Minerals Engineering 52 (2013) 62–73

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Minerals Engineering
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Gangue–reagent interactions during acid leaching of uranium

B.J. Youlton a,b,⇑, J.A. Kinnaird b
a
SGS South Africa, 58 Melville St., Booysens, Johannesburg, South Africa
b
Department of Geology, University of the Witwatersrand, Johannesburg, South Africa

a r t i c l e i n f o a b s t r a c t

Article history: During the acid leaching of uranium, gangue–reagent interactions have both negative and positive con-
Available online 29 April 2013 sequences. Gangue dissolution increases reagent costs, and in some cases can prevent the economic acid
leaching of an ore, but can also increase uranium mineral exposure and improve recoveries. Due to rapid
Keywords: dissolution kinetics, the acid consumption characteristics of the various carbonate species are readily pre-
Ore mineralogy dicted, however the same is not true of silicate gangue. Due to factors including slower leach rates, incon-
Leaching gruent dissolution, parabolic kinetics, and surface area, pH and temperature dependence, the gangue acid
Reaction kinetics
consumption characteristics of silicate minerals are significantly more complex. A detailed mineralogical
Hydrometallurgy
investigation and acid leach tests were conducted on sandstone-hosted uranium ore samples. The disso-
lution characteristics of the more common gangue phases were determined. The study demonstrated that
gangue–reagent interactions can be predicted from mineralogical data, thus reducing technical risk dur-
ing processing.
Ó 2013 Elsevier Ltd. All rights reserved.

1. Introduction (Lottering et al., 2008). As the gangue dissolves, so the proportion

of the mineral of interest that is exposed to the leach liquor in-
Uranium ores are processed by either an acid or an alkali leach creases, resulting in improved recoveries.
(Abhilash et al., 2009). Acid leaches are typically preferred to alkali The gangue–reagent interactions that occur during the acid
methods, as they frequently offer more rapid dissolution kinetics leaching of U, were investigated in order to understand their effect
and are able to leach more efficiently at coarser grinds (Lunt on reagent consumption and U dissolution. Samples were obtained
et al., 2007). Alkali leaches are used where the reactivity of the gan- from two Karoo-aged U occurrences. One sample was obtained
gue prevents acid leaching (Merritt, 1971; Lunt et al., 2007). How- from a U prospect within the main Karoo basin (sample MKB1)
ever, under certain conditions it may not be possible to process an and three others (samples RAO, OAO and MSO) were obtained from
ore by alkali leach, for example if gypsum is present (IAEA, 1980). the Kayelekera mine in Malawi.
Therefore the nature of the gangue mineralogy can prevent the
economic leaching of U. It would therefore be desirable to better 1.1. Gangue mineral dissolution
understand the factors that influence gangue acid consumption
and develop a method of quantitatively predicting gangue acid Due to the rapid dissolution of carbonates, these minerals are
consumption from mineralogical data. typically considered to consume their stoichiometrically equiva-
The major advantage of being able to model gangue acid con- lent amount of acid during U leaching (IAEA, 1980). The dissolution
sumptions from mineralogy (rather than simply performing a leach of silicate minerals is more complex than that of carbonates. Due to
test), is that a model can be used to generate data for a range of the complex nature of silicate dissolution, it has been suggested
possible conditions, while separate leach tests would be necessary that the dissolution of these phases cannot be predicted (IAEA,
for each condition of interest. The availability of mineralogical data 1980). However, large amounts of research have been performed
also makes it possible to identify other potential mineralogical on the acid dissolution characteristics of silicate minerals since
problems, such as clays. 1980. Much of this research (for example Lowson et al., 2005)
In addition to contributing to acid consumptions, the dissolu- was aimed at understanding the behaviour of gangue minerals
tion of gangue minerals can aid in the recovery of valuable metals during acid mine drainage, however due to similarities in pH and
acid type, the information is readily transferred to U leaching.
⇑ Corresponding author at: SGS South Africa, 58 Melville St., Booysens, Johan- Several factors influence the dissolution characteristics of min-
nesburg, South Africa. erals. The following factors influence the rate of mineral dissolu-
E-mail address: Brandon.JayYoulton@sgs.com (B.J. Youlton). tion: mineral composition, time, temperature, pH, surface area

0892-6875/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.mineng.2013.03.030
 B.J. Youlton, J.A. Kinnaird / Minerals Engineering 52 (2013) 62–73 63

