ex-
achieve a successful breakage. perimentally obtain the force-time profile prior to calculation
of displacement and energy. The strain (ε) experienced by the
Experimental work and the measured particle rod is readily given by the Wheatstone bridge voltage values as
fracture characteristics with UFLC
The ultrafast load cell device. The UFLC is a 5-m-long
rod equipped with strain gauges and Wheatstone bridge circuits (8)
to measure the applied force at the moment of the fracture of
the particle. The particle exhibits an internal fracture energy where K is the constant value for a particular bridge configura-
that must be overcome in order to achieve successful break- tion and Vin and Vout are the input and output voltages of the
age. The duration of a breakage event is around 150 μs. This Wheatstone bridge circuit. The local force experienced by the
device captures applied force signals at a high resolution dur- rod is related to the local strain ε given by
ing breakage. Next, these force signals are converted into total
energy applied. Figure 2 shows the dimensions of the rod and (9)
the locations of the strain gauges on the rod. The steel rod is 50 where Arod is the cross sectional area of the rod and Erod is the
mm in diameter with an anvil on top of the rod and a loading modulus of elasticity of the rod.
unit. There are two sets of BLH-type SPB 3-15-200 solid state
strain gauges on the steel rod. These solid state strain gauges Experimental calibration of UFLC. It is preferable to
are glued to the rod surface at a depth of 210 mm and 794 mm, calibrate the UFLC prior to actual tests. First, the strain wave
measured from the top. Both upper and lower sets consist of that results from the impact of a steel ball and the rod is re-
four strain gauges. The four gauges are situated one each per corded at the instant of collision. Then, a comparison can be
quadrant of the rod circle. Each set of strain gauges is the half made between the measured and the predicted forces under
bridge component of a complete Wheatstone bridge. Signals known dynamic conditions. Figure 3 is an example for the
obtained from either upper (210 mm depth) or lower (794 mm experimental calibration, which shows the experimental force-
depth) bridge can be used in the experiments. A digital storage time profile compared with Hertzian impact theory. In this test,
oscilloscope, Nicolet Pro 40, amplifies and stores the signals a 2.88-cm-diameter steel ball was released from a height of

Figure 3 — Comparison between Hertzian theory (solid line) and UFLC response (circles).
0.44 cm. As seen in the figure, the experimental force values and so on. The last peak indicates the impact between the steel
and the theoretical force values are in good agreement. This ball and steel anvil. This peak is greater in magnitude than the
confirms that experimental calibration is accurate and can be peaks for the particle fracture. The first peak alone is considered
readily used for the particle fracture tests. in the fracture calculations. Once the voltage-time profile is
recorded, the local strain and force are calculated using Eq.
Experimental conditions for the UFLC experiments. The (8) and Eq. (9), respectively.
fracture energies of seven different size classes of limestone
were measured with the UFLC. These size classes were: 44.5 Determination of the local deformation from fracture
x 38.1 mm, 31.8 x 25.4 mm, 25.4 x 19.0 mm, 19.0 x 12.7 force. After computing the experimental force values as
mm, 12.7 x 9.7 mm, 9.7 x 7.8 mm and 7.8 x 6.6 mm. The described in the previous section, the relative displacements
experimental conditions for the seven size classes are shown shown in Fig. 5 were computed. The displacement represents
in Table 1. Obviously, mineral particles, especially the larger the displacement of the steel ball of mass m with impact veloc-
sizes, exhibit random internal strength. Therefore, increasing ity v0 of the striker ball. It is given by
the number of particles will increase the quality of the data.
In the experiments, the number of particles in each test was
(10)
between 20 and 40.
Figure 4 shows the response of the UFLC to a steel ball
impact on a mineral particle placed on the rod. The voltage The displacement u1(t) represents the displacement of the
trace shown in the figure must be carefully analyzed to compute top surface of the rod. It is given by
the force. The negative voltage values indicate compression,
which causes the fracture of the particle. The first peak in this
(11)
plot shows the primary fracture event, which ideally breaks a
particle into two equal parts. Next, the secondary and tertiary
fractures divide the particle into three, four and five pieces where ρrod is the density of the rod.
Table 1 — Experimental conditions for limestone fracture experiments.

Mean mass of Average height of
Experiment no. Particle size (mm) Ball mass (kg) Drop height (cm)
particles (g) particles (mm)
1 44.5 × 38.1 139.78 2.1008 25.40 28.31
2 31.8 × 25.4 41.71 2.1008 9.26 16.45
3 25.4 × 19.0 14.96 2.1008 6.94 15.45
4 19.0 × 12.7 9.47 1.1824 6.76 11.93
5 12.7 × 9.7 3.08 1.1824 3.16 9.36
6 9.7 × 7.8 1.29 0.2587 5.67 5.78
7 7.8 × 6.6 0.47 0.2587 2.97 4.32

Figure 4 — Voltage versus time profile showing points of primary, secondary and tertiary fracture in a ball-anvil impact.
Determination of the energy measures: adsorbed energy Er is the energy absorbed by the rod resulting in rod deforma-
by the rod and by the particle, the residual energy of the tion, Ep is the particle breakage or fracture energy, Eres is the
falling sphere and the coefficient of restitution. The input residual energy of the falling sphere and El is the energy loss.
energy is the most important factor controlling the breakage The input energy to the breakage event is given by
process. The input energy is shared by different energy events
during breakage. Equation (12) is the energy balance for par-
(13)
ticle breakage (Tavares, 1997).
(12)
Energy absorbed by the rod, Er, or the work of deformation
where Ek is the input energy to the particle by the steel ball, of the rod is given by
Figure 5 — Case 1: Rod deformation (a), ball deformation (b), energy of the rod (c) and residual energy of the ball (d).

Table 2 — Test cases to show differences in e, Ep, Er, Eres, u1 and u2 values.
Exp. no. Ball Mean particle Particle Drop Energy input Residual energy Coefficient of
mass (kg) size (mm) height (mm) height (cm) (Ek) (J) (Eres) (J) restitution (e)
Case 1 0.1092 - - 0.44 0.0044 0.0042 0.98
Case 2 2.1008 41.2 28.31 25.40 4.6512 4.3134 0.96
given by
(14) (16)
Determination of the residual energy of the ball, Eres, pro-
Energy absorbed by the particle or particle fracture energy vides information about the type of the impact. By definition,
is given by the coefficient of restitution is the ratio of rebound energy to
the energy of impact. Hence, in the context of fracture and
loss, the coefficient of restitution is
(15)
(17)
It is always possible to determine energy losses in the form
of heat, sound and friction. However, by assuming El to be The value of e, in nearly elastic impact events, is close to
negligible, the residual energy of the falling sphere, Eres, is unity.
Figure 6 — Case 2: Rod deformation (a), ball deformation (b), energy of the rod (c), energy of the particle
(d) and residual energy of the ball (e).

Figure 7 — The Weibull model fit to the experimental spe- Figure 9 — The Weibull model fit to the experimental spe-
cific fracture energy data of 44.5 x 38.1 mm particle size. cific fracture energy data of 19.1 x 12.7 mm particle size.
Figure 8 — The Weibull model fit to the experimental spe- Figure 10 — The Weibull model fit to the experimental
cific fracture energy data of 25.4 x 19.1 mm particle size. specific fracture energy data of 7.8 x 6.6 mm particle size.
Two different tests were done to show the e, Ep, Er, Eres, u1 following cumulative probability distribution:
and u2 values of the different impact events. In the first case
a 2.88 cm-diameter steel ball was released on the rod from a
(18)
height of 0.44 cm. This case illustrates steel-steel impact only.
In the second case, a 41-mm particle was fractured. The test
conditions for the cases are given in Table 2. The coefficient of
restitution value for case 1 (steel-steel impact) shows that the where Eu and m are the model’s scale and shape parameters,
impact is almost perfectly elastic. Changes in local deforma- respectively. Two-parameter Weibull model fits to the experi-
tions (u1, u2) and energy of the rod and residual energy of the mental data are shown in Figs. 7 through 10 for different size
ball (Er, Eres) are shown in Fig. 5. classes.
The coefficient of restitution value for case 2 (fracturing The Weibull model parameters are given in Table 3. The
of a coarse particle) also shows that the fracture event of the scale parameter of the model, Eu, increases with decreasing
particle is elastic in nature. Changes in local deformations (u1, size of the particle, as expected. This confirms the well-known
u2) and energy of the rod, residual energy of the ball and energy comminution law: the energy required to break a particle in-
of the particle (Er, Eres, Ep) are shown in Fig. 6. creases with decreases in particle size.
Figure 11 shows the fracture energy data for all sizes (44.5
Statistical analysis of the UFLC x 38.1 mm, 31.8 x 25.4 mm, 25.4 x 19.1 mm, 19.1 x 12.7 mm,
experimental data 12.7 x 9.7 mm, 9.7 x 7.8 mm and 7.8 x 6.6 mm) together, four
Two-parameter Weibull model for the specific fracture of which are shown in Figs. 7 through 10 as examples. The
energy distribution of the particles. In the case of particle comparison shown in Fig. 11 is helpful to see the effect of
fracture, tensile strength of the material in Eq. (5) is replaced particle size on fracture energy. Specific fracture energy of
by the specific fracture energy . The specific fracture en- the particle increases 10 times as the particle size decreases
ergy distribution of a certain size of particles is defined by the from 45 to 8 mm.

Figure 11 — The Weibull model fits the experimental specific fracture energy data
for different particle sizes.
Probabilistic fracture model as a function of applied im- event can be found by multiplying the amount of captured mass
pact energy. The determination of the amount of broken mass and breakage probability of particular size particles in that
in a particular collision event is the key to modeling breakage collision event. Hence, the probability fracture model forms
rates, and hence size distribution, via impact energy spectra the basis of impact energy-based breakage rates (Tuzcu, 2010;
(Bwalya et al., 2001; Datta and Rajamani, 2002; Tavares and Tuzcu and Rajamani, 2010).
Carvalho, 2009). This model is a link between collision events The applied energy Ek (J) for an impact event is obtained
occurring in a grinding mill and breakage rates of the particles. from DEM simulation. Next, Ek is converted into applied specific
The amount of broken mass under certain types of collision impact energy by dividing collision energy (J) by mean
Table 3 — Weibull model parameters for seven size classes obtained from UFLC fracture tests.
Weibull parameters
Particle
Confidence Confidence
size mm) Eu m
bound for Eu 95% bound for m 95%
44.5 x 38.1 2.538 2.770 2.488 2.589 2.540 2.999
25.4 x 19.1 6.645 2.600 6.435 6.856 2.277 2.924
19.1 x 12.7 9.688 1.431 9.233 10.140 1.287 1.575
12.7 x 9.7 11.520 1.441 10.270 12.760 1.109 1.773
9.7 x 7.8 13.410 1.402 12.680 14.130 1.231 1.573
7.8 x 6.6 30.260 1.894 29.140 31.380 1.686 2.102
Table 4 — Comparison between applied impact energy and measured fracture energy of the particle (Tuzcu and
Rajamani, 2010).
Particle Specific impact energy Median specific
The ratio of the energies
size applied, fracture energy,
(mm) (J/kg) /
(J/kg)
44.5 × 38.1 33.28 2.22 14.96
31.8 × 25.4 37.61 2.27 16.59
25.4 × 19.1 74.32 5.78 12.85
19.0 × 12.7 68.17 7.56 9.02
12.7 × 9.7 83.76 9.01 9.30
9.7 × 7.8 100.18 9.59 10.45
7.8 × 6.6 137.43 24.39 5.63

Figure 12 — Model fitting (Eq. (5)) of probability of breakage with size term xi and
energy term ( - ) for 44-x-38-mm particles (Tuzcu and Rajamani, 2010).
particle mass (kg) in size class i. is the synonym for . and z are the distribution parameters and xi is the mean particle
denotes the applied specific impact energy for a particular size of a particular size class. A typical fitted expression (Fig.
size class i. The other energy component of the model is the 12), for a 44-x-38mm particle :
percentile fracture energy value to break the particle size class (20)
i. This energy is called median specific fracture energy
and is obtained from the UFLC experiments. where the ratio of the energies / is 14.96, mean particle
Table 4 shows the applied specific impact energy for a size is 0.041148 m and the median fracture energy of the
particular size class, fracture energy of that size class and the size class is 2.224 J/kg.
ratio between applied impact energy and the particle’s fracture This model is the link between collision events occurring
energy. The applied impact energy is around 10 times the pure in a grinding mill and breakage rates of the particles. One can
fracture energy. In other words, almost 90% of the applied model the breakage rates of the mill material by obtaining
impact energy is not utilized in fracturing the particle. energy spectra of a grinding mill with DEM and using a proba-
The statistical approach for the evaluation of particle break- bilistic fracture model as a function of applied impact energy:
age was reviewed in the section, “Statistical approach for the
particle fracture.” Based on the former fundamental definitions
(Vogel and Peukert, 2003; Peukert, 2004; Weichert, 1988), the (21)
“effective energy” ( - ) was introduced in this study.
Effective energy is the difference between applied specific
where SiE is the breakage rate, K’ is the model constant, λk
impact energy ( in J/kg) and the measured median specific is the collision frequency and Ek is the energy level of the
fracture energy ( in J/kg) of the particle. Probability of collision event.
fracture of a particle directly depends on the applied impact Summary and conclusions
energy. The probabilistic fracture model guarantees that when The fracture measures of larger particles, 50 mm in size,
a certain size particle experiences an impact event whose have been demonstrated, for the first time, with the 50-mm
value is larger than its fracture energy value, the probability UFLC device. These measures are: local deformations in the
of breakage of the particle is finite. The model expression steel rod and in the falling sphere, energy absorbed by the
skips over very low magnitude collisions because they do rod, energy absorbed by the particle and residual energy of
not cause any fracture. the falling sphere.
Residual energy of the falling sphere yields an understanding
> of the type of coarse particle fracture. It was shown that the
collision event of a 40-mm particle is highly elastic in nature.
(19)
Specific fracture energy distribution of the particles was
≤ modeled based on the energy absorbed by the particle. The
two-parameter Weibull expression was used for the purpose
where Pf ( , XI) is the probability of fracture of the particular of modeling. Even for larger-size particles, the model fits the
size of the material at the applied specific impact energy ,c experimental data extremely well.

A probabilistic fracture model was given based on the impact Solid, Edward Arnold, London.
energy and the specific fracture energy ratio. This model is a Hofler, A., 1990, Fundamental Breakage Studies of Mineral Particles with an
Ultra-fast Load Cell Device, Ph.D. Thesis, Department of Metallurgical En-
link between energy events occurring in a grinding mill and gineering, University of Utah, Salt Lake City, Utah., 240 pp.
the breakage rates of the particles. There are thousands of low- King, R.P., and Bourgeois F., 1993, “Measurement of fracture energy during
level impacts occurring in a mill. These impacts may be termed single-particle fracture,” Minerals Engineering, Vol. 6, No. 4, pp. 353-367.
Krogh, S.R., 1980, “Crushing characteristics,” Powder Technology, Vol. 27,
noise and, according to this model, such low-energy impacts pp. 171-181.
do not break particles. When the impact energy considerably Peukert, W., 2004, “Material properties in fine grinding,” International Journal
exceeds fracture energy, the model interprets it as breakage of of Mineral Processing, Vol. 74S, pp. S3–S17.
Rumpf, H., 1973, “Physical aspects of comminution and new formulation of a
the particle. The probabilistic fracture model guarantees that law of comminution,” Powder Technology, Vol. 7, pp. 145-159.
when a certain size particle experiences an impact event whose Schoenert, K., 1972, “Role of fracture physics in understanding comminution
value is larger than its fracture energy value, the probability of phenomena,” AIME Transactions, Vol. 252, pp. 21-26.
breakage of the particle is finite. The model is only a function

Tavares, L.M., 1997, Microscale Investigation of Particle Breakage Applied to the
Study of Thermal and Mechanical Predamage, Ph.D. Dissertation, Department
of one variable, which is impact energy. of Metallurgical Engineering, University of Utah, Salt Lake City, Utah., 270 pp.
The approach shown in this study is readily applicable for Tavares, L.M., and Carvalho R.M.de, 2009, “Modeling breakage rates of coarse
plant-scale autogenous and semi-autogenous grinding mills.
particles in ball mills,” Minerals Engineering, Vol. 22, pp. 650-659.
Tavares, L.M., and King R.P., 1998, “Single-particle fracture under impact loading,”
Simply, the rock particles would be tested in the impact de- International Journal of Mineral Processing, Vol. 54, pp. 1-28.
vices and by integrating these results with the impact energy Tavares, L.M., and King R.P., 2002, “Modeling of particle fracture by repeated
spectra of the mill, one can predict the breakage probabilities impacts using continuum damage mechanics,” Powder Technology, Vol.
123, pp. 138-146.
of the particles. Tuzcu, E.T., 2010, An approach for the modeling of batch grinding with single
particle fracture studies and impact energy spectra, Ph.D. Dissertation,
Department of Metallurgical Engineering, University of Utah, Salt Lake
References City, Utah., 270 pp.
Bourgeois, F.S., and Banini, G.A., 2002, “ A portable load cell for in-situ ore Tuzcu, E.T., and Rajamani, R.K., 2011 “Modeling breakage rates in mills with
impact breakage testing,” International Journal of Mineral Processing, Vol. impact energy spectra and ultra fast load cell data,” Minerals Engineering
65, pp 31-54. , Vol. 24, pp. 252–260.
Bwalya, M.M., Moys, M.H. and Hinde, A.L., 2001, “The use of discrete element Vogel, L., and Peukert W., 2003, “Breakage behaviour of different materials-
method and fracture mechanics to improve grinding rate prediction,” Minerals construction of a mastercurve for the breakage probability,” Powder Tech-
Engineering, Vol. 14, No. 6, pp. 565-573. nology, Vol. 129, pp. 101-110.
Datta, A., and Rajamani, R.K., 2002, “A direct approach of modeling batch grinding Weichert, R., 1988, “Correlation between probability of breakage and fragment
in ball mills using population balance principles and impact energy distribu- size distribution of mineral particles,” International Journal of Mineral Pro-
tion,” International Journal of Mineral Processing, Vol. 64, No. 4, pp. 181-200. cessing, Vol. 22, pp. 1-8.
Fandrich, R.G., Clout J.M.F., and Bourgeois F.S., 1998, “The CSIRO Hopkinson Weichert, R., 1992, “Application of defect statistics and fracture mechanics for
bar facility for large diameter particle breakage,” Minerals Engineering, Vol. describing comminution processes,” Zement-Kalk-Gips Intl, Vol. 3, pp. 51-57.
11, No. 9, pp. 861-869. Weichert, R., Herbst J., 1986, “An ultra fast load cell device for measuring
Goldsmith, W., 1990, Impact: The Theory and Physical Behaviour of Colliding particle breakage,” World Congress Particle Technology, Vol. 2, pp. 3-14.