and incongruent dissolution (Ross, 1969; Brantley and Conrad, 2. Methodology

2008; Lüttge and Arvidson, 2008; Brantley, 2008).
Since minerals dissolve at a finite rate, the extent of dissolu- In order to understand the response of the gangue minerals dur-
tion is a function of time. However, the rate of dissolution can ing leaching, the head samples underwent detailed mineralogical
also vary with time. Generally two stages are seen during disso- characterisation prior to acid leaching.
lution, (1) an initial more rapid rate which gradually slows to (2)
steady-state dissolution (Brandt et al., 2003 and Brantley, 2008).
2.1. Gangue mineral characterisation
The U leach tests typically include the initial phase of rapid dis-
solution but, (depending on the constituent minerals and condi-
The samples were milled to the desired grind using a laboratory
tions of the leach, may not necessarily reach steady-state
scale rod mill. All of the samples were milled to a P80 of 212 lm.
dissolution. This decay from an initially rapid rate to steady state
Due to the large amount of MKB1 material, a second aliquot of this
conditions is typically referred to as parabolic kinetics (Brantley,
sample was milled to 75 lm and treated as a separate sample for
2008). However, in practice, the change in rate as a function of
the textural analyses and leach tests.
time is more readily modelled by an exponential decay function,
Both the head and leach residue samples were analysed by XRD
than a parabola.
and QEMScan bulk mineralogical analysis (BMA), to identify and
The rate of mineral dissolution is considered to vary with tem- quantify the gangue minerals present, and determine the mean
perature according to the Arrhenius equation (Brantley and Con-
grain size and degree of exposure of each gangue phase.
rad, 2008). The XRD analyses were performed using the guidelines of
k ¼ A expðEa RTÞ ð1Þ McCusker et al. (1999). The powder samples were micronised
and then analysed using a Panalytical X’pert Pro diffractometer
where k is the rate constant at a given temperature, A is the pre-
and Co Ka radiation. The resulting data was processed using High-
exponential factor, Ea is the activation energy, R is the ideal gas con-
Score Plus software and the PanICSD database. Rietveld refinement
stant and T is the absolute temperature (Brantley and Conrad,
was used to determine the quantities of each gangue phase.
2008). Using the Arrhenius equation it is possible to adapt kinetic
QEMScan BMA analyses, conducted according the methods de-
data collected at one temperature to a more desirable temperature
scribed by Gottlieb et al. (2000) and Coetzee et al. (2011), were also
(Brandt et al., 2003).
used in the gangue mineral quantification. The BMA analyses were
Dissolution rates are typically normalised to the surface
performed on transverse cut polished sections, using a QEMScan
area of the mineral (Lüttge and Arvidson, 2008). Many workers
based on a Carl Zeiss Evo 50 scanning electron microscope with
(including Lowson et al. (2005); Brandt et al. (2003); Knauss
four SiLi EDX detectors. The BMA and XRD data were validated
and Wolery (1989)) favour the BET (Brunauer et al., 1938)
against each other and against major element XRF data. In addition
method of surface area determination. This method allows for
to XRF analyses, the samples were also analysed by titration to
surface area determination by measuring the adsorption of an
determine their Fe2+ content.
inert gas onto the surface of the sample. However, this is
The BMA data was also used to determine the textural charac-
not as readily adapted to complex samples consisting of sev-
teristics of the gangue. BMA analyses are more rapid and cost effec-
eral minerals in various concentrations, such as is typically
tive than other QEMScan techniques and therefore more readily
the case with U ores.
applied to variability studies. For this reason the BMA was chosen
In addition to temperature and mineral surface area depen-
over particle map analysis (PMA). However, BMA analyses are
dence, the release rate of an element from a dissolving mineral is
more prone to stereological bias than two dimensional scans, such
influence by incongruent dissolution. Incongruent dissolution de-
as PMA (Sutherland et al., 1988), and it was necessary to stereolog-
scribes the case where elemental release rates are not proportional
ically correct the grain size data.
to the stoichiometry of the mineral (Brantley, 2008).

1.2. Reagents used in uranium leaching 2.2. Uranium mineral characterisation

Sulphuric acid is typically used to achieve the low pH required The U mineral characterisation was performed by QEMScan
for acid U leaching (Ho and Quan, 2007). This acid has two acidic trace mineral search (TMS) using the same instruments used for
protons. The dissociation of the first proton has a sufficiently high the BMA analyses. The mineral identification was validated by
equilibrium constant that it can be considered to proceed to com- manual scanning electron microscopy with associated energy dis-
pletion, while the second dissociation has an equilibrium constant persive X-ray analysis.
of 1.2  102 (Brown et al., 2003).
During acid leaching hexavalent U minerals tend to dissolve 2.3. Leach tests
readily, while tetravalent U minerals require oxidation to the hexa-
valent state prior to dissolution (Lunt et al., 2007). In the process- The batch acid leach tests were conducted using the guidelines
ing of the Witwatersrand ores of South Africa, MnO2 in the form of given by the IAEA (1980 and 1990). Approximately 2 kg split ali-
pyrolusite, is the preferred oxidant (Lottering et al., 2008). At quots of each sample were used. Due to the large amount of
Olympic Dam sodium chlorate is used (Miki and Nicol, 2009). MKB1 material, it was possible to leach this sample at a number
Other oxidants include SO2/O2 (Ho and Quan, 2007), hydrogen per- of different pH and Eh conditions and at two different grinds (P80
oxide and oxygen (Venter and Boylett, 2009). In this study only 212 and 75 lm). The limited amount of material in the Kayelekera
MnO2 was considered. It has been found that these oxidising samples limited these leach tests to one test per sample
agents do not act on the U minerals directly, but instead serve to (P80 212 lm).
oxidise iron to the Fe3+ state, which in turn oxidises the U accord- The leaches were performed at a solid to liquid ratio of 1:1, in
ing to Eq. (2) (Lottering et al., 2008). This equation shows that the 5 L plastic beakers. Agitation was achieved by overhead stirrers.
dissolution of MnO2 consumes two moles of sulphuric acid for each Temperature was controlled to between 35 and 40 °C. The pH
mole of MnO2 dissolved. was controlled using concentrated sulphuric acid and the redox
potential was controlled using MnO2, both Associated Chemical
2Fe2þ þ MnO2 þ 4Hþ ! 2Fe3þ þ Mn2þ þ 2H2 O ð2Þ
Enterprises, Platinum Line, analytical reagent grade.
64 B.J. Youlton, J.A. Kinnaird / Minerals Engineering 52 (2013) 62–73

A one hour preconditioning period was used. During this time of 10%, and Eq. (4) gives 20% dissolution, then the concentration of
the pH was controlled, but no attempt was made to maintain the the mineral in the leach residue would be 8% (ignoring the effect of
redox potential (IAEA, 1990). After one hour of preconditioning the minerals dissolution on the total mass of the solids).
the MnO2 was added and this was considered to mark the begin-
ning of the leach. 3.2. Surface area
Slurry samples were taken after 1, 3, 8 and 24 h. These were fil-
tered and the solutions submitted for U and Th by ICP-MS and Na, Due to the complex mineralogy of the samples, geometric sur-
K, Al, Mg, Fe and Si by ICP-OES. The solids were rinsed with dilute face areas were chosen over the BET method. For most minerals
sulphuric acid (pH 1.5). All of the residues were analysed by XRD a spherical model was applied, where the stereologically corrected
and the 3 and 24 h samples were submitted for U and Th analysis mean grain size (from the QEMScan data) was used to estimate the
by pressed pellet XRF and major elements by XRF borate fusion. surface area of the sample, according to Eq. (5) (modified from Tes-
ter et al., 1994).

3. Modelling of gangue dissolution and reagent consumption

Ageo ¼ 6=Uq ð5Þ
where Ageo is the specific geometric surface area (in m2/g), U is the
Based on the results of the XRD analyses and the ICP-OES anal- particle diameter (in lm) and q is the density of the mineral (in g/
yses of the pregnant leach solution (PLS), the rates of decay of the cm3).
various mineral phases were determined. In general the ICP-OES The spherical assumption was considered too simple to reliably
results were favoured over the XRD data due to their greater pre- model the phyllosilicates. Based on the work of Hodson (2006), the
cision. However, in the cases of minerals which did not contain un- phyllosilicates were modelled as cuboids with equal lengths and
ique elements, it was necessary to use the XRD data. Fortunately breadths. Hudson used a 2 lm thickness for smaller grains and
these minerals were characterised by rapid dissolution and for this 4 lm for larger grains. In this study the thickness was taken as a
reason the error in the XRD data was small when compared to the linear function of the grain size, rather than using the Hudson’s
decrease in concentration in each time interval. two classes. Hudson ignored the basal surface areas of the grains,
In general the rates were modelled on the leach tests of the while the entire phyllosilicate surface area was considered in the
MKB1 sample and then tested against the Kayelekera samples. present study. This was done to maintain the similarity with BET
However, this was not possible for smectite and illite, which do surface areas.
not occur in the MKB1 sample. The surface areas calculated using either Tester et al. (1994) or
Hodson (2006) method tend to under estimate the true surface
area of the mineral as they do not consider the effect of fractures
3.1. Dissolution rates
and other surface roughness. This surface roughness can be calcu-
lated using Eq. (6) (Helgeson et al., 1984).
An exponential decay function was used to account for the de-
crease in the rate of dissolution of the various mineral phases with Rs ¼ Aads =Ageo ð6Þ
time (Eq. (3)). Eq. (3) was adapted from an equation used in radio-
where Rs is the surface roughness, Aads is the BET surface area and
active decay. This equation is given by Serway and Faughn (2003).
Ageo is the geometric surface area.
Using published dissolution studies that included both grain
R ¼ R0 eðktÞ þ z ð3Þ
size and BET surface area data, the surface roughness of each min-
eral was calculated. It was found, based on the published data, that
where R is the rate at a given time (t), R0 is the initial rate, k is the
the roughness of many minerals is a function of the grain size.
decay constant and z is an approximation of the steady state disso-
Therefore based on the data from several studies, linear relation-
lution rate. In practice the initial rate was usually so much more ra-
ships between grain size and surface roughness were established.
pid than the steady state rate that, for most minerals, it was a
Such detailed surface area data was not available for zeolite and
reasonable approximation to set the steady state rate as zero. How-
so a simple geometric surface area was used for laumontite.
ever, for leaches with a duration significantly longer than 24 h, it
Because the QEMScan does not readily distinguish grain bound-
may be necessary to use a more precise treatment of the steady
aries of very fine adjacent grains of the same mineral, it was not
state condition.
possible to determine surface areas for illite and smectite. A sur-
Where this approximation was not valid, it was necessary to de-
face area of 42 m2/g was used for illite (Bibi et al., 2011). No at-
velop a function to predict the steady state rate. The relationship
tempt was made to estimate the surface area of smectite
between pH and the steady state dissolution of many minerals is
because, the relationship between total surface areas and reactive
approximately parabolic (at least at the low pH used in acid U
surface areas are too complex to allow for surface area normalisa-
leaching), for example Lowson et al. (2005) with chlorite, and Koh-
tion of smectite (Metz et al., 2005).
ler et al. (2003) for illite. Based on these results, parabolic functions
were developed for the determination of z. In the same way, para-
3.3. Mineral dissolution and acid consumption
bolic functions were developed to calculate R0 from the pH of the
leach test. The value of the decay constant was determined from
The amount of acid consumed in the dissolution of a mineral
the dissolution data. Again, a parabolic function was used to relate
depends on the composition of the mineral. Eqs. (7)–(15) show
the value of the decay constant to the pH.
the acid dissolution of selected minerals. Calcite follows Eq. (7)
Taking the definite integral of Eq. (3) with respect to time (T)
(Venter and Boylett, 2009), laumontite follows Eq. (8), chlorite
from 0 to t hours gives Eq. (4).
Eq. (9) (modified from Lowson et al. (2005) to more closely match
Z t the composition of the chlorite in the present study), muscovite is
ekt  1
R dT ¼ R0 þ zt ð4Þ shown in Eq. (10) (Knauss and Wolery, 1989 and Oelkers et al.,
0 k
2008), smectite is shown in Eq. (11), adapted from Amram and Ga-
Because most rates are surface area normalised, multiplying Eq. nor (2005) and Metz et al. (2005), illite in Eq. (12) after Kohler et al.
(4) by the surface area gives the percentage dissolution of the min- (2003), plagioclase Eq. (13), K-feldspar Eq. (14) (both after Stillings
eral. For example, if a mineral occurs in the ore in a concentration and Brantley (1995)), quartz is shown in Eq. (15) (Blum et al.,
 B.J. Youlton, J.A. Kinnaird / Minerals Engineering 52 (2013) 62–73 65

1990). As can be seen from Eq. (15), the dissolution of quartz does CaCO3 þ 2Hþ ! CaSO4 þ CO2 " þH2 O ð7Þ
not consume acid. For this reason quartz will not be considered
3þ
further. CaAl2 Si4 O12 :4H2 O þ 8Hþ ! Ca2þ þ 2Al þ 4H4 SiO4 ð8Þ