TECHNICAL NOTE
Beneficiation of refractory rock

phosphate by calcination and flotation
S. Khoshjavan and B. Rezai
MSC student and professor, respectively, Department of Mining and Metallurgical Engineering,
Amirkabir University of Technology, Iran
Abstract
Separation of refractory rock phosphate (P2O5 = 11.5%) from the Dalir area, Iran, containing quartz, calcite
and other impurities, by calcination and flotation processes has been successfully used to upgrade the phosphate
values. Petrographic studies of this ore showed that collophanite was the major phosphate mineral and the main
gangue minerals were calcite, dolomite and quartz. The results of characterization studies showed that the libera-
tion degree of apatite occurred below the average grain size of 140 μm. Preliminary flotation tests were used to
process the phosphate samples. Results of preliminary flotation tests showed that they don’t contain any desirable
efficiency (grade or recovery) of P2O5. Calcination was the best process for preconcentration of this ore. In the
desliming stage, about 14.4% of total P2O5 was removed. Encouraging concentrate grades were obtained after
flotation with anionic and cationic flotation, successively. The reagent schemes that have been used in this study
consisted of COCO-amine acetate and fatty acid as silicate and apatite collectors, respectively, as well as fuel oil
and anionic poly acryl amid as promoter collectors. The optimum pH values for direct and reverse flotations of
phosphate were 11 and 6, respectively. Experiments conducted using d80=140 µm deslimed fractions has yielded
an acceptable grade of more than 30% P2O5 with a recovery of more than 62%. Finally, a laboratory flowsheet
for the processing of Dalir refractory phosphate ore has been proposed.
Key words: Refractory rock phosphate; Flotation; Calcination; Characterization; Flowsheet
Introduction tion), chemical dissolution of carbonates with organic acids,

About 80% of the global production of phosphates calcination of phosphate ores and flotation techniques. These
comes from the beneficiation of sedimentary phospho- techniques have been studied by researchers in phosphate
rites (Lawer et al., 1980). Low-grade phosphate rocks samples from many different regions, such as Florida, South
are not usually suitable for direct use in acidulation Africa, Egypt, India, Uganda, Zambia, Brazil and other coun-
plants, unless their P2O5 content increases to 30% tries (Negm et al., 2002; Emich, 1984; EPA, 1993; Ciccu et
or more using conventional methods such as crush- al., 1972; Abdel Moneim, 1971, Taggart, 1964; Lovell, 1976;
ing, screening and drying, or some other physical Lukomona et al., 2005; Gu, 2002; Sengul et al., 2006; Gu,
separation process, such as washing and desliming 2002; Ayiskan, 1973; Hignett et al., 1977; Lawver et al., 1978a;
(Good, 1976). Lodha et al., 1984; Guan, 2009).
More studies have been carried out to try to reduce When the gangue minerals have different wetting proper-
the calcium carbonate content of phosphate rocks by ties, flotation is found to be technically and economically the
flotation and/or calcination (Zafar et al., 1995, Abdel- most attractive method of beneficiation (Prasad et al., 2000).
Khalek et al., 2009). Hignett et al. (1977) claimed With respect to flotation, there are two types of phosphate ore
that flotation seems to work better on ores containing gangues:
well-crystallized carbonates.
By quenching the hot calcinated rock in water, the Siliceous ores: Many researchers used different methods
major impurities usually pass through the desliming to beneficiate the siliceous phosphate rocks (Abdel-Zaher et
process, which is then mechanically separated from al., 2008; Yu et al., 1999; Lukomona et al., 2005; Schreider,
the coarser high grade “sand” concentrate fraction 1981; Al-Thyabat Salah et al., 2011)
(Good, 1976). Calcareous ores: The flotation technique cannot be easily
Many different techniques have been used to pro- applied to the sedimentary phosphates because of very simi-
cess and upgrade phosphate ores. These techniques lar physico-chemical properties of carbonates and phosphate
are size reduction and screening, attrition scrubbing (Abdel-Zaher et al., 2008).
and classification, electrostatic separation, magnetic
separation, gravity separation (heavy media separa- Dalir area phosphate ores have a 23-million ton reserve, with
Paper number MMP-10-045. Original manuscript submitted August 2010. Revised manuscript accepted for publication June

Table 1 — Chemical analysis of rock phosphate samples. acceptable grade of more than 30% P2O5 and a recovery of
more than 62% was obtained (see Fig. 6).
Chemical Chemical
% %
composition composition
Sample characterization
P2O5 11.99 Al2O3 1.66 Sample preparation. In this study, approximately 300 kg
CaO 36.36 Fe2O3 1.67 of the Dalir phosphate deposits were sampled. Samples were
SiO2 24.49 MgO 1.01
subjected to primary and secondary crushing until 100% of
particles passed through a 2-mm sieve (closed cycle with roll
K2O 0.66 MnO 0.1 crusher). The sampling techniques were adopted using Jones
Na2O 0.34 L.O.I 21.82 riffles and coning and quartering and representative samples
from each area were prepared for further studies.
Chemical analysis: The head sample was obtained by coning
an average grade of 11.9% P2O5. This deposit has presented in and quartering techniques and the results of chemical analysis
sedimentary shale and shale stone rocks. The main constituents are tabulated in Table1.
of the Dalir-area phosphate deposits are 11.9% P2O5, 36.36% X-Ray analysis: X-ray analysis was used to identify the
CaO, 24.49%SiO2 and 21.82% L.O.I. The main minerals are main minerals. XRD analysis showed that the sample consists
calcite (34.53 wt%), quartz (24.49 wt%), dolomite (4.651 wt%) of calcite, apatite and quartz as major minerals. From the
and apatite (28.31 wt%). results of XRD and chemical analysis of the ore sample, the
In this investigation, after the sample characterization and main minerals of the deposits were determined to be quartz
petrographic studies beneficiation were applied, preliminary (24.49 %wt), calcite (36.36 %wt), dolomite (4.65 %wt) and
flotation tests were used to process these samples. Results from apatite (28.31 %wt). Table 1 presents the chemical analysis
the preliminary flotation tests showed that without preconcen- of the samples used.
tration, processing of this ore had an undesirable efficiency
(grade and recovery). A typical result of preliminary flotation Petrographic studies. Petrographic investigation plays
tests is given in Table 2. Then the calcination process was used an important role in characterization studies. Almost 25 thin
to preconcentrate this ore. Finally, by using anionic - cationic sections were provided to understand the type of gangues and
flotation (two-stage flotation schemes), a concentrate with an valuable minerals, degree of liberation, type and amount of
Figure 1 — (a) Quartz inclusions in francolite pebble and context (usual (left) and polarized (right) optical microscope
images). (b) Phosphate particles with calcite and quartz inclusions (usual (left) and polarized (right) optical microscope
images).

Table 2 — Result from preliminary flotation tests.
Recovery P2O5
Wt. (%) Grade P2O5 (%)
Product (%)
Relative Total SiO2 CaO P2O5 Relative Total
Depressed product from direct flotation 27.77 24.16 26.33 35.45 14.01 28.19 25.87
Floated product from reverse flotation 25.05 21.80 13.82 40.96 11.24 20.80 19.09
Depressed product with orthophosphoric
47.17 41.04 26.04 39.74 14.60 51.01 46.82
acid (OPA) from reverse flotation
Total 100.00 86.99 100.00 91.78
inclusions of gangue minerals, shape of particle and other • Direct flotation: oleat sodium usage (1,000 g/t), pH (10),
mineralogical properties. Also, 11 thin sections from sieve sodium silicate usage (1,000 g/t), solid density of pulp
fractions were provided and studied with usual and polarized (18%) and conditioning time (3 min).
optic microscope. The results indicate that the main inclusions • Reverse flotation: oleat sodium usage (1,000 g/t), pH (4),
of gangue particle in francolite pebbles are quartz and calcite. ortho phosphoric acid (OPA) (1,000 g/t) and condition-
Also about 80% of quartz particles were smaller than 100 μm. ing time (3 min).
Dimensions of quartz inclusions in francolite pebbles were
about 15-60 μm. Apatite pebbles with inclusions have been The results of the preliminary flotation tests showed that the
shown in Figs. 1a and 1b. Calcite particles were fine crystalliz- grade and recovery were not acceptable. According to Table
ing and mainly located on the context of rock and inclusions. 2, a concentrate containing 14.6% P2O5 with a recovery of
Also, the results of SEM confirmed the presence of quartz 46.82% P2O5 was obtained, which was not a useful efficiency.
and calcite inclusions in apatite pebbles.
The study of sieve analysis with respect to P2O5, SiO2 and Calcination. Calcination was used to preprocess Dalir re-
CaO contents suggests that no sieve fraction can be selected fractory and low-grade sedimentary rock phosphate. More than
for beneficiation studies. Therefore, in all flotation tests, rock 10% of the world’s marketable phosphates are produced by the
phosphate samples were ground until d80=140 μm and deslimed calcination method. Traditionally, heat treatment of phosphate
at 10 µm, using the sedimentation beaker decantation technique, ores is defined as heating up the ore to a certain temperature
and subsequently subjected to flotation tests. to obtain a product with specific properties.
After the petrographic and liberation degree studies (by Calcination is the process of heating the ore to a high tem-
grain counting and sink and float tests), the liberation degree perature, ranging from 800° to 1,000° C to decompose the
of phosphate bearings achieved 140 μm. CaCO3 and MgCO3 to CaO, MgO and gaseous CO2. The CaO
and MgO formed are then removed as hydroxides by quenching
Beneficiation tests the calcined product in water and washing. Mineral formation
Preliminary flotation tests. Before preconcentration, varies as the temperature is increased from 0-1,350° C.
about 30 preliminary flotation tests with different methods The main objectives behind heating up the ore are:
and conditions were conducted. Results of these flotation
tests indicated that neither the grade nor the recovery rates 1. Removing water (120–150° C) (drying).
were desirable when beneficiating the refractory phosphate 2. Removing organic matter (650–750° C) (calcination of
ore. One set of these results is shown in Table 2. Before this organic material).
investigation, many researchers had studied the processing of 3. Dissociation of carbonates (850–1,000° C) (calcination
this ore; for example, Cyanamid of Poland Company, IFDC, of carbonate minerals such as dolomite and calcite).
Glokenz Institute and Madankav Engineering Company. The 4. Removal of fluorine (up to 1,350° C) (defluorination).
results of the preliminary flotation tests as reported here were
very similar to these researchers’ reports. For preconcentration, the calcination method was used. In
Some of the preliminary flotation test conditions were: this stage, the effects of three parameters on the calcination
Figure 2 — The effect of temperature and time on Figure 3 — The effect of time and temperature on the
weight loss. grade of P2O5.

Figure 4 — The effect of time and temperature on the
grade of CaO.
Figure 5 — The effect of grain size on the weight loss and
grade of P2O5 and CaO.
process were studied. These parameters were time (min), flotation tests. More than 50 sets of experiments were conducted
temperature (˚C) and grain size (micron): by varying the attrition time, pH, concentration of collector,
concentration of depressant, conditioning time for collector
Temperature: 850, 900, 950, 1,000˚ C and depressant and solids concentration.
Time: 60, 120, 180 min With the anionic - cationic flotation technique, processing
Particle size: 3,600, 1,600, 900, 600 and 400 µm of Dalir refractory phosphate ore was possible. At optimum
conditions, final flotation tests were examined and finally a
Figure 2 shows the effect of time and temperature on the laboratory scale flowsheet was suggested (see Fig. 6).
weight loss. The results of Fig. 2 show that the temperature
has the greatest effect on weight loss. Figure 3 shows that at Design of flowsheet
950 and 1,000˚ C, the phosphate grade reached its maximum Calcite and quartz were the main gangue minerals in the
value. Figure 4 shows that at 950˚ C, the CaO grade is at the Dalir phosphate deposit. Since these two minerals exhibit vastly
minimum value. The results of Fig. 5 show that the grain size different flotation behavior, in terms of their response to the
was not an effective influence on CaO and P2O5 contents and fatty acid and promoter collectors, it is difficult to separate
weight loss. phosphate-bearing minerals without preconcentration. Also,
In order to optimize the calcination conditions, various petrographic studies indicated that a major fraction of the quartz
parameters were investigated during the calcination experi- was in the fine-size range (minus 100 μm). Therefore, after the
ments. Optimum conditions in calcination process were the calcination and desliming, two-stage flotation schemes were
following conditions: conceived, in which calcite would be removed in the calcina-
tion stage and quartz in the cationic flotation stage. Phosphate-
Temperature: 950˚ C bearing mineral content was increased using anionic direct
Time: 120 min flotation. The flowsheet that is shown in Fig. 6 was designed
Grain size: grain size had small effect on calcination, so a to achieve beneficiation by removing the majority of gangue
d80=140 µm of samples was applied. minerals during the process.
The calcination temperature in this study ranges from Flowsheet details. Details of the suggested flowsheet are
850-1,000° C. The dissociation of carbonates is a highly en- as follows:
dothermic reaction that requires large fuel consumption. The
suggested dissociation reaction is as follows (Eq. (1)): (Kunii 1. Feed: In this investigation, the P2O5 content in the feed
and Levenspiel, 1969): was 11.9%.
2. Preparation and comminution: after preparation, samples
CaCO3 + heat → CaO  CO2 + 42.9 kcal/mol (1)
were ground to d80=140 µm.
At optimum conditions of calcination, about 50 kg of 3. Calcination: in this stage, under optimum conditions (2
sample were treated. After this process, calcinated products hours and 950° C temperature), about 50 kg of samples
were washed and scrubbed, and then -10 µm of slimes were were treated and the P2O5 content of samples was
removed by the decantation method. obtained, about 15.6%.
4. Washing and scrubbing: in this stage of the process
Flotation tests. After the calcination process and removal circuit, calcinated products were washed with water to
of CaO and MgO, the flotation process was used to beneficiate remove Ca and Mg oxides. Also, NH4OH was added
refractory phosphate ore. The results of these tests showed that for best removing of oxides.
with this process, refractory and low-grade sedimentary rock 5. Desliming: with the decantation of -10 µm particles,
phosphate could be satisfactorily beneficiated. about 14.4% of total phosphates were lost.
Batch flotation tests were conducted in a Denver-type flota- 6. Regulating and conditioning: a little NaOH for regulating
tion machine with an impeller speed of 1,200 RPM and a cell the alkalinity of pulp media was added.
capacity of 1,200 ml. Tap water was employed throughout the 7. Anionic flotation (rougher): anionic flotation was ex-

Figure 6 — Laboratory-scale flowsheet for the processing of Dalir refractory rock phosphate.
amined under these conditions: solid density of pulp had 31.09% P2O5 value, with 51.14% total recovery
(25%wt), oleat sodium usage (1,200 g/t), conditioning of P2O5.
time (3 min), pH (9), fuel oil (kerosene oil) (1,200 g/t), 9. Scavenger: in this stage, in order to increase the phosphate
RPM of impeller (1,250) and MIBC frother (20 g/t). recovery, depressed products from rougher flotation
Floated products of anionic flotation were scrubbed with anionic flotation can be processed. Scavenger
at a pH of about 6.5 to remove adsorbed collectors. flotation conditions were as follows: sodium oleat con-
Obtained products were applied to the cationic flotation centration (450 g/t), promoter of collector concentration
process. Depressed products were sent to the scavenger (kerosene 450 g/t), pH (9), conditioning time (2 min),
flotation step. and solid density of pulp (20%wt). In this stage, two
8. Cationic flotation: at this stage, cationic flotation was types of products were obtained: the depressed product
tested at a solid density of pulp (20%wt); COCO amine was tail (1) and the floated product was middling prod-
acetate concentration (600 g/t) was added in two stages, uct (according to the suggested flowsheet of Fig. 6).
conditioning time (3 min), pH (6.5), anionic poly acryl 10. Secondary anionic flotation: floated products from
amid (25 g/t), RPM of impeller (1,250) and MIBC cationic flotation had a high P2O5% value; therefore,
frother (20 g/t) conditions. The depressed product from for the recovery of phosphates from that fraction,
cationic flotation was the final concentrate (1) and it secondary flotation was used. Using this stage, about

10.69% of total phosphate was recovered. From sec- By using the suggested flowsheet, the total recovery of
ondary anionic floatation, a concentrate with 29.38% phosphate was 61.82%, with more than 30% P2O5 value.
P2O5 value can be obtained. Phosphate-bearing minerals had a high amount of quartz
11. Total recovery and grade of circuit: by using the sug- inclusion; therefore, the final concentrate had a high SiO2 value.
gested flowsheet, a product containing more than 31%
P2O5 with a total recovery 62% P2O5 can be obtained. Acknowledgments
Obtained concentrate can be used the fertilizer industry. The authors thank the Geological Survey of Iran for spon-
soring this project. Special thanks are due to Mr. Mosavvari
and Mr. Amini for their helpful discussions.
Discussion
Flotation of carbonaceous rock phosphate is very difficult, References
due to similar surface phenomena. It can be seen that calcina- Abdel Moneim, H.M., 1971, Geological investigations and physical beneficiation
tion is very useful to preconcentrate sedimentary low-grade of some low grade phosphate rocks in Egypt, M. Sc. Thesis, Ein- Shams
and carbonaceous phosphate ores. University.
In the first step of this investigation, calcination testing was
Abdel-Khalek, N.A., El-Shall, E., Abdel-Khalek, M.A., El-Mahdy, A.M., and El-Mofty,
S.E., 2009, “Carbonate separation from sedimentary phosphates through
performed to preconcentrate the samples. The effect of three bioflotation,” Minerals and Metallurgical Processing, Vol. 26, No. 2, pp. 85-93.
main parameters, including time, temperature and particle Abdel-Zaher M. Abouzeid, 2008, “Physical and thermal treatment of phosphate
size, on weight loss and P2O5 and CaO yield was tested. These ores - an overview,” Int. J. Miner. Process, Vol. 85, 59–84.
Ayiskan, 1973,” Beneficiation of Turkish Mazidag phosphate,” Cento Symposium
parameters were optimized. on the Mining and Beneficiation of Fertilizer Minerals, Istanbul.
In the second step of this research, bench scale flotations Al-Thyabat Salah, 2011, “A comparison of anionic and cationic flotation of a sili-
were performed to evaluate experimental batch flotation tests ceous phosphate rock in a column flotation,” Mining Science and Technology
(China), Vol. 21, pp. 147-151.
to enrich P2O5 values. Different methods were examined for Ciccu, R., Delfa, C., Alfanu, G.B., Carbini, P., Currelli, L., and Saba, P., 1972,
the beneficiating of Dalir-area phosphate ore. Anionic and cat- “Some tests of the electrostatic separation applied to phosphates with
ionic methods were the best ways to reach suitable efficiency. carbonate gangue,” International Mineral Processing Congress, University
of Cagliari, Italy.
Finally, flotation parameters were optimized and a suggested EPA, 1993, Phosphate Rock Processing, Mineral Products Industry, Emission
flowsheet was proposed. Factors, Section 11. 21, pp. 1–10. [www.epa.gov].
The phenomenon would have applications for upgrading Emich, G.D., 1984, “Phosphate rock,” Ind. Miner. Rocks, Vol. 2, pp. 1017–1047.
of low-grade refractory phosphate ores.
Good, P.C., 1976, Beneficiation of unweathered Indian calcareous phosphate
rock by calcination and hydration, US Bureau of Mines, Report No. 8154,
The results suggest that by using this method, it is possible to Washington.
produce a high-grade concentrate (31% P2O5) with 62% P2O5 Gu, Z., 2002, Fine Particle Flotation for Florida Dolomitic Phosphate Pebbles,
recovery. The results clearly show that the proposed flowsheet
M.S. Thesis, College of Engineering and Mineral Resources, West Virginia
University.
can be easily used in the upgrading of refractory phosphate ore. Guan, C., 2009, “Theoretical background of the Crago phosphate flotation
process,” Minerals and Metallurgical Processing, Vol. 26, No. 2, pp. 55-64.
Hignett, T.P., Doll, C.E., Livingston, O.H., and Raistrick, B., 1977, “Utilization
Conclusions of difficult ores,” L.J. Carpentier, Editor, New Developments in Phosphate
In this investigation, the processing of refractory low-grade Fertilizer Technology, Proceedings, Elsevier, Amsterdam, pp. 273-288.
Dalir-area phosphate was studied. Without preconcentration, Lawver, J.E., Raulerson, J.D., Cook, Charles, C., 1980, “New techniques in ben-
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and recovery. Florida high carbonate phosphates,” ISMA, Technical Economic Conferences,
Calcination is the best process for preconcentration of Dalir Orlando, FL, Preprints TA/78/ 1.
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the ore size that gives the appropriate heating results was found Lodha, T.R., Sinha, N.K., and Srivastava, A.C., 1984, “Characterization of low
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Lovell, V.M., 1976, Froth Characteristics in Phosphate Flotation, Gaudin Memorial
to be about 2 hours and 950° C, respectively. volume 1. AIME, New York.
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the processing of low-grade refractory phosphate deposits had
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African Journal of Science and Technology(AJST) Science and Engineering
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The laboratory-suggested flowsheet (Fig. 6) was used to Negm, A.A., and Abouzeid, A.-Z.M., 2002, Utilization of East Seba’eya Phos-
beneficiate Dalir refractory rock phosphate. The flowsheet had phate Plant Tailings, Final Report to the Academy of Scientific Research
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total recovery, respectively, were obtained. About 14.4% of the Yu, Y., and Zhang, J., 1999, US patent No. 5,865,318, Feb. 2, 1999
total phosphate is removed in desliming. The floating products
Zafar, I.Z., Anwar, M.M., and Pritchard, D.W., 1995, “Optimization of
thermal beneficiation of a low grade dolomitic phosphate rock,
of scavengers were middling products. Int. J. Miner. Process, Vol. 43, pp.123–134.

Influence of pebble mill operating
conditions on measurements
with an in-mill sensor
J. Alatalo* and B.I. Pålsson
Ph.D. student and Associate Professor, Minerals and Metals Research Laboratory,
Luleå University of Technology, Luleå, Sweden
* present address: Research and Development, LKAB, Luleå, Sweden
K. Tano
Research and Development Manager, LKAB, Malmberget, Sweden
Abstract
Autogenous grinding is a process of reducing the particle size distribution of an extracted ore by using the ore
itself as the grinding media. It is a process that is difficult to control and there is a lack of knowledge of the events
occurring inside the mill. To find out more about how the mill behaves under different processing conditions, a
full factorial test was performed with iron ore in a pilot-scale pebble mill at the LKAB R&D facility in Malm-
berget. To complement this work, a strain gauge detector was embedded in one of the mill’s rubber lifters, the
Metso Minerals continuous charge measurement (CCM) system, and was used to get more information about
the charge dynamics. The data from the experiments has been analyzed. For production purposes, an increase in
the number of particles smaller than 45 µm can be regarded as a probable increase in the production rate. The
analysis shows that there will be an increase in fines at 65% of critical speed, especially when the mill is 45% full.
This setting will also increase the power consumption, but improves the grindability of the ore even more. The
deflection of the lifters is smaller for lower critical speeds. A higher degree of filling also gives a smaller toe angle
and a higher shoulder angle as expected.
Key words: Comminution; Autogenous grinding; Pebble mill; Process optimization
Introduction of knowledge of what happens inside a mill. Since the environ-

Autogenous grinding is a process by which the ment inside the mill is too harsh for direct measurement and to
ore itself reduces the particle size distribution of get a better understanding of a mill’s performance, alternative
an extracted ore. It is a complex process due to the measurement systems are necessary. This can be done by, for
many factors that affect the process. First, the result example, measuring vibrations with sensors placed on a mill
is strongly dependent on the size distribution of the shell (Campbell et al., 2001), by the use of inductive sensors
ore fed to the mill (Fahlström, 1962). Also, the min- placed inside the mill (Kiangi and Moys, 2008) or by using an
eralogical properties of the ore influence the process acoustic method (Pax, 2001) to get information about events
and the feed rate regulates the mill properties. Finally, inside a mill. Different in-mill sensors have been made: Ma-
most settings need to be finely tuned for an optimal goutteaux has developed a mill sensor SensoMag (Clermont
grinding process. and de Haas, 2008) and the continuous charge measurements
The mills have high power consumption and most (CCM) system by Metso Minerals has good reproducibility,
energy will not be used to grind the material; less than reliability and a fast response time for varied process condi-
10% is used for grinding (Tano, 2005). There are large tions (Tano, 2005). The CCM system is used here in an attempt
economical benefits to be made with improved and to learn more about the charge dynamics in the experiments
optimized grinding settings. However, since the ore to discussed in this article.
a concentrator varies, the grindability of an ore is not Loussavaara Kiirunavaara AB, LKAB, mines iron ore,
constant over time. The mineralogy and the physical mainly magnetite in the north of Sweden to produce upgraded
properties may vary and result in varying optimal iron ore products for the steel industry. There is a demand for
operating conditions for the mill settings. the concentrators to maintain a high production rate with a
This means that autogenous grinding is a process steady quality to the pellet plants, and an understanding of the
that is difficult to control and also that there is a lack process is important to be able to achieve this goal.
Paper number MMP-11-024. Original manuscript submitted May 2011. Manuscript accepted for publication August 2011.
Discussion of this peer-reviewed and approved paper is invited and must be submitted to SME Publications Dept. prior to
May 31, 2012. Copyright 2011, Society for Mining, Metallurgy, and Exploration, Inc.

In one rubber lifter, a strain gauge detector is
embedded. This detector is a part of the continu-
ous charge measuring (CCM) system from Metso
Minerals. As the lifter bends backwards, the strain
gauge mounted on the leaf spring converts the de-
flection to an electric signal. The signal is amplified,
filtered and transmitted to a computer (Dupont and
Vien, 2001). When the CCM is operating, the speed,
charge level, toe-, shoulder- and charge angles and
a deflection signal are continuously updated in
the CCM monitoring program. The sensor is very
sensitive to changes in operating conditions and
has also shown good reliability and fast response
time (Tano, 2005).
Figure 1 shows a typical signal of one revolu-
tion, which can be described with a few positions.
Figure 1 — A simplified view of a typical deflection signal of one First, the lifter is in the air and unaffected, position
revolution from the CCM system and a schematic view of the mill. 1.Then it will reach the toe area, position 2. The
toe area commonly shows some turbulence and
here it is possible to detect slurry pooling. When
It is of interest to increase the production from grinding the lifter hits the charge, the deflection increases rapidly and
mills, and one way of doing this is to optimize the mill set- normally reaches the maximal deflection at the bottom of the
tings. However, it is important to first understand the responses mill, position 3. As the lifter continues to move through the
of how the mill behaves for different process conditions. To charge, the shockwaves from other lifter impacts can be de-
investigate this, a full factorial test was performed. The dif- tected, position 4. The deflection decreases as the mill leaves
ferent factors were volume-% solids, mill filling level and the the charge, which is referred to as the shoulder area, position
rotational speed of the mill. They were varied between 23 to 27 5. Finally, the lifter retracts from the charge and returns to its
volume-% solids, between 35% and 45% filling by volume and normal position, i.e., position 6.
65% and 85% of critical speed. The charge medium consisted
of 50% magnetite pebbles and 50% gangue pebbles by volume. Experimental conditions. The feed to the mill was a
magnetite pellet feed with a d50 of approximately 35 µm and
The experimental setup a density of 4.8 t/m3. The feed rate was kept constant at 0.85
LKAB has at their R&D facility in Malmberget, Sweden t/h to get a size distribution similar to the full-scale pebble
a pilot mill, which was used to obtain the necessary experi- mills at LKAB’s facilities at Kiruna, Sweden.
mental data. The grate-discharge mill is approximately 1.4 The charge consisted of a mixture of magnetite and gangue
m in diameter and 1.57 m in length and has 12 rubber lifters pebbles, each 50% by volume. The pebble feed rate was set to
installed. The lifters are 10 x10 cm and have a face angle of approximately 0.14 t/h to maintain a constant volume-% filling
45 degrees. Lifters and mantle pieces are made of rubber. The in the mill. The charge level is monitored by the CCM system.
mill is controlled from a process control room, from which it is The pebbles were between 10-35 mm in size.
possible to control the feed to the mill, as well as the additions Operational changes were made in volume-% solids, mill
of pebbles and water. Altering the speed of the mill requires a filling level and the rotational speed of the mill. They were
change of pulleys. This mill was used previously, when different varied between 23 and 27 volume-% solids, between 35% and
settings with a steel ball charge were investigated (Tano, 2005). 45% filling degree and 65% and 85% of critical speed.
Table 1 – Data from experiments.

Deg. Specific
% crit. Vol-% %<45 Net Toe Shoulder Grindability Pebbles Max
of surface
Exp speed solid µm power angle angle (kg<45µm / cons. defl.
filling area (cm2
(%) (%) (%) (kW) (deg) (deg) kWh net) (kg/kWh net) (mm)
(%) /cm3)
F1 65 27.1 25 85.7 0.89 9,781 35.6 190.8 22.9 7.0 1.04

F2 65 23.1 25 87.7 1.49 9,941 31.6 198.1 23.1 6.8 1.07
F3 85 27.1 25 86.6 1.41 9,871 29.8 187.7 22.7 6.8 1.69
F4 85 23.1 25 84.3 1.67 10,365 31.2 186.3 21.3 6.7 1.22
F5 75 25.1 35 87.9 2.30 11,812 28.2 190.1 22.2 7.0 1.47
F6 75 25.1 35 89.2 1.74 11,028 26.2 190.7 23.4 7.2 1.55
F7 65 23.1 45 88.9 2.15 10,713 25.3 198.7 22.8 7.1 1.31
F8 65 27.1 45 91.8 2.42 10,938 24.3 203.6 23.7 7.0 1.50
F9 85 23.1 45 87.2 2.34 11,427 27.2 208.3 21.9 7.0 2.16
F10 85 27.1 45 84.2 2.19 10,319 30.8 201.2 20.7 7.1 1.89
F11 80 25.1 35 86.4 2.19 10,799 30.3 194.5 21.7 7.1 1.91

Figure 2 — Plots of speed’s effect on amount of particles < 45 µm, the grindability and the maximum deflection. N is the
number of experimental runs, DF is the degree of freedom of the residuals, R2 is the percent of variation of the response
explained by the model, Q2 is the percent of the response predicted by the model according to cross validation, R2 Adj
is R2 adjusted for degrees of freedom, RSD is the residual standard deviation and Conf.lev. is the confidence level.
Results and discussion production result will be the case when a low percentage of
The full factorial test, with center points, was analyzed with critical speed is used; i.e., the lower rotational speed gives
the aid of a statistical program, MODDE (Umetrics, 2006). The better grinding. It will also introduce less stress on the lifters
factors are the degree of filling, the % of critical speed and and, by that, promote a longer lining life.
the volume-% solids. Data from the experiments are given in
Table 1. The responses are: percent of product that is <45 µm, Volume-% solids. For the volume-% solids, it is difficult
measured netpower (kW), specific surface area (cm²/cm³) by to interpret the results, since there are no significant effects.
permeability for product, toe and shoulder angles in degrees, This is most likely due to the too-small difference between
grindability (kg <45 µm/kWh net), pebble consumption (kg/ the high and low values used for this factor; the variation in
kWh net) and maximum deflection (mm) of the lifter when it the volume-% solids was not large enough. The original plan
first hits the charge. The grindability refers to the ease with called for a larger variation, but due to process restraints the
which materials can be comminuted (Wills, 1997). Note that variation became too small. However, there is an indication
experiment F11 should have been done at 75% of critical speed, that a higher volume-% solids will increase the grindability
but landed on 80% due to an error in changing pulleys. When and that the charge will climb higher in the mill. The result
analyzing the data, the interaction effects from volume-% solids from Tano’s experiments showed that the charge would have a
have been excluded, due to the low significance of volume-% lower toe angle and a higher shoulder angle at higher volume-%
solids as a main effect. solids (Tano, 2005).
In short, the results show that the responses in most cases
depend on the critical speed or on the degree of mill filling. Degree of filling. The main effect of the degree of filling
The critical speed has a significant effect on the number of of the mill can be seen in Fig. 3. When the mill is loaded with
particles less than 45 µm, on the grindability and on the maxi- the most material, the net power consumption will increase
mum deflection of the lifter in the toe region. The degree of by approximately 0.8 kW. This is the expected result, since
filling has a significant effect on the net power consumption, more material has to be rotated by the mill; i.e., more power
the specific surface area, the toe and shoulder angles, the pebble is necessary. With the highest degree of filling, the specific
consumption and the maximum deflection of the lifter in the surface area increases by ~ 500 cm2/cm3 and pebble consump-
toe region. In the following sections, the results are reported tion increases by just 0.2 kg/kWh net. When the mill is most
and discussed more in detail. filled it will deflect the lifter almost 0.4 mm more.
The extra material in the mill also causes a change in toe
Critical speed. The effect of changing the rotational speed and shoulder angles, which can be seen in the statistical data.
of the mill influences the amount of fine material produced, the Logically, the toe angle is approximately 5 degrees lower and
grindability of the ore and the maximum deflection. It can be the shoulder angle will be more than 10 degrees higher with
seen in Fig. 2 that the lower the percentage of critical speed, the higher degree of filling.
the more particles less 45 µm are created and the better the
grindability. The number of particles < 45 µm increases by Interaction effects. The interaction effects can be seen in
almost 3% and the grindability increases by almost 1.5 kg < Fig. 4. A high mill speed will decrease the effect the filling has
45 µm/ kWh net when the speed is at 65% of critical speed on the amount of particles < 45 µm produced. At a high speed,
instead of 85%. When the rotational speed is lower, the maxi- there is almost no difference in the production of particles <
mum deflection decreases by almost 0.5 mm (corresponding 45 µm whether the mill filling is low or high. At a low speed,
to ~27% of maximum deflection). This indicates that a better a fuller mill will yield more particles below 45 µm than a

Figure 3 – Plots of the degree of filling’s effect on the net power consumption, the specific surface area, the pebble con-
sumption and the toe and shoulder angle.
less-filled mill. Here, one may speculate that a slowly rotating for both cases when the speed is high.
mill highly filled creates a high internal grinding pressure in The pebble consumption will almost stay the same regardless
the charge that facilitates the generation of fines by attrition. of the speed of the mill when the degree of filling is high. For
The grindability will be highest for a highly filled mill at a a low degree of filling the pebbles consumption will decrease
low critical speed and only a little less when the critical speed as the speed of the mill increases. This would be consistent
and degree of filling are both low. The grindability is lower with a pebble consumption mostly caused by surface wear.
Figure 4 — Interaction plots between the percentage of critical speed and the degree of filling in the mill. The graphs
show, from left to right, the effect on amount < 45 µm, the effect on grindability and the effect on pebble consumption.

The method for mea-
suring the specific sur-
face area is uncertain
and, therefore, the lack
of significant effects for
this response is expected.
CCM deflection
curve. The CCM de-
flection curves from the
experiments when the
volume-% solid is kept
at a low value can be
seen in Fig. 5. For a low
degree of filling, it is clear
that the charge occupies
a smaller section of the
mill, represented by the
two gray curves. The toe
angles for the higher de-
grees of filling are lower Figure 5 — All signals come from experiments with low volume-% solids. Experiments with
for both high and low degree of filling are shown in black and those with low filling are shown in gray. Experiments
speeds, represented by with a low critical speed are shown with solid lines and the experiments with a high critical
the black lines (solid and speed are shown with dotted lines.
dashed). The lower speed
gives a smaller initial
maximum deflection, but
it increases as the lifter moves through the charge, which can type mill, while the present experiments were done in a mill
be seen in the solid lines. The maximum value occurs around that has a L/D ≈ 1.
120 degrees, which is when the lifter starts to move the charge Today, the full-scale pebble mills are run at slightly higher
upward but still experiences a large effect from charge pres- rotational speeds and have an almost 45% degree of filling. Since
sure. At high speeds, the lifter deflection is largest in the toe an efficient grinding of fine material is essential in pellet feed
area (dotted lines). production, it is strongly recommended that these experimental
findings should be verified in a full-scale mill. In addition, it
Conclusions is important to investigate how the throughput and the grate
For production purposes, an increase in the number of par- discharge are affected by a lower rotational speed. Also, that
ticles less than 45 µm can be regarded as a probable increase it probably is a great advantage to have variable speed control
in the production rate. of full-scale pebble mills, to be able to continuously adjust for
The analysis of the data shows that there will be an increase varying ore properties.
of fines when the mill turns at a low speed, especially when
combined with a high level of fill in the mill. The net power Acknowledgments
consumption will increase, primarily due to the higher filling The authors would like to thank LKAB for financial support
level; at the same time, the grindability will improve, but at and Metso Minerals for the use of the CCM system.
a greater rate. This is likely the result of increased attrition
in the charge. The higher degree of filling will, as expected, References
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give a smaller toe angle and a larger shoulder angle, simply Hinde, A., 2001, “SAG mill monitoring using surface vibrations,” Proceedings
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Calculating this increase as a possible improvement in energy Clermont, B. and de Haas, B., 2008, “Optimize mill performance by using on-
utilization indicates 3-4% better energy efficiency.
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UK, June 17-20, 17 p.
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lower speed but increases the more the mill is filled; however, ment,” Proceedings of the 33rd Ann. Can. Min. Proc., AGM, CIM, Ottawa,
it will still be lower than the maximum deflection at high pp. 51 - 67.
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consequence of a larger lifter deflection might be an increased load behaviour and power in a dry pilot mill: Experimental study,” Powder
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ers. This is also a good indicator that the rotational speed of com/modde.
the mill should be kept to a lower value. The comparison is

Wills, B.A., 1997, Mineral Processing Technology: An Introduction to the Practi-
cal Aspects of Ore Treatment and Mineral Recovery, 6th edition, Oxford,
interesting, since Fahlström did the experiments in a cascade- Butterworth-Heinemann, pp. 113.

Recovery of mercury
from spent silver oxide button cells
S. Aktas*and M.H. Morcali
Istanbul Technical University: Institute of Science & Technology and
Department of Chemistry and Metallurgy, respectively, Istanbul, Turkey
*E-mail: serdaraktash@yahoo.com
Abstract
The present work describes an investigation of a hydrometallurgical process for the recovery of mercury from
spent silver oxide button cells. The cell paste was leached in nitric acid to solubilize silver, mercury and zinc. The
optimum leaching conditions, in which mercury is entirely converted to Hg2+ ions and, therefore, does not co-
precipitate with silver chloride during treatment with potassium chloride solution, were 1.0 M HNO3, 45° C, 1
hour and 200 rpm. After the silver was removed from the solution, mercury was cemented out with zinc powder
with an efficiency greater than 99%. In the cementation experiments, the amount of zinc powder, shaking rate,
temperature and solution pH were investigated in detail. The mercury recovery (%) increased as the amounts
of zinc powder and the temperature were increased. Zinc hydroxide was precipitated from the waste solution
by the addition of sodium hydroxide. The Zn(OH)2 precipitate was then converted to zinc oxide. The proposed
process is proven to be simple, straightforward and environmentally friendly.
Key words: Mercury; Button cells; Hydrometallurgy; Cementation; Zinc
Introduction The objective of this work was to develop an effective

Button cells are currently used in hearing aids, hydrometallurgical process for the recovery of mercury from
digital thermometers, insulin pumps, portable medical spent silver oxide button cells.
monitors, hospital pagers, watches, toys and calcula-
tors (Buchmann, 2001). Because of their relatively Materials and methods
small external sizes and the need to provide maximum Maxell SR1120SW spent silver oxide button cells, which
energy in their small interiors, the internal buildup were supplied from a waste collection center in Istanbul,
of gases in button cells must be prevented. Such gas Turkey, were employed in this work. The spent silver oxide
accumulation can cause bulging and the consequent button cells were crushed, dried in an oven at 100° C, ground
rupture of the button cell. As a result, very small and finally sieved to remove the nonmetallic fractions. The
amounts of mercury continue to be used in button metallic fractions were then homogenized using a three-
cells to suppress the generation of internal gases, even dimensional shaker. After these treatments, a homogeneous
though mercury is a hazardous material that should mercury-containing cell powder was obtained and used for
be discarded in an environmentally responsible way the leaching experiments. The chemical composition of this
(Waltrich, 1972; Donald et al., 1991). cell powder is presented in Table 1.
According to the process for the treatment of spent After the silver, mercury and zinc were dissolved in a dilute
silver oxide batteries developed by the Korea Institute nitric acid solution, silver was selectively precipitated, which
of Geosciences and Mineral Resources, mercury is left mercury and zinc in the solution. The mercury content
recovered from spent silver oxide batteries by distilla- (Co) of the solution was measured using an atomic absorption
tion. After the mercury has been removed, silver and spectrophotometer (AAS) and inductively coupled plasma spec-
other fractions are leached using nitric acid. Silver trometer (ICP). The zinc content was titrimetrically measured
chloride is then precipitated from this solution with using 0.01 M EDTA. The solution pH was measured using a
sodium chloride, and the silver chloride is then reduced WTW pH 315i pH meter.
to metallic silver with sodium hydroxide and dextrose After the silver was removed from the leach solution,
(Sohn, 2003; Hanulik, 1993). In another process run metallic mercury was recovered using metallic zinc powder
by Batrec, a Swiss plant (Aktas, 2010), button cells (<150 μm) with a purity of 99.9% (Aldrich) inside a falcon
are easily sorted because of their small size, then tube placed in a temperature-controlled shaking bath. Solid/
placed together and heat treated in a distillation unit liquid separation was performed after each cementation ex-
to recover the mercury. The remaining content of the periment. The recovery (%) of this cementation process was
button cells is dispatched to a refinery in Germany calculated from the percentage of the cemented mercury using
for silver reclamation. the following equation:
Paper number MMP-11-017. Original manuscript submitted April 2011. Revised manuscript accepted for publication July

Figure 1 — Dissolution (%) at various acid concentrations Figure 2 — Dissolution (%) at various temperatures as a
as a function of the quantity of cell powder (1 h, 25° C, 5 function of the quantity of cell powder (1 h, 5 cc solution,
cc solution, 200 rpm). 1.0 M HNO3, 200 rpm).
Table 1 — The composition of the cell powder.

Elements Ag Zn Hg C S Fe Pb Cd Ni
% 62.09 13.55 0.54 2.48 0.0088 0.0040 <0.0100 N/A* N/A*
* Not available
Recovery (%) = [(Co−Ct)/Co] * 100 (1) which coprecipitate as mercury (I) chloride in the presence of
silver chloride during the precipitation process. This precipitate
where Co is the mercury concentration (103±1 ppm) of the would represent an undesirable impurity in the final product.
leach solution after the silver was removed, and Ct is the Ammonia solution was added to the precipitate to determine
concentration after the cementation. if mercury precipitated along with silver chloride. Aqueous
For each experiment, 5 cc of solution was used at various ammonia completely dissolves silver chloride to form an am-
temperatures and with various quantities of zinc powder. After mine complex. No precipitate (mercury (II) amidochloride
the cementation reaction, excess zinc was digested in 1.0 M or HgNH2Cl(s)) was observed, which indicated that mercury
H2SO4 to clean the product thoroughly. remained in the solution. This result was confirmed by ICP
measurements.
Results and discussion The results of the dissolution experiments indicated that
The process outlined in this paper can be used to recover the optimum leaching conditions under which mercury is
almost all of the mercury and zinc that are present in the spent completely converted to Hg+2 ions and does not precipitate
button cells used in this study. The dissolution (%) of mercury as mercury (I) chloride are 5 mL of 1.0 M HNO3, 45° C, 1 h,
incorporated in the spent button cells is displayed in Fig. 1. 200 rpm and 250 mg of cell powder.
As evident in Fig. 1, an increase in the molarity of the nitric After the leaching experiments were completed, a freshly
acid results in an increase in the dissolution (%) of mercury prepared 1 M KCl solution was added to the solution to selec-
in the spent button cells. The silver incorporated in the cell tively precipitate silver as silver chloride. At room temperature,
paste dissolves in nitric acid with an efficiency similar to that a silver precipitation efficiency of 99.9% was obtained after
of mercury, because of their similar electrochemical potentials. 60 min at 200 rpm. Silver chloride was precipitated because of
The silver and mercury precipitation characteristics are also its low solubility product constant, as shown in Eq. (2) (Lide,
similar in that both ions are quantitatively precipitated with 2004), whereas mercury remained in the solution:
chloride ions. At room temperature, mercury is converted to
AgCl(s) → Ag+(aq) + Cl¯(aq) Ksp = 1.8 × 10-10 (2)
mercury (I) ions, which precipitate in the presence of chloride
ions under the experimental conditions. A temperature-related The silver chloride was reduced to metallic silver with an ef-
experiment was undertaken to allow the observation of the ficiency greater than 99% by reaction with metallic zinc powder,
conversion of mercury (I) to mercury (II). Figure 2 shows as represented in Eq. (3), in 1.0 M HCl at room temperature
the effects of temperature on the dissolution (%) of mercury. at 200 rpm. Detailed information concerning this reaction is
As evident in the figure, the dissolution (%) of mercury available elsewhere (Aktas, 2010).
increases with increasing temperature, which is in agreement
2 AgCl(s) + Zn(s) → 2 Ag(s) + ZnCl2(aq) (3)
with results previously reported in the literature (Aktas, 2010).
Here, the formation of Hg(II) is complete at 45° C; therefore, After the silver chloride was removed by filtration, the re-
no mercury (II) chloride was observed to precipitate when maining solution was diluted to 5 L. The new solution, which
potassium chloride was added to the solution. Even though exhibited a pH value of 1.07, contained 103 ppm Hg2+ and
the dissolution (%) of silver exceeded 99% at 25° C in 2.0 M 2,585 ppm Zn2+. The recovery of the mercury is explained in
nitric acid solution, mercury was converted to mercury (I) ions, detail in the following section.

Figure 3 — Mercury recovery (%) as a function of the Figure 5 — Mercury recovery (%) at various temperatures as
quantity of zinc (1 h, 5 cc solution, 25° C, 200 rpm). a function of the quantity of zinc (1 h, 5 cc solution, 200 rpm).
Effects of the amount of zinc powder on mercury recovery as shown in Eqs. (4) and (5) (Lide, 2004; Nelson et al.,
(%). Figure 3 details the variation in mercury recovery (%) 2000; Makhloufi et al., 2000).
with different quantities of zinc. 2H+(aq) + 2e- → H2(g) E° = 0.00 V (4)
As evident in the figure, mercury recovery (%) increased
with increasing amounts of zinc powder, which is in agree- Zn+2(aq) + 2e- → Zn°(s) E° = −0.762 V (5)
ment with studies that investigated cementation efficiency with
regard to the quantity of the cementor (Aktas, 2008; Aktas et The standard reduction potential of Hg (Lide, 2004) is
al., 2010). The recovery was almost complete when more than given as follows:
45 mg of zinc powder was used. An increase in the amount of Hg2+ + 2e- → Hg(l) E° = +0.851 V (6)
the cementor increases the surface area of the zinc powder per
mercury ion. Therefore, the likelihood of interactions between The potential difference is calculated to be 1.61 V (Lide,
metallic zinc atoms and mercury ions present in the solution 2004; Ku et al., 2002). The overall reaction is expressed in
increases, which results in a higher cementation percent (Aktas, Eq. (7):
2008; Aktas, 2010; Aktas et al., 2010; Aktas, 2011). An excess
stoichiometric amount of cementor was required to recover Zn° + Hg2+ → Zn2+ + Hg(l) Etotal = +1.61 V (7)
the metal to be cemented from the solution. Two reasons for
the requirement of excess cementor may help elaborate the The reasons why zinc was preferred for the cementation
reaction mechanism. reaction include:
1. Fresh zinc surfaces are covered by freshly precipitated • The cell paste already contains zinc.
mercury, which prevents further reaction (Aktas, 2008; • Zinc is inexpensive and easy to obtain.
Aktas, 2010; Aktas et al., 2010). • Electrochemical potential between mercury and zinc is
2. Because of the acidic media, hydrogen ions are reduced sufficiently high to facilitate this cementation reaction
by zinc metal, which results in the formation of Zn2+ with high efficiency.
Figure 4 — Mercury recovery (%) at various shaking rates as Figure 6 — Solution pH at various temperatures as a
a function of the quantity of zinc (1 h, 25° C, 5 cc solution). function of quantity of zinc (1 h, 5 cc solution, 200 rpm).