ðMg3:75 Fe6:25 Al2 ÞðSi6 Al2 O20 ÞðOHÞ16 þ 32Hþ

Table 1
3þ
Acid consumption characteristics of selected minerals and MnO2. ! 75Mg2þ þ 6:25Fe2þ þ 4Al 6H4 SiO4 þ 12H2 O ð9Þ
Mineral Ideal acid cons (kg/ton)a Incongruent acid cons (kg/ton)a
3þ
Calcite 9.8 – KAl2 ðSi3 AlO10 ÞðOHÞ2 þ 10Hþ ! Kþ þ 3Al þ 3SiðOHÞ4 ð10Þ
Laumontite 6.4 3.8c
Chlorite 12.0b – ðCa0:22 Mg2:18 ÞðMg0:7 Fe2:3 AlÞðAl1:8 Si6:2 ÞO20 ðOHÞ4 þ 19:2Hþ þ 0:8H2 O
Muscovite 12.3 –
3þ
Smectite 11.1b – ! 22Ca2þ þ 2:88Mg2þ þ 2:3Fe2þ þ 2:8Al þ 6:2H4 SiO4 ð11Þ
Illite 10.7 –
Plagioclase 7.5b 6.1c
K-feldspar 6.8 2.7c K1:26 ðMg0:02 Fe0:19 Al3:80 ÞðAl1:26 Si6:75 ÞO20 ðOHÞ4 þ 16:86Hþ þ 3:07H2 O
MnO2 2.3 – 3þ
! 26Kþ þ 0:02Mg2þ þ 0:19Fe2þ þ 5:06Al þ 6:75H4 SiO4 ð12Þ
a
Calculated using Eqs. (7)–(15), assuming 1% dissolution of the mineral of
interest. When multiplied by the amount of the mineral that dissolved during the
Na0:93 Ca0:07 Al1:07 Si2:93 O8 þ 4:28Hþ þ 3:72H2 O
leach tests, these values can be used to calculate the acid consumed by each phase.
3þ
! 0:93Naþ þ 0:07Ca2þ þ 1:07Al
b
These values vary with mineral composition. þ 2:93H4 SiO4 ð13Þ
c
These values are strongly dependant on the element used to calculate the
dissolution rate of the mineral.
3þ
KAlSi3 O8 þ 4Hþ þ 4H2 O ! Kþ þ Al þ 3H4 SiO4 ð14Þ

Table 2 SiO2 þ H2 O ! H4 SiO4 ð15Þ

Major mineralogy as determined by XRD and QEMScan BMA.
Eqs. (7)–(15) represent the simplest case in which complete dis-
Sample MKB1 (Mass%) RAO (Mass%) OAO (Mass%) MSO (Mass%) solution occurs. However, as a result of incongruent dissolution,
Quartz 32.0 31.0 49.8 7.6 different elements can be released at different rates from the same
Plagioclase 25.5 40.7 40.1 16.6 mineral, resulting in significantly more complicated dissolution
K-feldspar 13.6 9.4 5.7 7.9 reactions. No attempt was made to correct the phyllosilicates for
Muscovite 2.1 0.5 0.9 –
incongruent dissolution. In case of these minerals, the rate was
Chlorite 6.8 8.7 – –
Illite – – – 48.7 either calculated from an element with an intermediate release
Smectite – 8.2 3.4 19.2 rate, or congruent dissolution was reached fairly early in the leach.
Laumontite 8.1 – – – It was not possible to treat the tectosilicates with this simple
Calcite 12.0 – – – approach. Feldspar release rates were determined using the rela-
Pyrite – 1.6 – –
Total 100.0 100.0 100.0 100.0
tive release ratios of Stillings and Brantley (1995). There was no
quantitative data published for laumontite and it was therefore

Table 3
Estimated mean surface areas (A) calculated from stereologically corrected gangue mineral grain sizes and roughness data (Rs).

Sample MKB1-212 (m2/g) MKB1-75 (m2/g) RAO (m2/g) OAO (m2/g) MSO (m2/g)
Determination A Rs A Rs A Rs A Rs A Rs
Quartz – – – – – – – – – –
Plagioclasea 0.67 11.14 1.18 11.32 1.02 11.06 0.65 10.38 0.39 11.89
K-feldspara 0.63 11.32 1.04 11.37 0.99 11.72 0.67 11.56 2.48 11.97
Laumontit 0.11 1.00 0.17 1.00 – – – – – –
Muscoviteb 1.96 13.77 3.43 13.78 1.04 13.87 2.91 13.89 – –
Chloritec 2.18 6.17 2.89 6.15 1.61 6.15 – – – –
Smectite – – – – – – – – – –
Illite – – – – – – – – – –
Calcited 0.22 2.48 0.33 2.48 – – – – – –
a
Feldspar roughness calculated using data from Knauss and Wolery (1986), Casey et al. (1991), Stillings and Brantley (1995) and Chen and Brantley (1997).
b
Muscovite roughness calculated using data from Nickel (1973), Knauss and Wolery (1989) and Kalendova et al. (2010).
c
Chlorite roughness calculated using data from Brandt et al. (2003), Lowson et al. (2005) and Hen et al. (2007).
d
Calcite roughness calculated using data from Anderson (1968), Oleg et al. (2005) and Oelkers et al. (2011).

Table 4
Uranium deportment, determined by QEMScan TMS, detailing the proportion of the total contained uranium hosted by each uranium mineral.

Sample MKB1-212 (%) MKB1-75 MKB1 (Ave) (%) RAO (%) OAO (%) MSO (%)
Uraninite 23.92 19.30 21.61 4.87 24.79 –
Coffinite 74.60 77.95 76.28 65.18 74.03 –
Uraniferous leucoxene 0.44 1.16 0.80 29.95 1.17 –
Thorite 1.04 1.59 1.31 – – –
Meta-uranocircite – – – – – 54.65
Meta-autunite – – – – – 45.35
Total 100.00 100.00 100.00 100.00 100.00 100.00
66 B.J. Youlton, J.A. Kinnaird / Minerals Engineering 52 (2013) 62–73

Fig. 1. QEMScan TMS particle maps showing U minerals from MKB1-212 (A and B), MKB1-75 (C and D), RAO (E and F), OAO (G and H) and MSO (I and J). The large scale bars in
all except B, C and D are 212 lm. Those in B are 0.6 lm, while those in C and D are 75 lm.
 B.J. Youlton, J.A. Kinnaird / Minerals Engineering 52 (2013) 62–73 67

Table 5
Uranium mineral exposure and association characteristics as determined by QEMScan TMS.