Figure 7 — The variation of zinc concentration with the Figure 8 — Zinc precipitation (%) as a function of
solution pH. solution pH.
The effects of the shaking rate on the dissolution (%). after 60 min using 5 mg of zinc powder at room temperature.
In this experimental series, mercury recovery (%) was inves- However, under the same conditions but at a temperature of 45°
tigated as a function of the shaking rate in the range of 40 to C, a recovery of 82% was achieved. The effect of temperature
200 rpm. The duration of the experiments was limited to 1 is more pronounced with lower quantities of zinc than with
hour. Figure 4 displays the variation in mercury recovery with higher quantities. It can be concluded that, if there is no pos-
different shaking rates. sibility of heating the solution that high, recovery efficiency
As shown in Fig. 4, shaking was an important parameter can be attained just by increasing the amount of zinc, because
that affected the cementation of mercury from the solution. The the possibility of interactions between metallic zinc atoms and
more rapid the shaking rate, the greater the obtained recovery mercury ions increases.
(%). A recovery of 60% was observed for 5 mg of zinc powder
at a shaking rate of 40 rpm, whereas the recovery increased to The effects of the quantity of zinc on the solution pH.
72% with a shaking rate of 200 rpm. This difference can be The variation of pH with different quantities of zinc was
attributed to the fact that the probability of contact between the studied in the temperature range of 25-45°C; the results are
metallic zinc atoms and mercury ions present in the solution shown in Fig. 6.
increases with increasing shaking rate, which results in higher As shown in Fig. 6, the solution pH increases dramatically
efficiencies (Aktas, 2010). The maximum agitation rate (200 with increasing amounts of zinc powder, which confirms that
rpm) was selected for the subsequent experiments. zinc preferentially reacts with free nitric acid in the medium
rather than cementing mercury out of the solution. For example,
The effects of temperature on the mercury recovery a pH value of approximately 5.3 was observed after 60 min
(%). The effects of temperature on the mercury recovery (%) when 30 mg zinc powder was used at 35° C. However, when
were studied in the range of 25-45° C; the results are displayed the quantity of zinc powder exceeded a certain amount (e.g., 30
in Fig. 5. mg), almost no change in solution pH was observed. This result
As shown in Fig. 5, temperature was observed to play an indicates that free acid is nearly neutralized by zinc powder.
important role in the recovery of mercury from the solution. The For industrial applications, it is suggested that the solution
cementation efficiency increased as the reaction temperature pH be adjusted using sodium hydroxide, which reduces the
was increased. For example, a recovery of 73% was observed unnecessary consumption of zinc.
Figure 9 — XRD pattern of the ZnO produced by heat treatment.

Figure 10 — The flowchart for the hydrometallurgical treatment of
spent silver oxide button cells.
After the mercury was recovered, the authors attempted As expressed in Eq. (8) (Lide, 2004), Zn(OH)2 exhibits a
to recover the zinc as zinc hydroxide. First, the cementation low solubility product constant. Zinc exhibits an amphoteric
solution and the zinc-containing solution from the silver chlo- character; therefore, it redissolves in the sodium hydroxide
ride–silver conversion reactions were combined. A new zinc solution to form a zinc hydroxide complex (Anacleto and
solution that contained 9,957 ppm Zn2+ with a pH value of Carvalho, 1996). Consequently, regular pH checks should be
1.02 was treated with NaOH to yield Zn(OH)2. The variation performed in industrial applications.
of the zinc concentration with solution pH is shown in Fig. Zn2+(aq) + 2OH¯(aq) → Zn(OH)2(s) Ksp = 3.0 × 10-17 (8)
7; Fig. 8 displays the zinc precipitation (%) as a function of
the solution pH. As evident in Fig. 8, zinc was precipitated as zinc hydroxide

Table 2 — Mass balance based on the 260 button cells.
Substance Quantity (g)
Amount of cell powder 95.35
Total silver amount in cell powder 59.20
Total mercury in cell powder 0.515
Total zinc in cell powder 12.92
Nitric acid consumption for leaching 120.15
Potassium chloride consumption for silver 40.87
Zinc consumption for AgCl–Ag conversion 23.27
Zinc consumption for cementation 30.58
with an efficiency greater than 99% in the pH range of 8-10. Acknowledgments

The zinc hydroxide was rinsed with cold water five times and The authors wish to thank TUBITAK for financial support
then heated to 600° C to yield zinc oxide. The XRD pattern under project 109M365. Special thanks are due to Güntaç
of the zinc oxide is displayed in Fig. 9. Zorlu (MSc student) for his invaluable discussions and Mr.
The flowchart for the hydrometallurgical treatment of spent Tayfun Aktas for making possible some analyses conducted
silver oxide button cells is shown in Fig. 10. outside the university.
Table 2 displays the mass balance based on the 260 button
cells employed in the present study.
References
Conclusion Aktas, S., 2008, “Silver recovery from silver-rich photographic processing solu-
In the present work, a hydrometallurgical process was de- tions by copper,” Canadian Metallurgical Quarterly, January, Vol. 47, No.
veloped to recover silver, mercury and zinc from waste silver
1, pp. 37–44.
Aktas, S., Morcali, M.H., and Yucel, O., 2010, “Silver recovery from waste
oxide button cells. More than 99% of the mercury incorporated radiographic films by cementation and reduction,” Canadian Metallurgical
in waste button cells could be dissolved with dilute nitric acid Quarterly, April, Vol. 49, No. 2, pp. 147–154.
solutions (1.0 M–2.0 M) even under moderate experimental Aktas, S., 2010, “Silver recovery from spent silver oxide button cells,” Hydro-
metallurgy, July, Vol. 104, Issue 1, pp. 106-111.
conditions. The optimum leaching conditions, in which mer- Aktas, S., 2011, “Rhodium recovery from rhodium-containing waste rinsing
cury is entirely converted to Hg2+ ions and, therefore, does not water via cementation using zinc powder,” Hydrometallurgy, February, Vol.
co-precipitate along with silver chloride during the treatment 106, Issues 1-2, pp. 71-75.
Anacleto, A.L., and Carvalho, J.R., 1996, “Mercury cementation from chloride
with potassium chloride solution, were 1.0 M HNO3, 45° solutions using iron, zinc and aluminium” Minerals Engineering, April, Vol.
C, 1 hour and 200 rpm. The dissolved silver was selectively 9, Issue 4, pp. 385-397.
precipitated with 1 M KCl solution, which ensured that the Buchmann, I., 2001, Batteries in a Portable World, 2nd Edition, Cadex Electron-
ics, 29 pp.
mercury and the zinc remained in the solution. The mercury Donald, L.B., Castlegar, D.A., and Boateng, D., 1991, “Method for the recovery
was subsequently recovered with an efficiency of more than of mercury from mercury-containing material,” U.S. patent 5,013,358.
99% using zinc powder. The mercury recovery efficiency Hanulik, J., 1993, “Liquid filling method for a high-temperature and high-pressure
increased with increasing amounts of zinc powder, as well as

vessel and apparatus therefor,” U.S. patent 5,120,490.
Ku, Y., Wu, M.H., and Shen, Y.S., 2002, “Mercury removal from aqueous solu-
with increasing temperature. The zinc powder was consumed by tions by zinc cementation,” Waste Management, November, 22, Issue 7,
free acid in the medium. It is advisable that solution pH should pp. 721-726.
be adjusted using sodium hydroxide to prevent the excessive
Lide, D.R., 2004, The Handbook of Chemistry and Physics, 85th Edition, CRC
press LLC.
consumption of zinc. The zinc-containing solutions stemming Makhloufi, L., Saidani, B., and Hammache, H., 2000, “Removal of lead ions
from the cementation solution and from the reaction of silver from acidic aqueous solutions by cementation on iron,” Water Research,
chloride with zinc powder were combined, and zinc hydroxide Vol. 34, pp. 2517-2524.
Nelson, A., Demopoulos, and G.P., Houlachi, G., 2000, “The effect of solution
was subsequently precipitated by the addition of sodium hy- constituents and novel activators on cobalt cementation,” Canadian Metal-
droxide. The Zn(OH)2 precipitate was then converted to zinc lurgical Quarterly, April, Vol. 39, No. 2, pp. 175-186.
oxide. The proposed process avoids environmental problems Sohn, J., 2003, “Collection and recycling of spent batteries in Korea,” International
Congress for Battery Recycling, Lugano, Switzerland.
and allows for the nonhazardous hydrometallurgical recovery Waltrich, P.F., 1972, “Removal of mercury from effluent streams,” U.S. Patent,
of mercury from waste silver oxide button cells. 3,704,875.

Purification of niobium oxide by
dissolution and solvent extraction
K.C. Nathsarma and B.B. Nayak
Institute of Minerals & Materials Technology, Bhubaneswar, Orissa, India
P. Brahmbhatt and S. Pradhan

Institute for Plasma Research, Bhat, Gandhinagar, Gujarat, India
Abstract
An attempt was made to extract niobium oxide from ~98.5% Nb2O5 using solvent extraction processes. Nb2O5
is used as the feed material in carbothermic reduction processes aimed at producing high-homogeneity, super-
conductor-grade niobium on a laboratory scale. The Nb metal used for superconductor applications requires a
residual resistivity ratio (RRR) > 300, which in turn needs a stringent purity of Nb and allows impurities (substi-
tutional and interstitial) in ppm levels only. In this paper, solvent extraction of niobium was studied under various
experimental conditions, such as effect of different extractants, concentration of methyl isobutyl ketone (MIBK)
in the organic phase and concentration of various acids. The concentrate was digested with hydrofluoric acid,
with ammonium fluoride (NH4F) as a stripping agent. The extraction of niobium from low hydrofluoric- (HF-)
bearing solution was found to be low. Thus, various concentrations of hydrofluoric acid and sulfuric acid, as well
as hydrofluoric acid and hydrochloric acid, were investigated towards obtaining a maximum amount of niobium
in the filtrate and a minimum amount of niobium in the residue. A McCabe - Thiele plot for extraction of niobium
from the aqueous phase, HF-bearing solution using HCl with 85% MIBK in kerosene has been constructed to
determine the O:A ratio and the number of stages of the process.
Key words: Solvent extraction; Hydrochloric acid; Inductively coupled plasma; Acids
Introduction techniques such as e-beam or vacuum arc melting are not ef-
Niobium naturally occurs with tantalum because fective due to the high boiling points and vaporization points
of the similarity in respective atomic sizes (Dennis, (BP) of these refractory elements. The melting points of these
1961). Niobium alloys, such as NbTi alloys and elements are: W = 3,410 °C, Ta = 2,996 °C, Mo = 2,610 °C.
Nb3Sn intermetallics, have been used as technical The boiling points are W = 5,930 °C, Ta = 5,425 °C and Mo =
superconductors (Miller, 1957). High-homogeneity 5,560 °C. In the preparation of UHP-Nb (ultra high purity Nb),
(Hi Ho), high-purity niobium is an essential ingredient the control of the Ta and W content is critical. The impurity
in realizing technical Nb3Sn superconductors through Ta bears chemical and physical similarities to Nb. Further, the
the “internal tin” route. In the ‘internal tin’ route of vapor pressure of W is low. Owing to these reasons, liquid-
fabricating Nb3Sn superconducting strands, Sn is liquid extraction is an appropriate process to eliminate Ta &
supplied by internal diffusion from the solid Sn rod W from Nb2O5 (Koethe and Moench, 2000).
in a copper billet. High homogeneity niobium rods are The starting material for niobium extraction, commercially
staked, as per the billet design, in deep drilled holes available Nb2O5, contains impurities both interstitial (C, O) and
on the billet. During the heat treatment of strands substitutional (Na, Mn, Ta, Fe) in nature. The aim of this work
drawn from such billets, Sn diffuses across the copper was to remove substitutional impurities up to an Nb purity of
matrix up to the Hi Ho Nb site and makes Nb3Sn lay- 99.7%. Solvent-extracted Nb2O5 thereafter was largely free
ers (Cardwell and Ginley, 2003). These Nb3Sn layers from such substitutional impurities. A subsequent carboth-
are responsible for current carrying capacity of the ermic reduction can then eliminate the remaining interstitial
superconductors in cryogenic temperatures. A purity impurities. The carbothermic reduction of niobium has been
exceeding 99.85% and homogeneity in niobium is extended to the direct preparation of Nb-Ti alloys and Nb3Sn
essential for high-current-carrying, high-field Nb3Sn. through the “internal tin’ route (Gupta et al., 2003).
The primary objective in this paper, which describes
an attempt to produce high-homogeneity niobium (Hi Process of extraction and separation
Ho Nb) of superconductor grade, was to reduce the The mined oxides of tantalum, Ta2O5, and niobium, Nb2O5,
refractory element impurities to the following level: are usually obtained after a breakdown treatment. The first step
Ta < 400 ppm, W + Mo < 20 ppm. Since the Nb2O5 in the process is the reaction of the oxides with hydrofluoric acid
obtained has a purity of 98.5%, it was not suitable (Krupin, 2000; Soisson et al., 1961; Ayanda and Adekola, 2011).
for further use. It was attempted to reduce impurities
by a solvent refining method, as pyrometallurgical Ta2O5 + 14HF → 2H2 [TaF7] + 5H2O (1)
Paper number MMP-11-019. Original manuscript submitted April 2011. Revised manuscript accepted for publication August

Figure 1 — Effect of [HCl] on extraction of niobium. Figure 2 — Effect of [H2SO4] on extraction of niobium.
Nb2O5 + 10HF → 2H2 [NbOF5] + 3 H2O (2) solution were measured in the separating funnel, into which
distilled water was added. Extractant solution in kerosene
The liquid extraction of the fluorides from aqueous solution was added to maintain an O: A ratio of 1:1. The organic and
is carried out by organic solvents like Aliquat 336, Alamine aqueous solutions were mixed for a period of 10 min. to ensure
336 (Hussaini and Rice, 2004), methyl isobutyl ketone (MIBK) complete extraction in the separating funnel. The mixture was
(Bludssus and Eckert, 1993; Htet and Kay, 2008) or Cyanex 923. then allowed to achieve phase separation and the organic phase
The complex niobium and tantalum fluorides are then extracted separated from the aqueous phase. Various other parameters,
separately from the organic solvent with water. Alternatively, such as the O/A ratio and aqueous and organic concentration
the solution is precipitated by adding potassium fluoride to of diluents, were optimized for maximum extraction of Nb.
produce a potassium fluoride complex, or precipitated with The stripping of the organic phase was performed using NH4F
ammonia as the pentoxide (Izabela and Maria, 1999). after the extraction of niobium. Chemical analysis of Nb2O5
before and after solvent extraction in the solution was done
Materials by inductively coupled plasma optical emission spectrometer
Sample collection, solutions and reagents. Nb2O5 was (ICP-OES Perkin Elmer Model: Optima 2100 DV).
procured with a purity level of 98.5 wt%. As mentioned earlier,
the required purity for superconductor-grade Nb is 99.97 wt%. Results and discussion
Effect of various extractants on solvent extraction of
Reagents. The organic reagent used for recovery of niobium niobium. The Nb – Ta leach liquor bearing 42.38 kg/m3 nio-
was MIBK. This was used for the extraction studies without bium and 0.1569 kg/m3 Ta was used to extract the niobium
further purification. Distilled kerosene was used as a diluent to employing different solvents, as shown in Table 1.
prepare the solvent in different concentrations. Other organic It was evident from above that the extraction of niobium
solvents used in the extraction of niobium were Aliquat 336, was highest with MIBK and least with Cyanex 921. Hence,
Alamine 336, Cyanex 923 and Cyanex 921. the extraction and separation studies for Nb and Ta were car-
ried out with MIBK in kerosene. Further, MIBK is a preferred
Experiment. The material containing Nb2O5 and Ta2O5 extractant due to its low density and low viscosity, which helps
was dissolved in HF. The volume of the leaching solution was to obtain high-purity products (Zhu and Cheng, 2011).
increased to one liter in a polyethylene volumetric flask. The
leached solution contained 67.37 kg/m3 Nb and 0.1703 kg/m3 Effect of [HCl]and H2SO4 on extraction of Nb. Htet
Ta, which was confirmed by inductively coupled plasma optical and Kay (2008) studied the extraction of niobium oxide from
emission spectroscopy analysis carried out on these samples. columbite-tantalite concentrate from the Thayet Kon Area in
The concentration of HF in the leach solution was 4.595 N. The Nay Phi Taw (Myanmar) using MIBK. They reported the co-
concentration of Nb in the leach solution was 396 times more lumbite and tantalite concentrate being leached with a mixture of
than that of Ta. The various concentrations of HF in the leach hydrofluoric acid and sulfuric acid. Further, various concentra-
Table 1 — Effect of various extractants on extraction of Nb and Ta.

%Nb %Ta
Extractant [Nb] Raff., kg/m3 [Ta] Raff., kg/m3 [Nb]Org kg/m3 [Ta]Org, kg/m3
extn. extn.
25% Aliquat 336 4.8375 0.0242 37.5425 0.1363 88.5 84.5
20% Alamine 336 16.425 0 25.955 0.1569 61.2 100
20% MIBK 2.3125 0.1235 40.0675 0.0334 94.5 21.3
0.25 M Cyanex 923 5.1375 0.0261 37.2425 0.1308 87.9 83.4
25% Cyanex 921 27.8438 0.015 14.5363 0.1419 34.3 90.4

influencing solvent, as described in the next section.
Effect of [MIBK] on the extraction of niobium. The

aqueous feed composed of an optimized concentration of (a)
HF (8.7272 N) and HCl (4.874 N) or (b) HF (8.7272 N) and
H2SO4 (10.7586 N) was mixed with varying concentrations
of MIBK, in order to further maximize niobium extraction. As
the MIBK concentration increased, the percentage of niobium
extraction also increased, as shown in Fig. 3. These experi-
mental data demonstrate the sigmoidal increase in niobium
extraction increases from 6.35 to 96.79% in the case of (a) and
1.52 to 98.86% in the case of (b), as described above. Further,
the extraction of Nb was found to be maximized with an 85%
concentration of MIBK. McCabe-Thiele plots were done for
case (a), since the concentration of HCl was found to be lower
Figure 3 — Effect of [MIBK] on the extraction of niobium compared to H2SO4.
in the presence of (a) [HF] +[HCl] and (b) [HF ] + [H2SO4].
B - % [Nb] extraction in (a), C - [Nb]Org in (a), D - [Nb] McCabe-Thiele plot for extraction of Nb using 85%
Raff in (a), E - % [Nb] extraction in (b), F - [Nb]Org in (b), MIBK in kerosene for case (a). The Nb-Ta solution was pre-
G - [Nb]Raff in (b). pared comprising of 13.474 gpL Nb, 8.7272 N HF and 4.847
N HCl. This solution was then exposed to 85% MIBK in dif-
ferent ratios to extract the maximum amount of niobium. The
McCabe-Thiele plot (Fig. 4) shows the extraction of niobium at
tions of hydrofluoric acid and sulfuric acid were used to obtain different O/A ratios using 85% MIBK. This plot indicates three
suitable conditions for the maximum extraction of niobium. In stages of Nb extraction at an O:A ratio of 2:5. The extractions
contrast, in the present investigation, hydrofluoric acid [HF] were found to be 70.3, 93.3 and 96.27%, respectively, in the
concentration was kept constant and concentrations of HCl and first, second and third stages.
H2SO4 were varied (Htet and Kay, 2008). The results are shown
in Figs. 1 and 2. Niobium extraction was carried out with 50% Countercurrent simulation study for extraction of Nb
MIBK in kerosene at a 1:1 phase ratio. The extraction percent- with 85% MIBK in kerosene at an O:A ratio of 2:5. In line
age of niobium was very low, with increasing concentrations with the predictions from the McCabe-Thiele plot, a three-
of HCl and H2SO4 for a fixed lower concentration of HF. The stage countercurrent extraction (CCS) from the Nb solution
concentration of extractant and the concentration of H2SO4 (13.474 kg/m3 Nb) with 85% MIBK in kerosene at an O:A
or HCl do not show any noticeable effect on the extraction of ratio of 2:5 was carried out with an objective to generate the
niobium at a fixed lower concentration of HF. loaded organic. The raffinates were then analyzed as shown in
The concentration of HF, therefore, was required to be in- Table 2. The generated loaded organic was subsequently used
creased to an optimum in order to achieve maximum extraction for the stripping studies.
of niobium. This optimum concentration (8.7272 N) of HF in As shown above, the % of Nb extraction in all raffinates
the solution was then kept constant. Concentrations of HCl exceeds 99% after the triple stage countercurrent extraction.
and H2SO4 were then increased from 2.437 to 6.0925 N and This validates the CCS extraction in the expected lines.
3.6216 to 14.3448, respectively. A sigmoidal increase in nio-
bium extraction from 12.75 to 46.48% in the case of HCl was Stripping of Nb-LO with NH4F solution. Next, it was
observed, as shown in Fig. 1. A similar increase was observed imperative to extract the Nb from the Nb-LO. For this pur-
in the extraction of niobium from 11.13 to 83.92% in the case pose, five mL each of the Nb-LO was stripped with various
of H2SO4, as shown in Fig. 2. Thus, the highest extraction of concentrations of NH4F from a total loaded organic solution
niobium was possible in (a) concentrations of HF (8.7272 N) of 33.38 kg m-3. From these experiments, it was observed that
and HCl (4.874 N) (b) concentrations of HF (8.7272 N) and the Nb stripping improves with increasing concentration of
H2SO4 (10.7586 N). This was subsequently parametrically NH4F limiting the maximum to 0.5 M of NH4F. A 0.5 M of
investigated with varying concentrations of MIBK as the NH4F strips Nb in excess of 95%. The strip raffinates details
are elaborated below in Table 3.
The stripping isotherm was subsequently carried out with
0.5 M NH4F.
McCabe-Thiele plot for stripping of Nb-LO with 0.5 M