Sample exposure and association categories MKB1-212 (Mass%) MKB1-75 (Mass%) RAO (Mass%) OAO (Mass%) MSO (Mass%)
Exposed 69.71 90.86 64.38 91.79 93.63
Locked in reactive minerals 5.94 2.02 20.90 3.11 6.33
Locked in low reactivity minerals 24.34 7.12 14.71 5.10 0.04
Total 100.00 100.00 100.00 100.00 100.00

Fig. 2. X-ray diffractograms showing the change in gangue mineralogy as the leaches progress. In each case diffractograms are in sequential order, with the head sample as
the upper diffractogram and the 25 h residue is the lowest. (A–D) represent the diffractograms collected from MKB1, RAO, OAO and MSO respectively.

necessary to determine these as part of the present study. Using MnO2 in U leaching to predict the MnO2 consumption. It was there-
these results the acid consumption characteristics of the tectosili- fore necessary to produce an equation for this purpose from the re-
cates were determined. The ideal acid consumption characteristics sults of this study.
of selected minerals are given in Table 1. Where necessary, the acid
consumption corrected for incongruent dissolution has also been 3.4. Free acid
given. These values, when multiplied by the mass percent of the
mineral that dissolved during the leach (calculated as the mass In this case free acid concentration refers to the acid that remains
of dissolved mineral relative to the mass of ore treated), can be in solution to maintain the low pH needed for U dissolution. Eq. (16)
used to calculate the amount of acid consumed in the dissolution gives the relationship between H+ activity and pH, and Eq. (17) gives
of that phase. the relationship between activity and concentration (Harris, 1999).
Manganese dioxide is the second reagent used in the U leaches.
pH ¼  log aHþ ð16Þ
The dissolution of this reagent also consumes acid according to Eq.
(2). It is therefore necessary to be able to accurately predict the
Ac ¼ ½Ccc ð17Þ
MnO2 demand of an ore. There was insufficient literature on
68 B.J. Youlton, J.A. Kinnaird / Minerals Engineering 52 (2013) 62–73

Table 6 where Kspgypsum is the solubility product constant of gypsum, Ai is

Leach conditions and uranium dissolution. the activity of the respective species (equal to the product of the
Test Sample P80 pH Eh U dissolution (%)* activity constant and the concentration), and KCaSO4 is the equilib-
A MKB1 212 0.97 499 89.47
rium constant for the formation of calcium sulphate ion pairs. Typ-
B MKB1 212 1.52 449 70.36 ical values for Kspgypsum range from 104.59 to 104.35 while KCaSO4
C MKB1 75 1.51 457 86.80 has a value of 102.31 (Reardon and Langmuir, 1976 and Messnaoui
D MKB1 212 2.02 413 67.71 and Bounahmidi, 2006).
E RAO 212 1.56 428 85.13
In addition to the activity coefficient, it is also necessary to con-
F OAO 212 1.47 485 83.06
G MSO 212 1.33 471 88.44 sider the second acid dissociation of sulphuric acid. The higher the
*
acid consumption of the ore, the more SO2 4 accumulates in solu-
Duplicate leach tests suggest that the error in the U dissolution is 3.89%.
tion (except where precipitates such as gypsum form). The in-
creased levels of SO2 4 forces the dissociation reaction to the left,
where Ac is the activity of ion C, [C] is the concentration (in mol/L) of forming HSO +
4 at the expense of H . For ores with high acid con-
C and cc is the activity coefficient. There are a number of methods of sumptions, the second dissociation of sulphuric acid is even more
determining the activity coefficient. These include the Debye–Hüc- significant than the hydrogen ion activity coefficient.
kel method, which can be used to determine the activity coefficient An Excel-based model was developed that considers the disso-
for solutions with an ionic strength less than 0.1 mol/L (Harris, lution of each major mineral phase, the MnO2 addition, the solu-
1999). Due to the high ionic strengths that can be reached in U tion composition, gypsum and ion pair formation, ionic strength
PLS, it was decided to use the Davies method (as recommended and activity coefficients, the free acid demand and the concentra-
by Samson et al., 1999). tions of the HSO 4 ion in solution. Due to the interdependence of
Both the Debye–Hückel and the Davies method are based on the the variables in the model, an iterative approach was used. The first
ionic strength of the solution, which is a function of solution com- iteration assumed that the activities of the various species equalled
position. The dissolution data obtained using Eq. (4) and Eqs. (7)– their concentration. Later iterations considered the activity coeffi-
(15) were used to determine the ion input into solution. However, cients. The model typically required four iterations to stabilise.
the composition of the solution (and therefore the ionic strength)
differs from this input composition for two reasons. The first in-
volves the formation of gypsum (Danielle et al., 2008) which re- 4. Results
moves both Ca2+ and SO2 4 from solution in equal molar
quantities. The second involves the formation of ion pairs in solu- 4.1. Head sample gangue mineral characterisation
tion (Reardon and Langmuir, 1976). The solubility of gypsum and
concentrations of the ion pairs are determined according to Eqs. The XRD and BMA analyses produced very comparable gangue
(18) and (19) respectively. mineral abundances and the composition of each sample is given
in Table 2. The arkose from the main Karoo basin (MKB1), the Kay-
Kspgypsum ¼ ACa2þ  ASO2 ð18Þ elekera reduced arkose ore (RAO) and oxidised arkose ore (OAO)
4

consist of subequal amounts of quartz and plagioclase with lesser

ACa2þ  ASO2 K-feldspar. MKB1 also contains calcite, laumontite, chlorite and
K CaSO4 ¼ 4
ð19Þ muscovite. The RAO also contains chlorite and pyrite. RAO and
ACaSO4
OAO contain smectite, but the highest smectite concentrations oc-

Fig. 3. Uranium dissolution as a function of time. The MKB leaches (tests A–D) are shown to the left in (A) and tests E to G (the Kayelekera leaches) are shown to the right in
(B). Based on the results of duplicate leach tests, the error in dissolution is estimated to be 3.89%.