NH4F. The Nb-LO was stripped with 0.5 M NH4F solution at
various O:A ratios. The LO: SS ratios were varied from 1:5 to
5:1, keeping the total mixture volume at 18 mL. The mixture
samples were equilibrated for 10 min. Afterwards, the raffinates
were separated, diluted and analyzed with ICP-OES.
The McCabe-Thiele plot (Fig. 5) shows the stripping of
Nb-LO at a different O/A ratio with 0.5 M NH4F. This predicts
two stages of stripping at an O:A ratio of 2:1.
Figure 4 — McCabe-Thiele plot for extraction of Nb with Countercurrent stripping of Nb-LO with 0.5 M NH4F.
85% MIBK in kerosene. As per predicted by the McCabe-Thiele plot, the two-stage

Table 3 — Stripping of Nb-LO with NH4F solution.
[Nb]LO [Nb]SS % Nb
[SS], N
kg/m3 kg/m3 stripping
0.005 33.3818 30.5376 91.48
0.01 33.3818 30.7046 91.98
0.05 33.3818 30.9375 92.68
0.1 33.3818 30.5375 93.48
0.2 33.3818 31.375 93.99
0.5 33.3818 31.8625 95.45
Table 4 — Countercurrent stripping of Nb-LO

Strip solutions [Nb]SS kg/m3 %Nb Stripping
Figure 5 — A McCabe-Thiele plot for stripping of Nb-LO
with 0.5 M NH4F. SSa 58.0563 86.96
SSb 60.475 90.58
Table 2 — Counter-current simulation study for extraction SSc 63.3125 94.83
of Nb.
SSd 63.250 94.74
Raffinate samples [Nb]Raff kg/m3 % [Nb] extrac.
SSe 64.250 96.24
Ra 0.0467 99.65
SSf 65.5625 98.20
Rb 0.0798 99.41
SS1 67.0625 100
Rc 0.1014 99.25
Rd 0.1121 99.17
Re 0.1162 99.14 chloride route when compared to the sulfate route of extrac-
tion. The McCabe-Thiele plot for the extraction of niobium
Rf 0.1189 99.12
from the aqueous phase, HF- and HCl-bearing solution diluted
Rg 0.1250 99.07 with 85% MIBK indicates the need for three stages of extrac-
tion at an O:A ration of 2:5. The McCabe-Thiele plot predicts
two stages of Nb-LO stripping at an O:A ratio of 2:1. It was
countercurrent stripping (CCS) was found to be optimum. observed that 100% stripping of niobium from loaded organic
Thus, the niobium had to be stripped from the Nb-LO solution solvent was achieved. Niobium pentoxide (Nb2O5) powder of
with 0.5 M NH4F at an O:A ratio of 2:1. The results of these 98.5% purity and < 63 µm grain size was taken as the starting
investigations are shown in Table 4. raw material for carbothermic reduction in a normal-polarity
It was observed that 100% stripping of Nb from the loaded thermal plasma arc reactor.
organic phase was achieved and Nb in the strip solution was
enriched two times to 67.0625 kg/m3. From the solution, oxide References
hydrates of niobium were released. The released oxide hydrates Ayanda, O.A., and Adekola, F.A., 2011, “A review of niobium-tantalum separa-
were calcinated, yielding a product with more than 99% of
tion in hydrometallurgy,” Journal of Mineral & Materials Characterization &
Engineering, Vol.10, No. 3, pp. 245-256.
niobium in purity. The purified Nb2O5 would then serve as Bludssus, W., and Eckert, J., 1993, “Process for the recovery and separation of
the feeding material for obtaining superconductor-grade, high- tantalum and niobium,” United States patent 5209910.
purity and high-homogeneity niobium (Hi Ho Nb) through the Cardwell, D.A., and Ginley D.S., 2003, Handbook of Superconducting Materi-
als, Volume I: Superconductivity, Materials and Processes, IOP publishing
carbothermic reduction route. This carbothermic reduction Ltd, 653 pp.
is aimed at removing interstitial impurities of the resulting Dennis, W.H., 1961, Metallurgy of the Non-Ferrous Metals, Sir Isaac Pitman & Sons.
Hi Ho Nb. In this carbothermic reduction method, niobium Gupta, C.K., Bose, D.K., and Krishnamurthy, N., 2003, “Preparation of high purity
niobium,” Journal of the Less Common Metals, Vol.139, Issue 1, pp. 189-202.
pentoxide powder would be smelted in an arc plasma reactor Hussaini, O.M.EI., and Rice, N.M., 2004, “Liquid-liquid extractions of niobium
using carbon as the reductant to obtain the required purity of and tantalum from aqueous sulfate/fluoride solutions by a tertiary amine,”
99.97 wt%, which will subsequently be electron beam zone Hydrometallurgy, Vol. 72, pp. 259-267.
refined (Nayak et al., 2010).

Htet, H.H., and Kay, T.L., 2008, “Study on extraction of niobium oxide from
columbite-tantalite concentrate,” World Academy of Science, Engineering
and Technology, Vol. 46, pp. 133-135.
Conclusion Izabela, N., and Maria, Z., 1999, “Niobium compounds: preparation, character-
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The extraction of Nb and Ta from the HF leach solution 99, No.12, pp. 3603-3624.
using MIBK in kerosene was low. It was also observed that Koethe, A., and Moench, J.I., 2000, “Preparation of ultra high purity niobium
the extraction of niobium was negligible when working with material transactions,” JIM, Vol. 41, No. 1, pp. 7-16.
solutions with a low concentration of HF acid. It was then

Krupin, G., 2000, “Treating niobium and/or tantalum containing raw materials,”
WO/2000/024943.
observed that the percent extraction of niobium from a binary Miller, G.L., 1957, Metallurgy of the Rarer Metals-6: Tantalum and Niobium,
solution comprised of either HF and H2SO4 or HF and HCl Isaac Pitman & Sons LTD.
was better in the presence of a higher concentration of MIBK
Nayak, B.B., Mishra, B.K., and Pradhan, S., 2010, “Smelting of Niobium pent-
oxide in a transferred arc argon plasma and characterization of the smelted
for a fixed low concentration of HF. The highest extraction product,” High Temperature Material Processes, Vol. 14, No. 3, pp. 233-244.
of Nb observed was 96.79%, and it came from the solution Soisson, D.J., McLafferty, J.J., and Pierret, J.A., 1961, “Staff-industry collabora-
comprised of 8.73 N HF and 4.87 N HCl with no detectable tive report,” Tantalum and Niobium Industrial and Engineering Chemistry,
Vol. 53, No.11, pp. 861-868.
trace of other metals. The niobium extraction prefers the chlo- Zhu, Z., and Cheng, C.Y., 2011, “Solvent extraction technology for the separation
ride route, as a lower concentration of HCl is involved in the and purification of niobium and tantalum,” Hydrometallurgy, Vol.107, pp. 1-12.

Leaching characteristics of copper
refractory ore in sulfate media
R. van der Merwe and H. Kasaini*
Graduate student and professor, respectively, Chemical and Metallurgical Engineering Department
Tshwane University of Technology, Pretoria, South Africa
*E-mail: henry-kasaini@yahoo.com
Abstract
Refractory copper ores (CROs) in central Africa contain copper minerals that are locked up in a micacious solid
matrix or associated with carbonate, sulfide and phosphate minerals. Several researchers have reported that the
recovery of copper from CRO material by an acid-leaching process is not economically feasible, due to the pres-
ence of excess gangue-acid-consuming minerals such as calcites, dolomite, asbolane and iron oxides. Since the
proportion of acid-insoluble copper (CuS) is about 28% of total copper and total free sulfur is extremely small,
sulfide flotation was considered unfavorable. Consequently, hundreds of millions of tons of CRO material have
been stockpiled specifically at the Nchanga Mine of Zambia. In terms of copper distribution in CRO material, a
significant portion of total copper exists as carbonates (39%) and oxides (17%), while 28% of the copper is acid-
insoluble (CuS). The rest of the copper is in the form of carbonates (16%) and (hydr) oxides (17%). This means
that only about 72% of total copper is recoverable through the non-oxidative acid-leaching process. In this study,
batch leach tests were performed on CRO solids (d95 = 95%) to establish the gangue acid consumption values
at different feed pH values and to evaluate the leaching characteristics of copper, manganese and iron within
the CRO material. Subsequently, continuous leach tests were performed on CRO solids (106 um, 80% passing)
using optimum leach conditions derived from batch tests. This paper aims to show that sustainable copper recov-
ery can be achieved by selecting leaching conditions whereby gangue acid consumption (GAC) values become
significantly small and the final concentration of manganese and iron in the leach solution are appreciably low.
Key words: Acid leaching; Copper refractory ore (CRO); Gangue acid consumption (GAC); Kinetics
Introduction the digestion of copper refractory ores, rendered the treatment

Leaching of refractory copper (Sikamo et al., of CRO material unfeasible (Sikamo et al., 2008b; Whyte et
2008a; Deng & Chen, 1991), lateritic nickel (McDon- al., 2001). For such material, GAC has been held accountable
ald and Whittington, 2008) and even gold (Climo et for the presence of acid-soluble refractory minerals (Si-Al2O3,
al., 2000; Deng and Lia, 2002; Dunn and Chamber- Si-Fe3O4, Si-MgO and Si-MnO). Downstream processing of
lain, 1997) from complex minerals has been found leach solutions containing a high Fe/Mn ratio adversely affects
to be exceedingly difficult. Still, this subject is of selectivity in the solvent extraction. This is due to co-extraction
considerable interest to process engineers, who are and poor quality cathodes in the electrowinning process, where
currently undertaking feasibility research and com- low current efficiency and high overvoltage occur.
mercial projects in the central African countries with Currently, there are over 150 Mt of CRO material, assaying
similar refractory copper ore deposits containing huge between 0.98 and 1.20% copper, which have been stockpiled
amounts of acid -consuming minerals. in the last three decades. Owing to its high copper content, the
During the past three decades, several research stockpile has generated a lot of interest for investors and the
groups have attempted to develop leaching techniques proprietors. Commercial exploitation of the ore by means of
for refractory ore to enhance copper production at froth flotation is not feasible (Sikamo et al., 2008b; Notebaart,
Konkola Copper Mines Ltd. (KCM). The mineral- 1988), predominantly due to the low assays of free sulfur
ogy of CRO is complex and consists of micacious (0.09%).
copper, copper sulfides, copper carbonates, copper For the purpose of this study, all acid-soluble copper miner-
oxides, feldspar, dolomite, carbonaceous shell and als (carbonates) were regarded as one group, while the copper
siliceous minerals (Whyte et al., 2001). Nearly 60% (hydr) oxides locked in the refractory matrix made the second
of the copper exists as carbonates, hydroxides and group. The third group refers to acid-insoluble copper (copper
sulfides in the micaceous host minerals (Table 1). A sulfides), which account for about 28% of total copper (Table
combination of slow leaching kinetics and high gangue 1). The sulfides cannot be acid-digested under nonoxidative
acid consumption (GAC), which is associated with conditions. According to mineralogical data shown (Table 1),
Paper number MMP-10-036. Original manuscript submitted July 2010. Revised manuscript accepted for publication October

Table 1 — Distribution of copper in various host mineral phases of the CRO feed material provided by KCM.
Minerals Assay in CRO (%) wt.% Copper Chemical formula
Malachite 0.56 15.68 Cu2CO3(OH)2
Pseudomalachite 0.52 15.33 Cu5(PO4)2(OH)4
Asbolane & iron oxides 1.21 2.29 (Ni,Co)2-xMn4+(O,OH)4·nH2O

Copper sulfides 1.54 28.13 CuFeS2 and Cu2FeS4
Quartz 42.46 0.00 Polymorphs of SiO2
XAl(1-2) Si(3-2)O8,
Feldspar 8.29 0.00
where X = Na, K, Ca
Calcite and dolomite 2.14 0.00 CaCO3 and CaMg(CO3)2
XY2–3Z4O10(OH, F)2, where X = K, Na, Ba, Ca, Cs, (H3O),
Mica 43.27 38.57 (NH4); Y = Al, Mg, Fe2+, Li, Cr, Mn, V, Zn; and Z = Si, Al,
Fe3+, Be, Ti
Total 100.0 100.0
copper hydro (oxides) account for about 31% of the total copper. ing parameters that will have a positive impact on energy costs
About 41% of copper oxides are locked in the refractory matrix (milling), cost of reagents (GAC) and metal recovery (leach
(mica, asbolane and iron oxides) and do not dissolve easily. efficiency). Conversely, optimal conditions only focused on
Pyrometallurgical treatment of CRO was ruled out, because maximizing copper recovery, with no regard to the cost of the
the possible grade of the copper produced would not exceed leaching operations.
5% and, thus, could not cover smelting costs. Furthermore, The co-extraction of manganese and iron with copper in
the limited quantity of free sulfur in CRO (<0.09%) would the leach circuit also presents severe problems in downstream
not serve as a source of additional fuel to mitigate the costs processing of the mixed pregnant solution, particularly in the
of smelting. In the past, the high cost of sulfuric acid was a tank houses, where manganese may be codeposited with copper
strong prohibitive factor against processing CRO, until KCM to produce inferior-quality cathodes. Therefore, a secondary
installed and commissioned a smelter and acid leach plant objective is to assess and compare the leachabilities of copper,
in 2009. The most economical range for copper extraction is manganese and iron from the ore, so as to improve leaching
about 10 kg/t, if the acid is imported. If acid is produced on site, kinetics parameters to limit manganese and iron dissolution
20 - 30 kg/t is the cost-effective range. Many common copper (preferential leaching of copper) through shorter contact
oxide and carbonate minerals are known to contain copper in periods, while maintaining a low GAC. An added benefit is
the divalent state and are completely soluble in sulfuric acid that high copper recovery within short contact times would
at atmospheric temperature (Bingöl and Canbazoğlu, 2004). invariably lower capital and operational costs. It is, thus, nec-
Atmospheric leaching (AL) is a strongly favored copper extrac- essary to determine the best leaching conditions, which limits
tion method for acid soluble copper (carbonates and oxides), the coextraction of unwanted metals with copper. Therefore,
compared to high-pressure acid leaching (HPAL) (Gupta, the concept of preferential leaching by means of a kinetics
2003). However, the leaching kinetics of copper in the AL study of manganese and copper was investigated at different
process is slower than in the HPAL process, especially if the residence times.
feed is lean in copper assay (< 0.6%), which necessitates the
practice of multistage leaching at atmospheric temperatures Materials
(McDonald and Whittington, 2008). Copper sulfides present Ore and reagents. Dry solid samples were collected from
could hinder conventional leaching through the formation of the Nchanga Open Pit Mine, Chingola, Zambia. The particle
insoluble layers on the surface of particles which in turn can size distribution showed that the percentage of CRO feed mate-
affect mass transfer and copper recovery. It is, however, to be rial passing a mesh of 8,000 μm was 80%. Table 1 shows the
expected that the carbonate minerals will leach relatively more distribution of copper in the various host mineral phases of the
quickly and contribute significantly to rapid initial kinetics feed material provided by KCM. The feed assays for the target
(Bingöl and Canbazoğlu, 2004). The cupriferous mica, on the minerals were as follows: 1.08% Cu, 0.17% Mn and 3.6% Fe.
other hand, will be more reluctant to break down, due to the Sulfuric acid (98-100% analytical grade) was purchased
interstratified nature of the ore (Notebaard, 1988). from Set Point Instruments (Johannesburg, South Africa) and
The purpose of this study was to determine the leaching used as received in all the leach tests. Distilled water was only
characteristics of CRO material from leaching experiments used for the calibration and cleaning of the Ross pH probes
conducted in a batch reactor operating under atmospheric that were supplied by LaboTec (Midrand, South Africa) and
conditions. Consequently, because leaching in the TLP takes for acid base titrations.
place via a continuous circuit, leaching characteristics uncov-
ered during batch leach tests were verified on a laboratory-size Experimental procedure. Batch tests. Feed samples for
continuous leach pilot plant. For the purpose of the pilot plant batch leach tests were prepared by crushing the ore using a
experiments, sustainable and optimal leaching conditions are laboratory jaw crusher and then rod milled until 95% of the
compared. Sustainable conditions are chosen based on leach- particles had passed a mesh size of 106 μm. Milling the ore

Figure 1 — Schematic diagram of leach pilot plant apparatus.
finer than 106 μm would restrict the economic feasibility of ner similar to the batch test work, except that samples were
a hydrometallurgical approach. The samples were dried in an milled down to 95% (for the optimal test) and 80% (for the
oven (80° C), in order to remove moisture, and then stored in sustainable test) passing a 106 µm mesh, similar to milling
a dessicator. practices already in place at KCM. A feed slurry (25% solids)
Three batch tests were performed for each variable. All was prepared in 20-L storage agitators for both tests.
batch tests were performed in a 4-L vessel equipped with a Figure 1 illustrates the circuit configuration featuring a
mechanical stirrer (1,000 rpm) (Test rig from SX Kinetics, cascade of leach vessels referred to as the atmospheric leach-
ON, Canada). Table 2 depicts the experimental conditions for ing pilot plant (ALPP). The feed was introduced into the
the batch leach tests. For each run, 2 L CRO feed was placed ALPP from a 20-L, well-agitated polypropylene storage tank
in the reactor. The mixture was agitated thoroughly and then via a peristaltic pump. The agitation speed in each vessel was
heated to the desired temperature via a vertically submerged consequently increased to 1,600 rpm for full suspension and
heating element. When the chosen temperature was reached, adequate overflow in the ALPP. Samples were drawn from the
the desired pH was obtained (and subsequently maintained) final discharge at regular intervals.
by dropwise addition of H2SO4 to the mixture. It took about
8 minutes to reach steady state leaching conditions for each Results and discussion
test run. As a result, the first sample was drawn at 7 minutes. Rate equations. Copper carbonates react readily with
It was not possible to take samples any sooner. The slurry sulfuric acid, and the reaction is complete within 6 minutes
temperature and pH were kept constant, while samples (20 mL) (Bingöl and Canbazoğlu, 2004). Therefore, it was accepted
were drawn from the mixture at chosen intervals. The slurry in this study that carbonate and oxide minerals in the CRO
samples were filtered and the resulting clear pregnant solution would readily leach before the first sample was collected at
was analyzed for metal ions by means of an inductively coupled 7 minutes, while the copper sulfide minerals, as well as the
plasma-optical emission spectrophotometer (ICP-OES). other copper-containing minerals in the feed, would continue
Continuous pilot leach tests. Two pilot plant leach tests leaching at a significantly slower rate (Fig. 4). On the basis
were performed: of initial mineralogical data (Table 1), carbonates account
for 31% of the total copper. This was confirmed by the result
1. At optimum conditions: 80° C at a pH of 1.4. obtained, which showed that approximately 31% of copper
2. At sustainable conditions: 60° C at a pH of 1.8. was leached out of the CRO material before the first sample
was collected at 7 minutes.
Samples for pilot plant test work were prepared in a man- To compensate for differential leaching rates between the
Table 2 — Experimental parameters for batch leach tests

Percentage solids (wt. %) Temperature (ºC) pH
10, 15, 20, 25, 30, 40, 45 25 2
25 25, 35, 45 2
25 25 1.4, 1.8, 2, 2.2, 2.4, 2.6, 2.8

Figure 2 — Copper leaching efficiency at different % feed Figure 3 — Effect of pH on leaching efficiency of Cu, Mn
solids compared at different time intervals measured when and Fe respectively after 8 h contact time. Feed solids =
leaching CRO feed was at 25º C, pH = 2 and mixing speed 25%, temperature = 25° C, stirring speed = 1,000 rpm (batch
= 1,000 rpm (batch leach test). leach test).
mineral phases, the concentration vs. time graph in the case ship to percent solids. Moreover, final manganese recoveries,
of batch leaching data was modified so that the rates during reported at the end of each test, were consistently demonstrated
the initial seven minutes, where rapid copper dissolution takes to be approximately 6% lower than copper. Iron, on the other
place, were isolated and then separately determined. The sec- hand, was not affected by the change in slurry density, as
tion where the dissolution clearly proceeds at a slower rate leaching efficiencies below 0.7% were consistently reported.
was considered first. Subsequently, the copper concentration Nevertheless, the final choice of the optimum density for
continuously increased with leaching time, after the first sample leaching depends not only on the process design variables,
was taken at seven minutes, and since the proceeding section such as the rate of extraction, throughput of solids and metal
was shown to be linear (R2 nearly 1), it was assumed that the production, but also on the economics of scale. In this study,
reactions were zero order. 25% of solid content was taken as an operating condition that
would enhance leaching and at the same time provide a Cu-
(1) rich pregnant solution for the solvent extraction as practiced at
Konkola Copper Mines, Nchanga tailings leach plant (TLP).
where [Cu] and [Cu]0 represent the final and initial copper Effect of feed pH. The effect of the slurry pH (1.4 to 2.8)
concentrations, respectively, k the rate constant and t the time on the extraction of copper, manganese and iron as gathered
in minutes. Therefore, only the gradients were of interest. The from the final leach solution after 8 h is summarized in Fig
approach for determining the kinetics associated with continu- 3. Under similar batch test conditions with 25% feed solids,
ous leaching of CRO ore was adopted by dividing the graph it was established that manganese was leached from the ore
into two sections; namely, the initial and proceeding reaction faster than copper or iron at pH < 1.6. The rates of extracting
rates (k1 and k2). manganese and copper into aqua solution were similar within
These constants could then also be used to quantify whether the pH range 1.6 - 2.8. Despite the fact that iron is more ubiq-
copper was preferentially leached to manganese on the basis uitous in the openpit CRO, its leaching efficiency was the
of their extraction rates. This was accomplished by applying lowest (< 5%) compared to copper (57%) and manganese (>
separation factors, which are essentially the ratio of the rate 85%) under atmospheric conditions and low pH.
constants of copper and manganese, and which produce the Effect of leaching temperature. The effect of temperature
dimensionless values (k(Cu)/k(Mn)). A value higher than 1 on the leaching behavior of CRO material was investigated
would suggest that copper was preferentially leached, while in the temperature range 25 - 45 ºC. The digestion of copper
a value less than 1 would indicate that the unwanted metal in CRO material is sensitive to slurry temperature (Fig. 4). In
leached out faster. this study, the slurry pH and density in the reactor were kept
constant at 2.0 and 25% solids, respectively. By increasing
Batch leach tests. Effect of percentage solids. Batch tests the slurry temperature from 25 to 45 ºC, the amount of copper
were conducted under ambient conditions at different contact extracted was doubled after 8 hours of contact time. Similar
periods (1, 4 and 8 hours) in a sulfuric acid media (pH 2) leaching characteristics were observed for manganese and, to a
with mechanical mixing (1,000 rpm). The percent solids were much lesser extent, iron. The integrated rate method, as previ-
varied between 15 and 45%. Figure 2 shows that the percent ously described by Eq. (1), was used to evaluate the order of
leach efficiency of Cu is inversely proportional to the percent reaction, whereby the initial and proceeding rates were used to
of feed solids, irrespective of particle residence time in the determine the rate constants (k1 and k2), and is depicted in Fig.
reactor. It is clear from Fig. 2 that copper extraction (> 50%) 4. Therefore, the Arrhenius relationship within a temperature
from CRO was enhanced by a low percentage of solids in the range of 25 to 100º C (ln[k]vs. 1/T) was employed to determine
feed (< 30%). This result was attributed to the fact that the the activation energy for Cu and Mn dissolution, as illustrated
mass transfer of ionic species from the particle surface into in Fig. 5. Table 3 provides a summary of k values for copper
the bulk solution and vice versa was negatively affected by and manganese at various temperatures. Overall, the initial rate
high numbers of particle-to-particle collisions. (k1) nearly doubled as the temperature increased from 25 to
Manganese extraction indicated a similar indirect relation- 35° C. A further increase in temperature by 10° C only yielded

Figure 4 — A linear regression of leach data to establish k2 Figure 5 — Determination of the activation energy (Ea)
values at different temperatures (batch leach test). for copper and manganese leaching using the Arrhenius
equation (batch leach test).
a slight increase in both initial and preceding copper leach- well as temperature, on GAC when leaching CRO were not
ing rates. The estimated minimum activation energy estimate as significant as the impact of pH modification.
required to digest copper from CRO material was found to be In this study, optimum leaching of copper under ambient
50 kJ/mol.K, while that for manganese was about 43 kJ/mol.K conditions was distinctively achieved at a low slurry pH (1.4)
(Fig. 5) under the current test conditions. This result indicates because acid leaching of CRO material at pH > 1.8 did not
that the activation energy estimate required to digest copper yield satisfactory results. However, GAC was evaluated over
at pH 2 from CRO was 10% higher than that for manganese a wide range of slurry pHs (1.4 – 2.8) under batch conditions
and that the order of the reactions was 1. (contact time = 8 h) (Fig. 6). The GAC values at pH 1.4,
The sensitivity of copper leaching rates to the change in 2.0 and 2.8 were approximately 32 kg/t, 8 kg/t, and 22 kg/t,
temperature was an indication that surface-controlled reac- respectively. The optimum target for acid consumption at a
tions were predominant during the leaching of the milled CRO tailings leach plant is between 10-15 kg/t. The best option to
material. The Ea for copper was found to be higher than that reduce GAC is thus to maintain the slurry pH between 1.6 and
of manganese, and this result confirms the higher separation 2.4. Any lower or higher pH would promote the dissolution
factors reported for these two metals (Table 3). Hence, the of other metals present in the ore, as can be appreciated from
potential/pH graphs (Pourbaix, 1974).
value indicated copper extraction was favored with
Continuous pilot leach tests. In this study, the overall
an increase in temperatures. objective was to effectively increase copper recoveries opti-
Although the leaching efficiency for copper at a higher mizing parameters that could assist to cut down operational
temperature (45 to 93° C) was not investigated in batch tests, costs associated with high GAC and co-extraction of iron and
due to excessive evaporation of the solution at atmospheric manganese. Two pilot plant leach studies were conducted using
pressure, the concept was tested under continuous pilot leach the knowledge gained from the preceding batch test findings.
tests (temp = 80° C). The two pilot tests are listed below:
Gangue acid consumption. Costs of reagents are directly 1. Using batch test findings only in order to achieve the
related to the GAC of solids. The amount of acid consumed highest possible Cu recovery, irrespective of GAC
per ton of solids (GAC) treated is a critical parameter in the (optimal leach).
control of operational costs associated with direct (lime uti- 2. Using batch tests results to select optimum parameters,
lization at neutralization units) and indirect (replacement or which can be used to reduce operational costs and
maintenance of corroded pipes and vessels) operations. From enhance sustainable copper recovery. This means
GAC data collected during the first batch leach tests (Table 2), achieving sustainable leach efficiency in terms of low
it can be deduced that the effect of the percent feed solids, as energy consumption (comminution, leaching tempera-
Table 3 — Rate constants, leach efficiencies and separation factors achieved for Cu, Mn and Fe under batch test
conditions.
Temp.
Copper (Cu) Manganese (Mn) Separation factors
(ºC)
L Eff. 480 L Eff. 480 k1(Cu)/ k2(Cu)/
k1 mol/Lt·s k2 mol/Lt·s k1 mol/Lt·s k2 mol/Lt·s
min % min % k1(Mn) k2(Mn)
25 8.94 ×10-6 0.26 ×10-6 35.6 1.4 ×10-6 0.06 ×10-6 35.3 7.6 5.3
35 14.2 ×10-6 0.29×10-6 52.8 2.1 ×10-6 0.06 ×10-6 36.9 7.9 5.8
45 14.8 ×10-6 0.42 ×10-6 56.7 2.2 ×10-6 0.09 ×10-6 41.4 8.0 5.7

Figure 6 — The difference between total acid and free acid
measured when leaching CRO feed at 25º C, % solids = 25%
Figure 7 — Leaching kinetics of copper, manganese and
and mixing speed = 1,000 rpm (batch leach test).
iron at optimal conditions (temperature = 80° C, pH = 1.4;
PSD = 95% passing 106 µm) (continuous leach test).
ture), low reagent costs (reduced GAC) and reduced subsequent copper leaching experiments; thus, intensive mill-
metal solution impurities. ing would not benefit leaching of CRO significantly. Taking
this into account, the sample was milled to 80% passing 106
Optimal leaching conditions derived from batch tests meant µm, as this was the minimum size already reachable at KCM.
that the pilot plant run was conducted at pH 1.4, temperature Approximately 75% of the copper was leached out within
80° C and ore PSD of 95% passing 106 µm. 80° C was the four hours at 25% feed solids and a mixing speed of 1,600
maximum allowable temperature of the ALPP at atmospheric rpm. The pregnant solution was tested for dissolved copper,
pressures. The % feed solids was kept at 25%, even though the manganese and iron ions, and it was found that the optimum
batch test had revealed a trend where the % feed solids below leaching conditions for copper also enhanced the leaching of
15% was most optimum (Fig. 2): it is poor practice to leach those metals. Manganese dissolution (Fig. 7) reached 99% leach
at such low densities, since the water required by the plant to efficiency under optimum conditions, a figure 24% higher than
leach a significant amount of CRO would be disproportionate. that of copper, while at sustainable conditions, the manganese
The determination of the sustainable condition, however, leach efficiency was 10% lower than the 34% reached when
focused on using the data obtained from preceding batch test leaching copper (graph not shown). The same was observed
work to maximize copper recovery, while still limiting acid when leaching iron, as it was insignificantly low, at below
consumption and operating at conditions that would be more 1% at sustainable conditions; it increased seven fold under
realistic and feasible when leaching CRO. Leaching at a pH less optimum conditions. Acid consumption was also observed to
than 1.4 would create challenges associated with corrosion and be much closer to the limit of 15 kg/t, at close to 19 kg/t at
additional acid requirements, while significantly increasing the sustainable conditions (Table 4), and comparable to that which
acid consumption of the process (Fig. 6). In addition, coleaching was predicted in batchwise conditions at a pH between 1.6
significant quantities of unwanted metals would occur (Fig. 3) and 1.8. The optimum conditions fell short and exhibited acid
and, therefore, a pH of 1.8 was considered most appropriate. consumption reaching above 50 kg/t, consequently rendering
Higher temperatures, although a must for leaching CRO, as leaching of CRO under those conditions very uneconomical.
pointed out by Notebaard (1988), would ultimately increase On the basis of kinetics, it was found that the optimal con-
energy requirements. The temperature for effective leaching ditions outperform the sustainable leaching conditions within
should be optimized to limit consumption of energy without the first 15 min. The difference in copper concentration at the
compromising the leach kinetics. A leaching temperature of point where the first sample was collected (Fig. 8), signified
60° C was ultimately settled on. that at optimal conditions, copper initially leaches nearly four
Energy costs can be optimized through assessment of leach times faster in comparison with the rate at sustainable condi-
efficiency versus particle size data. The optimum particle size tions. However, after the initial 15 min hike, based on k2 values
should be one that allows minerals to be well-liberated and does (gradients in Fig. 8), copper from slow-leaching minerals did
not allow an escalation in the cost of milling (size reduction). leach slightly faster under sustainable conditions.
Furthermore, Notebaard (1988) reported that additional mill- Separation factors reported for iron (Table 4) were even
ing or selective grinding of non-mica particles did not benefit lower than for manganese when leaching at optimal conditions.
Table 4 — Rate constants, leach efficiencies and separation factors achieved for Cu, Mn and Fe under continuous tests (pH 1.4,
80º C for optimal conditions and pH 1.8, 60º C for sustainable conditions).
Separation factor
k2 mol/L·s L Eff. Cu Total acid Free acid Acid consumed
Test k2(Cu)/ k2(Cu)/
240 min (%) (kg/t) (kg/t) (kg/t)
k2(Mn) k2(Fe)
Optimal 0.63 x10-7 75.5 114.4 61.5 52.9 2 1.2
Sustainable 0.68 x10-7 33.6 34.0 14.1 19.9 13 13

be approximately 34%, and the separation factors achieved
for Cu/Mn and Cu/Fe were in the order of 10, while the GAC
value was about 20 kg/t.
From optimal continuous leaching studies, it was established
that approximately 100% of total acid-soluble copper (which
is 72% of total copper) and 4% of acid-insoluble copper can
be recovered at moderate feed temperature. The rate of cop-
per extraction in the first 7 minutes was so fast that it fitted
a zero order reaction model due to dissolution of carbonates;
afterwards, however, the rate increased gradually due to slow
leaching kinetics of oxides locked in the micaceous matrix.
Generally, the rates of manganese and iron dissolution were
found to decrease with increase in feed temperature and, hence,
Figure 8 — Proceeding (k2) leaching rates under optimum the higher separation factors that were attained for Cu/Mn and
and sustainable leaching conditions. Leaching rates Cu/Fe at pH 1.8 and 60º C. Further studies are recommended
were determined from the first order rate equation fitted to elucidate the leaching kinetics of CRO material under oxi-
(continuous leach test). dative conditions.
Acknowledgments
This was an indication that, even though copper leaching from The financial support of Xstrata South Africa, which is
micaceous minerals remained as expected, manganese and intended to train postgraduate students in extractive metal-
iron leaching rates improved, as these were benefiting from lurgical engineering, is greatly appreciated, as is the Nuclear
the low pH being used during optimal leaching. Therefore, co- Energy Corporation of South Africa Ltd., for time allowed for
extraction of manganese and iron would be beyond acceptable completing this article.
levels if the low pH (optimal) option was pursued. Conversely,
sustainable leaching reported higher separation factors (13) References
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the higher pH (sustainable) option.

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industry, PhD thesis, Delft, Technische Universiteit.
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25% solids to 15% solids (at pH 2), copper recoveries would refractory ores,” Hydrometallurgy 2008, Proceedings of the Sixth International
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almost the same (around 10 kg/t). This result underscored the Sikamo, J., Kalumba, B., Mulenga, S.B., and Mwale, J., 2008b, “Recovery
need to optimize all leach parameters using a continuous pilot improvement strategies at Konkola Copper Mines PLC, Nchanga Tailings
Leach Plant,” Hydrometallurgy 2008, Proceedings of the Sixth International
leach test unit. In the continuous leaching study, atmospheric Symposium, C.A. Young, P.R. Taylor, C.G. Anderson and Y. Chai, Editors,
leach conditions were optimized by studying copper, manga- Society of Mining, Metallurgy and Exploration (SME), Inc., Littleton, CO.
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INDEX
MINERALS & METALLURGICAL PROCESSING

VOLUME 28, 2011
A relate to the Caron process: a review. M&MP Vol 28, No. 4

(November) p. 169
Aalto University School of Electrical Engineering, Espoo, Finland Ausburn, K., Baum, W.
Remes, A., Koivo, H. M&MP Vol 28, No. 2 (May) p. 62 HPGR comminution for optimization of copper leaching. M&MP
Adsorption Vol 28, No. 2 (May) p. 77
Surface thermodynamics and extended DLVO theory of Autogenous grinding
Leptospirillum ferrooxidans cells’ adhesion on sulfide Influence of pebble mill operating conditions on measurements
minerals. M&MP Vol 28, No. 3 (August) p. 151 with an in-mill sensor. M&MP Vol 28, No. 4
Advances in the cyanidation of silver (November) p. 193
Deschênes, G., Rajala, J., Pratt, A.R., Guo, H., Fulton, M.,
Mortazavi, S. M&MP Vol 28, No. 1 (February) p. 37 B
Aktas, S., Morcali, M.H.
Recovery of mercury from spent silver oxide button cells. M&MP Baum, W., Ausburn, K.
Vol 28, No. 4 (November) p. 198 HPGR comminution for optimization of copper leaching. M&MP
Alacer Gold Corporation, Turkey Vol 28, No. 2 (May) p. 77
Kaczmarek, A., Orser, S. M&MP Vol 28, No. 3 (August) p. 133 Bayer process
Alatalo, J., Pålsson, B.I., Tano, K. Kaolinite microflotation and electrokinetic properties. M&MP
Influence of pebble mill operating conditions on measurements Vol 28, No. 1 (February) p. 8
with an in-mill sensor. M&MP Vol 28, No. 4 Beneficiation
(November) p. 193 Beneficiation of a fine-sized cassiterite-bearing magnetite ore.
Al-Hussein Bin Talal University, Jordan Siqing Liu, Ye Cao, Xiong Tong, Peng Li M&MP Vol 28, No.
Al-Thyabat, S. M&MP Vol 28, No. 2 (May) p. 110 2 (May) p. 88
Al-Thyabat, S., Yoon, R.-H., Shin, D. Beneficiation of high-ash, Indian non-coking coal by dry jigging.
Floatability of fine phosphate in a batch column flotation cell. Gouri Charan, T., Chattopadhyay, U.S., Singh, K.M.P., Kabiraj,
M&MP Vol 28, No. 2 (May) p. 110 S.K., Haldar, D.D. M&MP Vol 28, No. 1 (February) p. 21
Aluminosilicate minerals Beneficiation of refractory rock phosphate by calcination and
Synthesis and performance of novel hydroxycarbamoyl flotation.
carboxylic acids for the flotation of diaspore and Khoshjavan, S., Rezai, B. M&MP Vol 28, No. 4 (November)
aluminosilicate minerals. M&MP Vol 28, No. 3 p. 187
(August) p. 126 Bioleaching
Aluminum/ aluminum ores Surface thermodynamics and extended DLVO theory of
Kaolinite microflotation and electrokinetic properties. M&MP Leptospirillum ferrooxidans cells’ adhesion on sulfide
Vol 28, No. 1 (February) p. 8 minerals. M&MP Vol 28, No. 3 (August) p. 151
Aluminum precipitation Botz. M.; Kaczmarek, A.; Orser, S.
Enhanced settling of fine silica by indirect A.C. Managing copper in leach solution at the Çöpler Gold Mine:
electrocoagulation. M&MP Vol 28, No. 3 (August) p. 117 laboratory testing and process design. M&MP Vol 28,
Amelunxen, P., Meadows, D. No. 3 (August) p. 133
Not another HPGR trade-off study! M&MP Vol 28, No. 1 Brahmbhatt, P., Pradhan, S., Nathsarma, K.C., Nayak, B.B.
(February) p. 1 Purification of niobium oxide by dissolution and solvent
Aminpro Chile, Santiago, Chile extraction. M&MP Vol 28, No. 4 (November) p. 204
Amelunxen , P. M&MP Vol 28, No. 1 (February) p. 1 Brazil
Amirkabir University of Technology, Iran Kaolinite microflotation and electrokinetic properties. M&MP
Khoshjavan, S., Rezai, B. M&MP Vol 28, No. 4 Vol 28, No. 1 (February) p. 8
(November) p. 187 Bubble size measurement
Anameric, B., Kawatra, S.K. New image-processing algorithm for measurement of bubble size
Shrinking-core model for pig iron nugget production. M&MP distribution from flotation froth images. M&MP Vol 28,
Vol 28, No. 1 (February) p. 24 No. 3 (August) p. 146
Araujo, A.C., Peres, A.E.C., Rodrigues, O.M.S.
Kaolinite microflotation and electrokinetic properties. M&MP C
Vol 28, No. 1 (February) p. 8
Arcelormittal, Cedex, France Calcination
Araujo, A.C. M&MP Vol 28, No. 1 (February) p. 8 Beneficiation of refractory rock phosphate by calcination and
Asselin, E. flotation. M&MP Vol 28, No. 4 (November) p. 187
Thermochemistry of the Fe, Ni and Co-NH3-H2O systems as they CANMET, Natural Resources Canada, Ottawa, ON

Deschênes, G., Pratt, A.R., Fulton, M., Mortazavi, S. M&MP Vol Column flotation
28, No. 1 (February) p. 37 Floatability of fine phosphate in a batch column flotation cell.
Caron leach process M&MP Vol 28, No. 2 (May) p. 110
Thermochemistry of the Fe, Ni and Co-NH3-H2O systems as they Comminution
relate to the Caron process: a review. M&MP Vol 28, No. 4 Coarse particle fracture with the ultrafast load cell. M&MP Vol
(November) p. 169 28, No. 4 (November) p. 176
Cassiterite-magnetite ore HPGR comminution for optimization of copper leaching. M&MP
Beneficiation of a fine-sized cassiterite-bearing magnetite ore. Vol 28, No. 2 (May) p. 77
M&MP Vol 28, No. 2 (May) p. 88 Influence of pebble mill operating conditions on measurements
Çelik, M.S., Ozdemir, O., Gupta, V., Miller, J.D., Çınar, M. with an in-mill sensor. M&MP Vol 28, No. 4
Production of trona concentrates using high-intensity dry (November) p. 193
magnetic separation followed by flotation. M&MP Vol 28, Computational fluid dynamics
No. 2 (May) p. 55 Study of hydrocyclone classification of coal fines by CFD
Center for Advanced Separation Technologies (CAST), Virginia modeling and laboratory tests. M&MP Vol 28, No. 2
Polytechnic Institute and State University, Blacksburg, VA (May) p. 102
Yoon, R.-H., Shin, D. M&MP Vol 28, No. 2 (May) p. 110 Constitutive relationship for electrokinetic dewatering of
Central Institute of Mining & Fuel Research, Dhanbad, Jharkhand, phosphatic clay slurries.
India McKinney, J.P., Orazem, M.E. M&MP Vol 28, No. 1 (February)
Gouri Charan, T., Chattopadhyay, U.S., Singh, K.M.P., Kabiraj, p. 49
S.K., Haldar, D.D. M&MP Vol 28, No. 1 (February) p. 21 Copper/ copper ores
Central South University, Changsha, China HPGR comminution for optimization of copper leaching.
Yu-ren Jiang, Rui Feng, Zhi-gang Yin, Yun-lai Yi M&MP Vol M&MP Vol 28, No. 2 (May) p. 77
28, No. 3 (August) p. 126 Leaching characteristics of copper refractory ore in sulfate
Chattopadhyay, U.S., Singh, K.M.P., Kabiraj, S.K., Haldar, D.D., media. M&MP Vol 28, No. 4 (November) p. 208
Gouri Charan, T. Managing copper in leach solution at the Çöpler Gold Mine:
Beneficiation of high-ash, Indian non-coking coal by dry jigging. laboratory testing and process design. M&MP Vol 28,
M&MP Vol 28, No. 1 (February) p. 21 No. 3 (August) p. 133
Chen G., Peng J.H., Chen J. Response surface methodology for optimization of copper
Optimizing conditions for wet grinding of synthetic rutile using leaching from a low-grade flotation middling.
response surface methodology. M&MP Vol 28, No. 1 M&MP Vol 28, No. 3 (August) p. 139
(February) p. 44 Copper refractory ore (CRO)
Chen J., Chen G., Peng J.H. Leaching characteristics of copper refractory ore in sulfate
Optimizing conditions for wet grinding of synthetic rutile using media. M&MP Vol 28, No. 4 (November) p. 208
response surface methodology. M&MP Vol 28, No. 1 Cost analysis
(February) p. 44 Not another HPGR trade-off study! M&MP Vol 28, No. 1
China (February) p. 1
Response surface methodology for optimization of copper Cyanidation
leaching from a low-grade flotation middling. M&MP Advances in the cyanidation of silver. M&MP Vol 28, No. 1
Vol 28, No. 3 (August) p. 139 (February) p. 37
CIMAV, Complejo Industrial Chihuahua, Chihuahua Cyanide leaching
González-Anaya, J.A. M&MP Vol 28, No. 2 (May) p. 94 Managing copper in leach solution at the Çöpler Gold Mine:
CINVESTAV, Unidad Saltillo, Ramos Arizpe, Mexico laboratory testing and process design. M&MP Vol 28,
González-Anaya, J.A., Nava-Alonso, F. M&MP Vol 28, No. 2 No. 3 (August) p. 133
(May) p. 94
Çınar, M., Çelik, M.S., Ozdemir, O., Gupta, V., Miller, J.D.
Production of trona concentrates using high-intensity dry D
magnetic separation followed by flotation. M&MP Vol 28,
No. 2 (May) p. 55 Dan Liu, Mengyang Lv, Jian Liu, Shuming Wen, Lijun Liu
Clay-settling areas Response surface methodology for optimization of copper
Constitutive relationship for electrokinetic dewatering of leaching from a low-grade flotation middling.
phosphatic clay slurries. M&MP Vol 28, No. 1 M&MP Vol 28, No. 3 (August) p. 139
(February) p. 49 Derin, B., Yücel, O., Reddy, R.G.
Electrokinetic dewatering of phosphatic clay settling areas: Sulfide capacity modeling of FeOx-MO-SiO2 (MO=CaO, MnOx,
numerical simulation and economic assessment. M&MP MgO) melts. M&MP Vol 28, No. 1 (February) p. 33
Vol 28, No. 2 (May) p. 71 Deschênes, G., Rajala, J., Pratt, A.R., Guo, H., Fulton, M.,
Coal Mortazavi, S.
Beneficiation of high-ash, Indian non-coking coal by dry jigging. Advances in the cyanidation of silver. M&MP Vol 28, No. 1
M&MP Vol 28, No. 1 (February) p. 21 (February) p. 37
Coal processing Dewatering
Study of hydrocyclone classification of coal fines by CFD Constitutive relationship for electrokinetic dewatering
modeling and laboratory tests. M&MP Vol 28, No. 2 of phosphatic clay slurries. M&MP Vol 28, No. 1
(May) p. 102 (February) p. 49
Coarse particle fracture with the ultrafast load cell. Dhawan, N., Rajamani, R.K., Tuzcu, E.T.
Tuzcu, E.T., Dhawan, N., Rajamani, R.K. M&MP Vol 28, No. 4 Coarse particle fracture with the ultrafast load cell. M&MP Vol
(November) p. 176 28, No. 4 (November) p. 176
Coello Velázquez, A.L., Menéndez Aguado, J.M., Hechavarría Diaspore
Pérez, J.R., Sánchez, A.B., Rodríguez, B.A. Synthesis and performance of novel hydroxycarbamoyl
Toward determining the behavior of fragmentation functions carboxylic acids for the flotation of diaspore and
during the impact crushing of minerals. M&MP Vol 28, aluminosilicate minerals. M&MP Vol 28, No. 3
No. 2 (May) p. 82 (August) p. 126