Table 7
Ore ferrous iron concentrations, leach conditions, measured and calculated manganese dioxide consumptions.

Test Sample Fe2+ pH Eh MnO2 Meas (kg/ton) MnO2 Calc. (kg/ton)

A MKB1 0.83 0.97 499 17.88 12.1
B MKB1 0.83 1.52 449 6.94 6.8
C MKB1 0.83 1.51 457 11.69 7.6
D MKB1 0.83 2.02 413 2.93 2.9
E RAO 4.52 1.56 428 32.93 32.9
F OAO 0.48 1.47 485 1.45 1.5
G MSO 0.48 1.33 471 0.00 0.0
 B.J. Youlton, J.A. Kinnaird / Minerals Engineering 52 (2013) 62–73 69

Fig. 4. Modelled acid dissolution of calcite (A), laumontite (B), chlorite (C), muscovite (D), plagioclase (E) and K-feldspar (F) expressed as a function of pH and time. Measured
and calculated smectite (G) and illite (H) dissolution are also shown; however these are only expressed as a function of time. It was not possible to determine the dissolution
characteristics of smectite and illite as a function of pH because the samples that contain these minerals were only leached at pH 1.5.

cur in MSO. The dominant phase in MSO is illite, with lesser plagio- is the second coarsest phase (at both grinds). Estimated specific
clase and minor K-feldspar and quartz. surface areas were needed for the surface area normalisation of
Stereologically corrected grain sizes indicate that in each sam- the rates. These values (calculated from the grain size data) are
ple, quartz is the coarsest phase, followed by plagioclase and then presented in Table 3. For reference the surface roughness values
K-feldspar in the Kayelekera samples. In the MKB1 sample calcite used in the calculations are also shown.
70 B.J. Youlton, J.A. Kinnaird / Minerals Engineering 52 (2013) 62–73

4.2. Uranium mineral characterisation the depletion of chlorite and the formation of gypsum. Trace
amounts of gypsum also formed in the residues of RAO (Fig. 2B).
The MKB1 sample had a head grade of 208 ppm U3O8. Both RAO RAO also showed depletion of chlorite and changes in the shape
and MSO have significantly higher U grades (2369 ppm and and position of the smectite peak.
1635 ppm U3O8 respectively), while OAO only has a grade of Variation in the smectite peak shape and position were the only
387 ppm U3O8. changes seen in the residues of OAO (Fig. 2C). However, these
The U deportments of MKB1 and OAO are similar (Table 4 and changes are more clearly seen in MSO (Fig. 2D) where the higher
Fig. 1). In these samples the majority of the U is present in coffinite smectite concentration made the changes more obvious. It can be
(U(SiO4)1x(OH)4x) with lesser amounts occurring in uraninite seen that the interlayer spacing of the smectite progressively col-
(UO2). RAO differs from these samples in that uraniferous leucox- lapses from 17.1 Å in the head sample to 14.4 Å in the 9 h residue.
ene, rather than uraninite, is the second most important U mineral. This is accompanied by a marked broadening of the peak. However,
The U deportment of MSO is completely different from any of the in the 25 h residue, the interlayer spacing increases to 16.7 Å, with
arkose samples, with subequal amounts of U occurring in meta- a significantly narrower peak than in the 9 h residue.
uranocircite (Ba(UO2)2(PO4)26H2O) and meta-autunite The U dissolutions at the end of the 24 h leach period are given
(Ca(UO2)2(PO4)26H2O). in Table 6; the leach conditions are also shown. Fig. 3A shows the U
The exposure and association characteristics of each sample are dissolution curves for the four MKB1 leaches and Fig. 3B shows the
summarised in Table 5. Exposed grains are those that have a pro- Kayelekera leaches. Two data points are missing from Fig. 3A.
portion of their surface that is exposed at the edge of a particle. These are Test B, 4 h and Test C, 9 h. Due to the high concentrations
These are grains that would be available for dissolution. MKB1 of silica (resulting from zeolite dissolution), the MKB1 samples
exposure was not particularly high at 80% passing 212 lm and gelled after a few days. This gelling occurred before it was possible
24% of U mineral grains are locked in low reactivity gangue. How- to complete the analyses of the PLS for these two points.
ever, there was a significant improvement in exposure at 80% pass- In the MKB1 leaches, Tests A and C showed very similar disso-
ing 75 lm, where only 7% of U mineral grains occur in low lutions, with progressively lower dissolution in B and D. The Kay-
reactivity gangue. The proposition of exposed grains in RAO was elekera dissolutions were all above 80%, with dissolutions
also low (64%), however a significant amount of the locked grains increasing from OAO through RAO to MSO. However, examination
occur within reactive gangue. of the dissolution curves (Fig. 3B) show that OAO reached maxi-
The exposures of OAO and MSO were both high, with 92% of mum dissolution (of 91.21%) at 4 h and MSO reached maximum
grains in OAO and 94% in MSO showing some degree of exposure. dissolution (of 97.31%) at 9 h. Thereafter, both samples show a de-
crease in the percentage U dissolution.
4.3. Analysis of leach products
5. Modelling of gangue dissolution
X-ray diffractograms showing changes in the gangue mineral-
ogy, in response to acid leaching, are given in Fig. 2. Only one of Using the results of the Fe2+ titrations on the head samples, the
the MKB1 leaches has been shown. This leach was at a P80 of 212 MnO2 consumptions and the redox potential of the leach tests, Eq.
and a pH of 1.52. The other leaches show similar trends, except (20) was found to predict the MnO2 consumption with reasonable
that the leaches at lower pH or finer grind show more rapid gangue accuracy (Table 7). However, as shown in Eq. (2) the consumption
dissolution, while the leach at higher pH showed slower of MnO2 involves Fe2+ in the PLS and therefore Eq. (20) relies on the
dissolution. assumption that the Fe2+ dissolution characteristics, of an ore, are
The most noticeable changes in the mineralogy of the MKB1 the same as those in this study. Since Fe dissolution is a function
sample (Fig. 2A) is the disappearance of calcite and laumontite, of pH, Eq. (20) also assumes a relationship between the pH and

Table 8
Variables used in modelling gangue dissolution in Eqs. (21)–(23) as well as their measures of fit.