Dumlupinar University, Kutahya, Turkey Leaching characteristics of copper refractory ore in sulfate
Çınar, M. M&MP Vol 28, No. 2 (May) p. 55 media. M&MP Vol 28, No. 4 (November) p. 208
Gent, M., Menéndez, M., Torno, S., Toraño, J.
E Study of hydrocyclone classification of coal fines by CFD
modeling and laboratory tests. M&MP Vol 28, No. 2
Elbow Creek Engineering, Inc., Billings, MT (May) p. 102
Botz, M. M&MP Vol 28, No. 3 (August) p. 133 Gold/ gold ores
Electrocoagulation Gold recovery optimization of a refractory concentrate by ultrafine
Enhanced settling of fine silica by indirect A.C. grinding – a laboratory study.
electrocoagulation. M&MP Vol 28, No. 3 (August) p. 117 González-Anaya, J.A., Nava-Alonso, F., Pecina-Treviño, E.T.
Electrokinetic dewatering of phosphatic clay settling areas: M&MP Vol 28, No. 2 (May) p. 94
numerical simulation and economic assessment. González-Anaya, J.A., Nava-Alonso, F., Pecina-Treviño, E.T.
McKinney, J.P, Orazem, M.E. M&MP Vol 28, No. 2 (May) p. 71 Gold recovery optimization of a refractory concentrate by
Electrokinetic separation ultrafine grinding – a laboratory study. M&MP Vol 28, No.
Constitutive relationship for electrokinetic dewatering 2 (May) p. 94
of phosphatic clay slurries. M&MP Vol 28, No. 1 Gouri Charan, T., Chattopadhyay, U.S., Singh, K.M.P., Kabiraj,
(February) p. 49 S.K., Haldar, D.D.
Electrokinetic dewatering of phosphatic clay settling areas: Beneficiation of high-ash, Indian non-coking coal by dry jigging.
numerical simulation and economic assessment. M&MP Vol 28, No. 1 (February) p. 21
M&MP Vol 28, No. 2 (May) p. 71 Grinding mill
Empresa Geominera Oriente, Cuba Coarse particle fracture with the ultrafast load cell. M&MP Vol
Hechavarría Pérez, J.R. M&MP Vol 28, No. 2 (May) p. 82 28, No. 4 (November) p. 176
Enhanced settling of fine silica by indirect A.C. electrocoagulation. Guo, H., Fulton, M., Mortazavi, S., Deschênes, G., Rajala, J.,
Ifill, R.O.; Etsell, T.H. M&MP Vol 28, No. 3 (August) p. 117 Pratt, A.R.
ESI-UAdeC, Nueva Rosita, Mexico Advances in the cyanidation of silver. M&MP Vol 28, No. 1
Pecina-Treviño, E.T. M&MP Vol 28, No. 2 (May) p. 94 (February) p. 37
Etsell, T.H.; Ifill, R.O. Gupta, V., Miller, J.D., Çınar, M., Çelik, M.S., Ozdemir, O.
Enhanced settling of fine silica by indirect A.C. Production of trona concentrates using high-intensity dry
electrocoagulation. M&MP Vol 28, No. 3 (August) p. 117 magnetic separation followed by flotation. M&MP Vol 28,
No. 2 (May) p. 55
F
H
Finland
Simulation and pilot experiments on pyrite concentrate Haldar, D.D., Gouri Charan, T., Chattopadhyay, U.S., Singh,
separation in a Floatex density separator. M&MP Vol 28, K.M.P., Kabiraj, S.K.
No. 2 (May) p. 62 Beneficiation of high-ash, Indian non-coking coal by dry jigging.
Floatability of fine phosphate in a batch column flotation cell. M&MP Vol 28, No. 1 (February) p. 21
Al-Thyabat, S., Yoon, R.-H., Shin, D. M&MP Vol 28, No. 2 Hanumantha Rao, K.; Vilinska, A.
(May) p. 110 Surface thermodynamics and extended DLVO theory of
Flotation Leptospirillum ferrooxidans cells’ adhesion on sulfide
Beneficiation of high-ash, Indian non-coking coal by dry jigging. minerals. M&MP Vol 28, No. 3 (August) p. 151
M&MP Vol 28, No. 1 (February) p. 21 Health and safety
Beneficiation of refractory rock phosphate by calcination and Real-time monitoring of arsenic, cadmium, copper and lead
flotation. M&MP Vol 28, No. 4 (November) p. 187 concentrations in workplace smelter particulates using a
New image-processing algorithm for measurement of bubble size TSI 8520 DustTrak. M&MP Vol 28, No. 1 (February) p. 13
distribution from flotation froth images. M&MP Vol 28, Hechavarría Pérez, J.R., Sánchez, A.B., Rodríguez, B.A., Coello
No. 3 (August) p. 146 Velázquez, A.L., Menéndez Aguado, J.M.
Production of trona concentrates using high-intensity dry Toward determining the behavior of fragmentation functions
magnetic separation followed by flotation. M&MP Vol 28, during the impact crushing of minerals. M&MP Vol 28,
No. 2 (May) p. 55 No. 2 (May) p. 82
Synthesis and performance of novel hydroxycarbamoyl HPGR comminution for optimization of copper leaching.
carboxylic acids for the flotation of diaspore and Baum, W., Ausburn, K. M&MP Vol 28, No. 2 (May) p. 77
aluminosilicate minerals. M&MP Vol 28, No. 3 HPGR technology
(August) p. 126 HPGR comminution for optimization of copper leaching. M&MP
FLSmidth Minerals, Bethlehem, PA Vol 28, No. 2 (May) p. 77
Meadows, D. M&MP Vol 28, No. 1 (February) p. 1 Not another HPGR trade-off study! M&MP Vol 28, No. 1
Fragmentation (February) p. 1
Toward determining the behavior of fragmentation functions Hydrochloric acid
during the impact crushing of minerals. M&MP Vol 28, Purification of niobium oxide by dissolution and solvent
No. 2 (May) p. 82 extraction. M&MP Vol 28, No. 4 (November) p. 204
Freeport-McMoRan Mining Company, Safford, AZ Hydrocyclone classification
Baum, W., Ausburn, K. M&MP Vol 28, No. 2 (May) p. 77 Study of hydrocyclone classification of coal fines by CFD
Fulton, M., Mortazavi, S., Deschênes, G., Rajala, J., Pratt, A.R., modeling and laboratory tests. M&MP Vol 28, No. 2
Guo, H. (May) p. 102
Advances in the cyanidation of silver. M&MP Vol 28, No. 1 Hydrometallurgy
(February) p. 37 Recovery of mercury from spent silver oxide button cells. M&MP
Vol 28, No. 4 (November) p. 198
G Thermochemistry of the Fe, Ni and Co-NH3-H2O systems as they
relate to the Caron process: a review. M&MP Vol 28, No.
Gangue acid consumption (GAC) 4 (November) p. 169

I Kaolinite microflotation and electrokinetic properties.
Rodrigues, O.M.S., Araujo, A.C., Peres, A.E.C. M&MP Vol 28,
Ifill, R.O.; Etsell, T.H. No. 1 (February) p. 8
Enhanced settling of fine silica by indirect A.C. Kasaini, H., van der Merwe, R.
electrocoagulation. M&MP Vol 28, No. 3 Leaching characteristics of copper refractory ore in sulfate
(August) p. 117 media. M&MP Vol 28, No. 4 (November) p. 208
Image analysis Kawatra, S.K., Anameric, B.
New image-processing algorithm for measurement of bubble size Shrinking-core model for pig iron nugget production. M&MP
distribution from flotation froth images. M&MP Vol 28, Vol 28, No. 1 (February) p. 24
No. 3 (August) p. 146 Khoshjavan, S., Rezai, B.
Impact crushing Beneficiation of refractory rock phosphate by calcination and
Toward determining the behavior of fragmentation functions flotation. M&MP Vol 28, No. 4 (November) p. 187
during the impact crushing of minerals. M&MP Vol 28, Kinetics
No. 2 (May) p. 82 Leaching characteristics of copper refractory ore in sulfate
India media. M&MP Vol 28, No. 4 (November) p. 208
Beneficiation of high-ash, Indian non-coking coal by dry jigging. Kinross Gold Corporation, Toronto, ON
M&MP Vol 28, No. 1 (February) p. 21 Rajala, J. M&MP Vol 28, No. 1 (February) p. 37
Purification of niobium oxide by dissolution and solvent Koivo, H., Remes, A., Tuikka, A.
extraction. M&MP Vol 28, No. 4 (November) p. 204 Simulation and pilot experiments on pyrite concentrate
Industrial minerals separation in a Floatex density separator. M&MP Vol 28,
Enhanced settling of fine silica by indirect A.C. No. 2 (May) p. 62
electrocoagulation. M&MP Vol 28, No. 3 (August) p. 117 Kunming University of Science and Technology, Kunming, China
Influence of pebble mill operating conditions on measurements Chen G., Peng J.H., Chen J. M&MP Vol 28, No. 1
with an in-mill sensor. (February) p. 44
Alatalo, J., Pålsson, B.I., Tano, K. M&MP Vol 28, No. 4 Jian Liu, Shuming Wen, Dan Liu, Mengyang Lv
(November) p. 193 M&MP Vol 28, No. 3 (August) p. 139
Inmet Mining Corporation, Pyhäsalmi Mine Oy, Pyhäsalmi, Siqing Liu, Ye Cao, Xiong Tong, Peng Li
Finland M&MP Vol 28, No. 2 (May) p. 88
Tuikka, A. M&MP Vol 28, No. 2 (May) p. 62
Institute for Plasma Research, Bhat, Gandhinagar, Gujarat, India L
Brahmbhatt, P., Pradhan, S. M&MP Vol 28, No. 4 (November)
p. 204 Larson, R.R., Pahler, L.F., Thiese, M.S., McDonald, J.P.
Institute of Minerals & Materials Technology, Bhubaneswar, Real-time monitoring of arsenic, cadmium, copper and lead
Orissa, India concentrations in workplace smelter particulates using a
Nathsarma, K.C., Nayak, B.B. M&MP Vol 28, No. 4 TSI 8520 DustTrak. M&MP Vol 28, No. 1 (February) p. 13
(November) p. 204 Leaching
Instituto Superior Minero Metalúrgico de Moa, Cuba Advances in the cyanidation of silver. M&MP Vol 28, No. 1
Coello Velázquez, A.L. M&MP Vol 28, No. 2 (May) p. 82 (February) p. 37
Iron/ iron ores HPGR comminution for optimization of copper leaching.
Shrinking-core model for pig iron nugget production. M&MP M&MP Vol 28, No. 2 (May) p. 77
Vol 28, No. 1 (February) p. 24 Response surface methodology for optimization of copper
Sulfide capacity modeling of FeOx-MO-SiO2 (MO=CaO, MnOx, leaching from a low-grade flotation middling.
MgO) melts. M&MP Vol 28, No. 1 (February) p. 33 M&MP Vol 28, No. 3 (August) p. 139
Istanbul Technical University, Istanbul, Turkey Thermochemistry of the Fe, Ni and Co-NH3-H2O systems as
Aktas, S., Morcali, M.H. M&MP Vol 28, No. 4 they relate to the Caron process: a review.
(November) p. 198 M&MP Vol 28, No. 4 (November) p. 169
Çelik, M.S. M&MP Vol 28, No. 2 (May) p. 55 Leaching characteristics of copper refractory ore in sulfate media.
Derin, B., Yücel, O. M&MP Vol 28, No. 1 (February) p. 33 van der Merwe, R., Kasaini, H. M&MP Vol 28, No. 4
(November) p. 208
J Lead nitrate
Advances in the cyanidation of silver. M&MP Vol 28, No. 1
Jian Liu, Shuming Wen, Dan Liu, Mengyang Lv, Lijun Liu (February) p. 37
Response surface methodology for optimization of copper Lijun Liu, Mengyang Lv, Jian Liu, Shuming Wen, Dan Liu
leaching from a low-grade flotation middling. M&MP Response surface methodology for optimization of copper
Vol 28, No. 3 (August) p. 139 leaching from a low-grade flotation middling.
M&MP Vol 28, No. 3 (August) p. 139
K LKAB, Malmberget, Sweden
Tano, K. M&MP Vol 28, No. 4 (November) p. 193
Kabiraj, S.K., Haldar, D.D., Gouri Charan, T., Chattopadhyay, Luleå University of Technology, Luleå, Sweden
U.S., Singh, K.M.P. Alatalo, J., Pålsson, B.I. M&MP Vol 28, No. 4
Beneficiation of high-ash, Indian non-coking coal by dry jigging. (November) p. 193
M&MP Vol 28, No. 1 (February) p. 21 Vilinska, A.; Hanumantha Rao, K.M&MP Vol 28, No. 3
Kaczmarek, A.; Orser, S.; Botz, M. (August) p. 151
Managing copper in leach solution at the Çöpler Gold Mine:
laboratory testing and process design. M&MP Vol 28, M
No. 3 (August) p. 133
Kaolin Magnetic separation
Kaolinite microflotation and electrokinetic properties. M&MP Beneficiation of a fine-sized cassiterite-bearing magnetite ore.
Vol 28, No. 1 (February) p. 8 M&MP Vol 28, No. 2 (May) p. 88

Production of trona concentrates using high-intensity dry M&MP Vol 28, No. 2 (May) p. 62
magnetic separation followed by flotation. M&MP Vol 28, Study of hydrocyclone classification of coal fines by CFD
No. 2 (May) p. 55 modeling and laboratory tests.
Managing copper in leach solution at the Çöpler Gold Mine: M&MP Vol 28, No. 2 (May) p. 102
laboratory testing and process design. The solitary grain liberation model: a description of a mineral
Botz. M.; Kaczmarek, A.; Orser, S. M&MP Vol 28, No. 3 liberation model for low-grade ores.
(August) p. 133 M&MP Vol 28, No. 3 (August) p. 159
Massinaei, M.; Mehrshad, N. Toward determining the behavior of fragmentation functions
New image-processing algorithm for measurement of bubble size during the impact crushing of minerals.
distribution from flotation froth images. M&MP Vol 28, M&MP Vol 28, No. 2 (May) p. 82
No. 3 (August) p. 146 Morcali, M.H., Aktas, S.
McDonald, J.P., Larson, R.R., Pahler, L.F., Thiese, M.S. Recovery of mercury from spent silver oxide button cells.
Real-time monitoring of arsenic, cadmium, copper and lead M&MP Vol 28, No. 4 (November) p. 198
concentrations in workplace smelter particulates using a Mortazavi, S., Deschênes, G., Rajala, J., Pratt, A.R., Guo, H.,
TSI 8520 DustTrak. M&MP Vol 28, No. 1 (February) p. 13 Fulton, M.
McKinney, J.P., Orazem, M.E. Advances in the cyanidation of silver. M&MP Vol 28, No. 1
Constitutive relationship for electrokinetic dewatering of (February) p. 37
phosphatic clay slurries. M&MP Vol 28, No. 1
(February) p. 49
Electrokinetic dewatering of phosphatic clay settling areas: N
numerical simulation and economic assessment.
Nathsarma, K.C., Nayak, B.B., Brahmbhatt, P., Pradhan, S.
M&MP Vol 28, No. 2 (May) p. 71
Purification of niobium oxide by dissolution and solvent
Meadows, D., Amelunxen, P.
extraction. M&MP Vol 28, No. 4 (November) p. 204
Not another HPGR trade-off study! M&MP Vol 28, No. 1
Nava-Alonso, F., Pecina-Treviño, E.T., González-Anaya, J.A.
(February) p. 1
Gold recovery optimization of a refractory concentrate by
Mehrshad, N.; Massinaei, M
ultrafine grinding – a laboratory study. M&MP Vol 28, No.
New image-processing algorithm for measurement of bubble
2 (May) p. 94
size distribution from flotation froth images.
Nayak, B.B., Brahmbhatt, P., Pradhan, S., Nathsarma, K.C.
Menéndez Aguado, J.M., Hechavarría Pérez, J.R., Sánchez, A.B.,
Rodríguez, B.A., Coello Velázquez, A.L.
New image-processing algorithm for measurement of bubble size
Toward determining the behavior of fragmentation functions
distribution from flotation froth images.
during the impact crushing of minerals. M&MP Vol 28,
Mehrshad, N.; Massinaei, M. M&MP Vol 28, No. 3
No. 2 (May) p. 82
(August) p. 146
Menéndez, M., Torno, S., Toraño, J., Gent, M.
Niobium oxide
Study of hydrocyclone classification of coal fines by CFD
modeling and laboratory tests. M&MP Vol 28, No. 2
(May) p. 102
Not another HPGR trade-off study!
Mengyang Lv, Jian Liu, Shuming Wen, Dan Liu, Lijun Liu
Amelunxen, P., Meadows, D. M&MP Vol 28, No. 1
Response surface methodology for optimization of copper
(February) p. 1
leaching from a low-grade flotation middling.
Mercury O
Recovery of mercury from spent silver oxide button cells.
M&MP Vol 28, No. 4 (November) p. 198 Optimization
Michigan Technological University, Houghton, MI Influence of pebble mill operating conditions on measurements
Anameric, B., Kawatra, S.K. M&MP Vol 28, No. 1 with an in-mill sensor. M&MP Vol 28, No. 4
(February) p. 24 (November) p. 193
Miller, J.D., Çınar, M., Çelik, M.S., Ozdemir, O., Gupta, V. Optimizing conditions for wet grinding of synthetic rutile using
Production of trona concentrates using high-intensity dry response surface methodology.
magnetic separation followed by flotation. M&MP Vol 28, Chen G., Peng J.H., Chen J. M&MP Vol 28, No. 1
No. 2 (May) p. 55 (February) p. 44
Mine design Orazem, M.E., McKinney, J.P.
Not another HPGR trade-off study! M&MP Vol 28, No. 1 Constitutive relationship for electrokinetic dewatering of
(February) p. 1 phosphatic clay slurries. M&MP Vol 28, No. 1
Mineral liberation (February) p. 49
Solitary grain liberation model: a description of a mineral Electrokinetic dewatering of phosphatic clay settling areas:
liberation model for low-grade ores. M&MP Vol 28, No. 3 numerical simulation and economic assessment.
(August) p. 159 M&MP Vol 28, No. 2 (May) p. 71
Ministry of Education, Kunming, China Orser, S.; Botz, M.; Kaczmarek, A.
Lijun Liu M&MP Vol 28, No. 3 (August) p. 139 Managing copper in leach solution at the Çöpler Gold Mine:
Modeling and simulation laboratory testing and process design. M&MP Vol 28,
Electrokinetic dewatering of phosphatic clay settling areas: No. 3 (August) p. 133
numerical simulation and economic assessment. Ozdemir, O., Gupta, V., Miller, J.D.
M&MP Vol 28, No. 2 (May) p. 71 University of Utah, Salt Lake City, UT M&MP Vol 28, No. 2
Managing copper in leach solution at the Çöpler Gold Mine: (May) p. 55
laboratory testing and process design. Ozdemir, O., Gupta, V., Miller, J.D., Çınar, M., Çelik, M.S.
M&MP Vol 28, No. 3 (August) p. 133 Production of trona concentrates using high-intensity dry
Simulation and pilot experiments on pyrite concentrate magnetic separation followed by flotation. M&MP Vol 28,
separation in a Floatex density separator. No. 2 (May) p. 55