Mineral Variablea a b c Measure of fitb

Calcite R0 30.48 155.89 396.53 0.947
k 0.08 0.38 0.89
z 0.00 0.00 0.00
Laumontite R0 878.27 3605.07 3870.56 0.981
k 0.79 3.25 3.50
z 0.00 0.00 0.00
Chlorite R0 6.35 23.10 21.92 0.991
k 0.00 0.00 0.95
z 0.42 1.83 2.04
Muscovite R0 2.93 4.56 4.83 0.923
k 0.54 1.07 0.57
z 0.00 0.00 0.00
Plagioclase R0 1.75 7.99 9.61 0.854
k 0.43 0.53 1.09
z 0.00 0.00 0.00
K-feldspar R0 1.21 5.08 5.67 0.994
k 0.46 0.17 2.13
z 0.00 0.00 0.00
a
Both R0 and z are given in terms of the proportion of the mineral of interest (expressed as a percentage) dissolved per hour normalised to the specific surface area or
percent/(m2/g h).
b
The measure of fit was obtained by comparing the measured mineral dissolution data with calculated dissolution data. The parameter used above is the square of the
correlation coefficient.
 B.J. Youlton, J.A. Kinnaird / Minerals Engineering 52 (2013) 62–73 71

Fig. 5. A comparison of the acid consumed in each of the leaches with the amount predicted by the model. Plots (A–G) represent leaches A–G respectively (see Table 7 for the
conditions of each leach). In several of the plots, especially (E), there is a large discrepancy between the measured and calculated data in the early hours of the leach. This is
because the model assumed all the MnO2 was added at the first hour, while in the leach tests the MnO2 was added progressively throughout the leach. Duplicate leach tests
suggest that the error in the measured acid consumption is 4.91%, while the average error in the calculated acid consumption (determined by comparing the measured and
calculated acid consumptions) is 8%.
72 B.J. Youlton, J.A. Kinnaird / Minerals Engineering 52 (2013) 62–73

Eh conditions used in the leach. The assumption being that when tion. The substitution of these cations could have resulted in the in-
more oxidising conditions are used, then the leaches would also crease in the interlayer spacing. This substitution may also be the
be performed at lower pH. reason for the decrease in U dissolution in the later stages of the
leach.
MnO2 ¼ 38:58 log½Fe2þ  þ 0:1069 Eh  38:09 ð20Þ OAO and MSO were not the only samples to contain smectite.
The modelled dissolutions of the various gangue phases are RAO contained more smectite than OAO, but this sample did not
shown in Fig. 4. For most minerals the dissolutions are shown as show the same decrease in dissolution in the later stages of the
a function of both time and pH. However, because the samples that leach. There are two likely reasons. The first is that in RAO 20%
contained smectite and illite were all leached at approximately pH of the U occurred in grains locked in reactive gangue. This U was
1.5, it was not possible to plot the dissolution of these minerals in released more slowly as time was required to dissolve the gangue.
pH-time space. These were plotted as a function of time at pH 1.5. This prevented this leach from developing an early maximum. The
The variables and a measure of fit, comparing the modelled and second is that the RAO solution contained very high concentrations
measured dissolution data for each mineral (except smectite and of other elements, especially Mn from the oxidiser. These elements
illite), are given in Table 8. The variables used for smectite were may have preferentially substituted into the smectite.
3.60 for R0, 0.50 for k and 0 for z. Those used for illite were
0.0031 for R0, 0.40 for k and 0 for z. 6.2. Gangue dissolution
R0 ¼ a1 pH2 þ b1 pH þ c1 ð21Þ
The dissolution characteristics of several common gangue min-
2 erals were determined. These results show that gangue dissolution
k ¼ a2 pH þ b2 pH þ c2 ð22Þ
increases with decreasing pH and grain size. The rate of dissolution
of most minerals follows an exponential decay function, from an
z ¼ a3 pH2 þ b3 pH þ c3 ð23Þ initially rapid rate to a much slower one as the leach progresses.
The results of the measured acid consumptions, compared with The dissolution rates of calcite and laumontite are rapid and
those predicted by the model are shown in Fig. 5. The Eh control both phases were completely dissolved, (although laumontite is
was maintained by addition of MnO2, which is an important acid subject to incongruent dissolution and it is likely that an amor-
consumer. However, due to the slow dissolution of MnO2, it was phous Si–Al solid phase is still present in the residues at the end
necessary to add small amounts and then monitor the changes in of the leach).
Eh over time. It was, therefore, not possible to add all of the neces- Chlorite dissolution was also rapid, but not as rapid as that of
sary MnO2 at the start of the leach. The model assumes that all calcite or laumontite. Depending on the pH and specific surface
MnO2 was added after the hour of preconditioning and for this rea- area, between about 7% and 47% of the contained chlorite can dis-
son there is a discrepancy between the measured and calculated solve within the duration of an acid leach. Muscovite dissolution
acid consumptions in the early stages of the leach (especially for was much slower and only about 12% dissolved at pH 0.97. While
Test E). Besides the MnO2 discrepancy, the calculated acid con- the feldspars do dissolve, the rate of this dissolution was very slow.
sumptions closely approximate the measured consumptions. Neither plagioclase nor K-feldspar showed more than 2%
dissolution.
Considering both the rate at which gangue phases dissolve, and
6. Discussion
the amount of acid they consume during dissolution, carbonates
are the most aggressive gangue acid consumers, followed by lau-
6.1. Uranium dissolution
montite (although this phase does not occur in many U deposits)
and chlorite. Muscovite, smectite and illite were moderate acid
A comparison of the MKB1 exposure data (Table 5) obtained by
consumers, while only minor dissolution of plagioclase and K-feld-
QEMScan TMS, with U dissolution in the leach tests (Table 6) found
spar dissolved. The dissolution characteristics of these minerals
that, in tests B and D, the amount of exposed U agreed well with
can be used both in assessing the reagent consumption of an ore
the percentage U dissolution. The finer grind used in test C allowed
and the effect of U mineral texture (particularly exposure and asso-
for significantly higher U dissolution and again there was agree-
ciation) on U dissolution.
ment between the exposure and dissolution data. However, the
dissolution seen in Test A far exceeds the predicted value based
on the U mineral exposure. In order to achieve such high dissolu-
tions, significant amounts of locked U must have been exposed 7. Conclusions
by the aggressive conditions of the leach.
The U minerals in OAO and MSO both had very high degrees of The following conclusions can be drawn from the results of this
exposure (>91%), but the final U dissolution in these samples was study:
less than 89%. The maximum dissolution in both of these samples
was not achieved at 24 h, with OAO reaching a maximum dissolu- (1) The dissolution of gangue minerals can result in substantial
tion of 91% at 4 h and MSO reaching maximum dissolution increases in U mineral dissolution.
(97%) at 9 h. After these maxima, both leaches showed progres- (2) The presence of smectite can result in the loss of U from
sive decreases in U dissolution. This could either be the result of solution as the leach progresses. High concentrations of zeo-
U precipitation from solution, or may be due to the smectite. lite in the ore can also be deleterious both increasing acid
Both of these samples contain smectite. XRD analysis of the consumption and causing gelling of the PLS.
leach residues show a progressive collapse in the interlayer spacing (3) It is possible to estimate the percentage U dissolution, dur-
of the smectite from the head sample (at 17 Å) to the 9 h residue ing acid leaching, from QEMScan TMS data. For a non-refrac-
where it reached 14 Å). Thereafter the interlayer spacing in- tory ore, at moderate conditions (pH 1.5, 35–40° C, 24 h
creased, reaching 17 Å in the 25 h residue. It is possible that duration) the percentage U dissolution approximately
the interlayer collapse is the result of H+ replacement of the inter- equals the proportion of the U mineral grains that show
layer cations. Then as the ionic strength of the solutions increased, some degree of exposure. At lower pH conditions (1.0)
other larger cations (including U) became available for substitu- the U dissolution may exceed the sum of exposed U grains
 B.J. Youlton, J.A. Kinnaird / Minerals Engineering 52 (2013) 62–73 73

and those associated with reactive gangue. At higher pH constants, effective surface area, and hydrolysis of feldspar. Geochimica et
Cosmochimica Acta 48, 2405–2432.
(2.0) the U dissolution is lower than the proportion of
Hen, F., Durand, C., Cerepi, A., Brosse, E., Giuntini, J.C., 2007. DC conductivity, cation
exposed grains (presumably due to slow leach kinetics). exchange capacity, and specific surface area related to chemical composition of
(4) Provided detailed data are available, it is possible to use pore lining chlorites. Journal of Colloid and Interface Science 311, 571–578.
mineralogical data to predict the acid dissolution character- HO, E.M., Quan, H., 2007. Iron (II) oxidation by SO2/O2 for use in uranium leaching.
Hydrometallurgy 85, 183–192.
istics of gangue minerals with reasonable accuracy. These Hodson, M.E., 2006. Searching for the perfect surface area normalizing term – a
predictions can be used in conjunction with free acid calcu- comparison of BET surface area-, geometric surface area- and mass normalized
lations to predict the acid consumption characteristics of the dissolution rates of anorthite and biotite. Journal of Geochemical Exploration
88, 288–291.
ore. To estimate the gangue acid consumption of a particular IAEA, 1980. Significance of Mineralogy in the Development of Flowsheets for
ore, the values in Table 8 can be used. For more accurate Processing of Uranium Ores. International Atomic Energy Agency, Vienna, pp.
data, these values should be calibrated for a particular U 1–161.
IAEA, 1990. Manual on Laboratory Testing for Uranium Ore Processing.
deposit by comparison of mineralogical and leach test data. International Atomic Energy Agency, Vienna, pp. 1–127.
Similarly Eq. (20) may need to be calibrated for a particular Kalendova, A., Vesely, D., Kalenda, P., 2010. Properties of paints with hematite
deposit. coated muscovite and talc particles. Applied Clay Science 48, 581–588.
Knauss, K.G., Wolery, T.J., 1986. Dependance of albite dissolution kinetics on pH and
time at 25 °C and 75 °C. Geochimica et Cosmochimica Acta 50, 2481–2497.
Knauss, K.G., Wolery, T.J., 1989. Muscovite dissolution kinetics as a function of pH
and time at 70 °C. Geochimica et Cosmochimica Acta 53, 1493–1501.
Acknowledgements Kohler, S., Dufaud, F., Oelkers, E.H., 2003. An experimental study of illite dissolution
kinetics as a function of pH from 1.4 to 12.4 and temperature from 5 to 50 °C.
The authors would like to thank Paladin Energy for contributing Geochimica et Cosmochimica Acta 67, 3583–3594.
Lottering, M.J., Lorenzen, L., Phala, N.S., Smit, J.T., Schalkwyk, G.A.C., 2008.
most of the U ore used in this study and SGS South Africa for spon- Mineralogy and uranium leaching response of low grade South African ores.
soring instrument and batch reactor time. The advice of Johan O’ Minerals Engineering 21, 16–22.
Connell, Louis Coetzee, Maria Klaas and Annegret Lombard is also Lowson, R.T., Comarmond, J.M.C., Rajaratnam, G., Brown, P.L., 2005. The kinetics of
the dissolution of chlorite as a function of pH and at 25 °C. Geochimica et
greatly appreciated. Cosmochimica Acta 69, 1687–1699.
Lunt, D., Boshoff, P., Boylett, M., El-Ansary, Z., 2007. Uranium extraction: the key
process drivers. The Journal of the South African Institute of Mining and
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