P Real-time monitoring of arsenic, cadmium, copper and lead
concentrations in workplace smelter particulates using a
Pahler, L.F., Thiese, M.S., McDonald, J.P., Larson, R.R. TSI 8520 DustTrak.
Real-time monitoring of arsenic, cadmium, copper and lead McDonald, J.P., Larson, R.R., Pahler, L.F., Thiese, M.S. M&MP
concentrations in workplace smelter particulates using a Vol 28, No. 1 (February) p. 13
TSI 8520 DustTrak. M&MP Vol 28, No. 1 (February) p. 13 Recovery of mercury from spent silver oxide button cells.
Pålsson, B.I., Tano, K., Alatalo, J. Aktas, S., Morcali, M.H. M&MP Vol 28, No. 4
Influence of pebble mill operating conditions on measurements (November) p. 198
with an in-mill sensor. M&MP Vol 28, No. 4 Reddy, R.G., Derin, B., Yücel, O.
(November) p. 193 Sulfide capacity modeling of FeOx-MO-SiO2 (MO=CaO, MnOx,
Particle fracture MgO) melts. M&MP Vol 28, No. 1 (February) p. 33
Coarse particle fracture with the ultrafast load cell. M&MP Vol Reduction
28, No. 4 (November) p. 176 Shrinking-core model for pig iron nugget production. M&MP Vol
Particulate control 28, No. 1 (February) p. 24
Real-time monitoring of arsenic, cadmium, copper and lead Refractory ores
concentrations in workplace smelter particulates using a Gold recovery optimization of a refractory concentrate by
TSI 8520 DustTrak. M&MP Vol 28, No. 1 (February) p. 13 ultrafine grinding – a laboratory study. M&MP Vol 28,
Pebble mill No. 2 (May) p. 94
Influence of pebble mill operating conditions on measurements Remes, A., Tuikka, A., Koivo, H.
with an in-mill sensor. M&MP Vol 28, No. 4 Simulation and pilot experiments on pyrite concentrate
(November) p. 193 separation in a Floatex density separator. M&MP Vol 28,
Pecina-Treviño, E.T., González-Anaya, J.A., Nava-Alonso, F. No. 2 (May) p. 62
Gold recovery optimization of a refractory concentrate by Response surface methodology
ultrafine grinding – a laboratory study. M&MP Vol 28, No. Optimizing conditions for wet grinding of synthetic rutile using
2 (May) p. 94 response surface methodology. M&MP Vol 28, No. 1
Peng J.H., Chen J., Chen G. (February) p. 44
Optimizing conditions for wet grinding of synthetic rutile using Response surface methodology for optimization of copper
response surface methodology. M&MP Vol 28, No. 1 leaching from a low-grade flotation middling.
(February) p. 44 M&MP Vol 28, No. 3 (August) p. 139
Peng Li, Siqing Liu, Ye Cao, Xiong Tong Response surface methodology for optimization of copper leaching
Beneficiation of a fine-sized cassiterite-bearing magnetite ore. from a low-grade flotation middling.
M&MP Vol 28, No. 2 (May) p. 88 Jian Liu, Shuming Wen, Dan Liu, Mengyang Lv, Lijun Liu
Peres, A.E.C., Rodrigues, O.M.S., Araujo, A.C. M&MP Vol 28, No. 3 (August) p. 139
Kaolinite microflotation and electrokinetic properties. M&MP Rezai, B., Khoshjavan, S.
Vol 28, No. 1 (February) p. 8 Beneficiation of refractory rock phosphate by calcination and
Phosphate mining flotation. M&MP Vol 28, No. 4 (November) p. 187
Constitutive relationship for electrokinetic dewatering of Rodrigues, O.M.S., Araujo, A.C., Peres, A.E.C.
phosphatic clay slurries. M&MP Vol 28, No. 1 Kaolinite microflotation and electrokinetic properties. M&MP
(February) p. 49 Vol 28, No. 1 (February) p. 8
Phosphate/ phosphate ore Rodríguez, B.A., Coello Velázquez, A.L., Menéndez Aguado, J.M.,
Beneficiation of refractory rock phosphate by calcination and Hechavarría Pérez, J.R., Sánchez, A.B
flotation. M&MP Vol 28, No. 4 (November) p. 187 Toward determining the behavior of fragmentation functions
Floatability of fine phosphate in a batch column flotation cell. during the impact crushing of minerals. M&MP Vol 28,
M&MP Vol 28, No. 2 (May) p. 110 No. 2 (May) p. 82
Pradhan, S., Nathsarma, K.C., Nayak, B.B., Brahmbhatt, P. Rui Feng, Zhi-gang Yin, Yun-lai Yi, Yu-ren Jiang
Purification of niobium oxide by dissolution and solvent Synthesis and performance of novel hydroxycarbamoyl
extraction. M&MP Vol 28, No. 4 (November) p. 204 carboxylic acids for the flotation of diaspore and
Pratt, A.R., Guo, H., Fulton, M., Mortazavi, S., Deschênes, G., aluminosilicate minerals. M&MP Vol 28, No. 3
Rajala, J. (August) p. 126
Advances in the cyanidation of silver. M&MP Vol 28, No. 1
(February) p. 37
Production of trona concentrates using high-intensity dry magnetic S
separation followed by flotation.
Ozdemir, O., Gupta, V., Miller, J.D., Çınar, M., Çelik, M.S. Sánchez, A.B., Rodríguez, B.A., Coello Velázquez, A.L.,
M&MP Vol 28, No. 2 (May) p. 55 Menéndez Aguado, J.M., Hechavarría Pérez, J.R.
Purification of niobium oxide by dissolution and solvent extraction. Toward determining the behavior of fragmentation functions
Nathsarma, K.C., Nayak, B.B., Brahmbhatt, P., Pradhan, S. during the impact crushing of minerals. M&MP Vol 28,
M&MP Vol 28, No. 4 (November) p. 204 No. 2 (May) p. 82
School of Mines, Oviedo University, Asturias, Spain
R Torno, S., Toraño, J., Gent, M., Menéndez, M. M&MP Vol 28,
No. 2 (May) p. 102
Rajala, J., Pratt, A.R., Guo, H., Fulton, M., Mortazavi, S., Separation
Deschênes, G. Simulation and pilot experiments on pyrite concentrate
Advances in the cyanidation of silver. M&MP Vol 28, separation in a Floatex density separator. M&MP Vol 28,
No. 1 (February) p. 37 No. 2 (May) p. 62
Rajamani, R.K., Tuzcu, E.T., Dhawan, N. Shin, D., Al-Thyabat, S., Yoon, R.-H.
Coarse particle fracture with the ultrafast load cell. Floatability of fine phosphate in a batch column flotation cell.
M&MP Vol 28, No. 4 (November) p. 176 M&MP Vol 28, No. 2 (May) p. 110

Shrinking-core model Ternary slags
Shrinking-core model for pig iron nugget production. Sulfide capacity modeling of FeOx-MO-SiO2 (MO=CaO, MnOx,
Anameric, B., Kawatra, S.K. M&MP Vol 28, No. 1 MgO) melts. M&MP Vol 28, No. 1 (February) p. 33
(February) p. 24 Thermochemistry of the Fe, Ni and Co-NH3-H2O systems as they
Shuming Wen, Dan Liu, Mengyang Lv, Jian Liu, Lijun Liu relate to the Caron process: a review.
Response surface methodology for optimization of copper Asselin, E. M&MP Vol 28, No. 4 (November) p. 169
leaching from a low-grade flotation middling. Thiese, M.S., McDonald, J.P., Larson, R.R., Pahler, L.F.
M&MP Vol 28, No. 3 (August) p. 139 Real-time monitoring of arsenic, cadmium, copper and lead
Silica concentrations in workplace smelter particulates using a
Enhanced settling of fine silica by indirect A.C. TSI 8520 DustTrak. M&MP Vol 28, No. 1 (February) p. 13
electrocoagulation. M&MP Vol 28, No. 3 (August) p. 117 Tin/ tin ores
Silver/ silver ores Beneficiation of a fine-sized cassiterite-bearing magnetite ore.
Advances in the cyanidation of silver. M&MP Vol 28, No. 1 M&MP Vol 28, No. 2 (May) p. 88
(February) p. 37 Toraño, J., Gent, M., Menéndez, M., Torno, S.
Simulation and pilot experiments on pyrite concentrate separation Study of hydrocyclone classification of coal fines by CFD
in a Floatex density separator. modeling and laboratory tests. M&MP Vol 28, No. 2
Remes, A., Tuikka, A., Koivo, H. M&MP Vol 28, No. 2 (May) p. 102
(May) p. 62 Torno, S., Toraño, J., Gent, M., Menéndez, M.
Singh, K.M.P., Kabiraj, S.K., Haldar, D.D., Gouri Charan, T., Study of hydrocyclone classification of coal fines by CFD
Chattopadhyay, U.S. modeling and laboratory tests. M&MP Vol 28, No. 2
Beneficiation of high-ash, Indian non-coking coal by dry jigging. (May) p. 102
M&MP Vol 28, No. 1 (February) p. 21 Toward determining the behavior of fragmentation functions
Siqing Liu, Ye Cao, Xiong Tong, Peng Li during the impact crushing of minerals.
Beneficiation of a fine-sized cassiterite-bearing magnetite ore. Coello Velázquez, A.L., Menéndez Aguado, J.M., Hechavarría
M&MP Vol 28, No. 2 (May) p. 88 Pérez, J.R., Sánchez, A.B., Rodríguez, B.A. M&MP Vol
Slime 28, No. 2 (May) p. 82
Floatability of fine phosphate in a batch column flotation cell. Trona
M&MP Vol 28, No. 2 (May) p. 110 Production of trona concentrates using high-intensity dry
Solitary grain liberation model: a description of a mineral magnetic separation followed by flotation. M&MP Vol 28,
liberation model for low-grade ores. No. 2 (May) p. 55
Wiegel, R.L.M&MP Vol 28, No. 3 (August) p. 159 Tshwane University of Technology, Pretoria, South Africa
Solvent extraction van der Merwe, R., Kasaini, H. M&MP Vol 28, No. 4
Purification of niobium oxide by dissolution and solvent (November) p. 208
extraction. M&MP Vol 28, No. 4 (November) p. 204 Tuikka, A., Koivo, H., Remes, A.
Study of hydrocyclone classification of coal fines by CFD modeling Simulation and pilot experiments on pyrite concentrate
and laboratory tests. separation in a Floatex density separator. M&MP Vol 28,
Torno, S., Toraño, J., Gent, M., Menéndez, M. M&MP Vol 28, No. 2 (May) p. 62
No. 2 (May) p. 102 Turkey
Sulfide capacity Managing copper in leach solution at the Çöpler Gold Mine:
Sulfide capacity modeling of FeOx-MO-SiO2 (MO=CaO, MnOx, laboratory testing and process design. M&MP Vol 28,
MgO) melts. No. 3 (August) p. 133
Derin, B., Yücel, O., Reddy, R.G. M&MP Vol 28, No. 1 Recovery of mercury from spent silver oxide button cells. M&MP
(February) p. 33 Vol 28, No. 4 (November) p. 198
Sulfide minerals Tuzcu, E.T., Dhawan, N., Rajamani, R.K.
Surface thermodynamics and extended DLVO theory of Coarse particle fracture with the ultrafast load cell. M&MP Vol
Leptospirillum ferrooxidans cells’ adhesion on sulfide 28, No. 4 (November) p. 176
minerals. M&MP Vol 28, No. 3 (August) p. 151
Surface thermodynamics and extended DLVO theory of U
Leptospirillum ferrooxidans cells’ adhesion on sulfide
minerals. Ultrafast load cell
Vilinska, A.; Hanumantha Rao, K.M&MP Vol 28, No. 3 Coarse particle fracture with the ultrafast load cell. M&MP Vol
(August) p. 151 28, No. 4 (November) p. 176
Synthesis and performance of novel hydroxycarbamoyl carboxylic Ultrafine grinding
acids for the flotation of diaspore and aluminosilicate Gold recovery optimization of a refractory concentrate by
minerals. ultrafine grinding – a laboratory study. M&MP Vol 28,
Yu-ren Jiang, Rui Feng, Zhi-gang Yin, Yun-lai Yi No. 2 (May) p. 94
M&MP Vol 28, No. 3 (August) p. 126 Universidade Federal de Minas Gerais, Belo Horizonte, Brazil
Synthetic rutile Rodrigues, O.M.S., Peres, A.E.C. M&MP Vol 28, No. 1
Optimizing conditions for wet grinding of synthetic rutile using (February) p. 8
response surface methodology. M&MP Vol 28, No. 1 Universidad Oviedo, Spain
(February) p. 44 Menéndez Aguado, J.M., Sánchez, A.B., Rodríguez, B.A.
M&MP Vol 28, No. 2 (May) p. 82
T University of Alabama, Tuscaloosa, AL
Reddy, R.G. M&MP Vol 28, No. 1 (February) p. 33
Tano, K., Alatalo, J., Pålsson, B.I. University of Alberta, Edmonton, AB
Influence of pebble mill operating conditions on measurements Ifill, R.O.; Etsell, T.H.M&MP Vol 28, No. 3 (August) p. 117
with an in-mill sensor. M&MP Vol 28, No. 4 (November) University of Birjand, Birjand, Iran
p. 193 Mehrshad, N.; Massinaei, M.M&MP Vol 28, No. 3 p. 146

University of British Columbia, Vancouver, BC X
Asselin, E. M&MP Vol 28, No. 4 (November) p. 169
University of Florida, Gainesville, FL Xiong Tong, Peng Li, Siqing Liu, Ye Cao
McKinney, J.P., Orazem, M.E. M&MP Vol 28, No. 1 Beneficiation of a fine-sized cassiterite-bearing magnetite ore.
(February) p. 49 M&MP Vol 28, No. 2 (May) p. 88
McKinney, J.P., Orazem, M.E. M&MP Vol 28, No. 2 (May) p. 71
University of Utah, Salt Lake City, UT Y
McDonald, J.P., Larson, R.R., Pahler, L.F., Thiese, M.S. M&MP Ye Cao, Xiong Tong, Peng Li, Siqing Liu
Vol 28, No. 1 (February) p. 13 Beneficiation of a fine-sized cassiterite-bearing magnetite ore.
Ozdemir, O., Gupta, V., Miller, J.D. M&MP Vol 28, No. 2 (May) M&MP Vol 28, No. 2 (May) p. 88
p. 55 Yoon, R.-H., Shin, D., Al-Thyabat, S.
Tuzcu, E.T., Dhawan, N., Rajamani, R.K. M&MP Vol 28, No. 4 Floatability of fine phosphate in a batch column flotation cell.
(November) p. 176 M&MP Vol 28, No. 2 (May) p. 110
Yücel, O., Reddy, R.G., Derin, B.
V Sulfide capacity modeling of FeOx-MO-SiO2 (MO=CaO, MnOx,
MgO) melts. M&MP Vol 28, No. 1 (February) p. 33
van der Merwe, R., Kasaini, H. Yun-lai Yi, Yu-ren Jiang, Rui Feng, Zhi-gang Yin
Leaching characteristics of copper refractory ore in sulfate Synthesis and performance of novel hydroxycarbamoyl
media. M&MP Vol 28, No. 4 (November) p. 208 carboxylic acids for the flotation of diaspore and
Vilinska, A.; Hanumantha Rao, K. aluminosilicate minerals.
Surface thermodynamics and extended DLVO theory of M&MP Vol 28, No. 3 (August) p. 126
Leptospirillum ferrooxidans cells’ adhesion on sulfide Yu-ren Jiang, Rui Feng, Zhi-gang Yin, Yun-lai Yi
minerals. M&MP Vol 28, No. 3 (August) p. 151 Synthesis and performance of novel hydroxycarbamoyl
carboxylic acids for the flotation of diaspore and
aluminosilicate minerals.
W M&MP Vol 28, No. 3 (August) p. 126
Wardrop Engineering Inc., Toronto, ON Z
Guo, H. M&MP Vol 28, No. 1 (February) p. 37
Wet grinding Zhi-gang Yin, Yun-lai Yi, Yu-ren Jiang, Rui Feng
Optimizing conditions for wet grinding of synthetic rutile using Synthesis and performance of novel hydroxycarbamoyl
response surface methodology. M&MP Vol 28, No. 1 carboxylic acids for the flotation of diaspore and
(February) p. 44 aluminosilicate minerals.
Wiegel, R.L. M&MP Vol 28, No. 3 (August) p. 126
Solitary grain liberation model: a description of a mineral Zinc
liberation model for low-grade ores. M&MP Vol 28, No. 3 Recovery of mercury from spent silver oxide button cells. M&MP
(August) p. 159 Vol 28, No. 4 (November) p. 198

Recent Advances in
Mineral Processing
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an international peer-reviewed journal

Volume 28, Number 4

M&MP is excited to announce a new collaboration with the MPD division of

Call for Papers:

New subscriber special: subscribe to M&MP’s print and online option

Minerals & Metallurgical Processing now has an online-

Coarse particle fracture with the ultrafast load cell 176

TECHNICAL NOTE: Beneficiation of refractory rock phosphate

Influence of pebble mill operating conditions 193

Recovery of mercury from spent silver oxide button cells 198

Purification of niobium oxide by dissolution and solvent extraction 204

Leaching characteristics of copper refractory ore in sulfate media 208

Volume 28, No. 4

MINERALS & METALLURGICAL PROCESSING DIVISION Purpose:

Jon J. Kellar SME Officers:

Key words: Hydrometallurgy; Thermodynamics; Laterites

Introduction and cobalt are then separated by sulfide precipitation, solvent

MINERALS & METALLURGICAL PROCESSING 169 Vol. 28 No. 4 • November 2011

November 2011 • Vol. 28 No. 4 170 MINERALS & METALLURGICAL PROCESSING

Thermodynamics of the Caron process leach

MINERALS & METALLURGICAL PROCESSING 171 Vol. 28 No. 4 • November 2011

Figure 5 — Quasi-equilibrium Pourbaix diagram for the

November 2011 • Vol. 28 No. 4 172 MINERALS & METALLURGICAL PROCESSING

MINERALS & METALLURGICAL PROCESSING 173 Vol. 28 No. 4 • November 2011

November 2011 • Vol. 28 No. 4 174 MINERALS & METALLURGICAL PROCESSING

CP (T) = A + B x 10-3T + C x 105T -2 + D x 10-6T 2

MINERALS & METALLURGICAL PROCESSING 175 Vol. 28 No. 4 • November 2011

Key words: Comminution; Grinding energy; Particle fracture; Tumbling mill

Introduction model SAG/AG mills, where larger-size particles, up to sev-

November 2011 • Vol. 28 No. 4 176 MINERALS & METALLURGICAL PROCESSING

= cumulative probability of fracture at an energy level = probability of failure of size y particle

MINERALS & METALLURGICAL PROCESSING 177 Vol. 28 No. 4 • November 2011

Statistical approach for the particle fracture. The inter-

In the UFLC device shown in Fig. 1, a steel ball falls on a (5)

November 2011 • Vol. 28 No. 4 178 MINERALS & METALLURGICAL PROCESSING

MINERALS & METALLURGICAL PROCESSING 179 Vol. 28 No. 4 • November 2011

Table 1 — Experimental conditions for limestone fracture experiments.

November 2011 • Vol. 28 No. 4 180 MINERALS & METALLURGICAL PROCESSING

MINERALS & METALLURGICAL PROCESSING 181 Vol. 28 No. 4 • November 2011

November 2011 • Vol. 28 No. 4 182 MINERALS & METALLURGICAL PROCESSING

MINERALS & METALLURGICAL PROCESSING 183 Vol. 28 No. 4 • November 2011

November 2011 • Vol. 28 No. 4 184 MINERALS & METALLURGICAL PROCESSING

MINERALS & METALLURGICAL PROCESSING 185 Vol. 28 No. 4 • November 2011

breakage of the particle is finite. The model is only a function

November 2011 • Vol. 28 No. 4 186 MINERALS & METALLURGICAL PROCESSING

Beneficiation of refractory rock

Key words: Refractory rock phosphate; Flotation; Calcination; Characterization; Flowsheet

Introduction tion), chemical dissolution of carbonates with organic acids,

MINERALS & METALLURGICAL PROCESSING 187 Vol. 28 No. 4 • November 2011

November 2011 • Vol. 28 No. 4 188 MINERALS & METALLURGICAL PROCESSING

MINERALS & METALLURGICAL PROCESSING 189 Vol. 28 No. 4 • November 2011

November 2011 • Vol. 28 No. 4 190 MINERALS & METALLURGICAL PROCESSING

MINERALS & METALLURGICAL PROCESSING 191 Vol. 28 No. 4 • November 2011

According to the proposed flowsheet, two concentrates with

November 2011 • Vol. 28 No. 4 192 MINERALS & METALLURGICAL PROCESSING

Key words: Comminution; Autogenous grinding; Pebble mill; Process optimization

Introduction of knowledge of what happens inside a mill. Since the environ-

MINERALS & METALLURGICAL PROCESSING 193 Vol. 28 No. 4 • November 2011

Table 1 – Data from experiments.

F1 65 27.1 25 85.7 0.89 9,781 35.6 190.8 22.9 7.0 1.04

November 2011 • Vol. 28 No. 4 194 MINERALS & METALLURGICAL PROCESSING

MINERALS & METALLURGICAL PROCESSING 195 Vol. 28 No. 4 • November 2011

November 2011 • Vol. 28 No. 4 196 MINERALS & METALLURGICAL PROCESSING