Minerals Engineering 160 (2021) 106664

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Minerals Engineering
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Lime properties and dose effects on causticisation of synthetic Bayer liquor

C.A. du Plessis a, *, H. Lambert a, E. Hoummady a, R.G. McDonald b, D. Bedell b
a
Lhoist Recherche et Développement SA, Rue de l’industrie 31, B-1400 Nivelles, Belgium
b
CSIRO Mineral Resources, 7 Conlon St, Karawara, WA 6152, Australia

A R T I C L E I N F O A B S T R A C T

Keywords: The production of alumina (Al2O3) from bauxite via the Bayer process is underpinned by the use of lime in a
Lime variety of process reactions. One of the most important is the causticisation of process liquors, in which lime is
Slaking used to convert soluble sodium carbonate into caustic, i.e. sodium hydroxide. Causticisation is complicated by
Causticisation
unproductive side reactions with sodium aluminate that limit both the extent of causticisation and the efficiency
Alumina
Bayer
of lime use. Substantial industrial effort and literature has been devoted to optimising causticisation process
Tri-calcium aluminate (TCA) parameters (e.g. temperature, reaction time, liquor concentrations, and reactor mixing regimes) but little
Monocarbonate attention has been given to determining the impacts of lime properties and dose. In this study a test procedure
Hemicarbonate was developed and used to evaluate the impact of lime dose, in both slaked and dry quicklime formats, on
CO2 emissions causticisation performance. This was used to determine the effects of various lime properties, including (1)
Greenhouse gas (GHG) chemical composition (purity), (2) particle size and (3) reactivity on the causticisation of synthetic Bayer liquors.
The results show that, of these parameters, the differences in lime chemical composition had the most significant
impact. The methodology can be used to facilitate optimal lime reagent choice and dosage in industrial alumina
Bayer refineries. The potential impact of lime utilisation efficiency is also illustrated in the context of overall CO2
emission intensity.

1. Introduction 1.2. Reactions

1.1. Lime in the Bayer process
Lime is an essential reagent required in various process steps of the
Bayer process, in which bauxite ore is converted into alumina (Whit­
tington et al. 1997), as illustrated in Fig. 1. It is used for improving
conversion of goethite to hematite and dissolution of boehmite and
diaspore during digestion; control of liquor impurities such as silica,
oxalate, titanium and phosphorous; minimising soda losses to red mud;
providing filter aid for liquor clarification and for causticisation (Arıkan
et al. 2019; Wellington, 2015; Whittington, 1996; Whittington and
Cardile, 1996). Alumina Bayer refineries, accordingly, consume large
quantities of lime, ranging from approximately 50 kt per annum per
million tonnes of alumina production, for a plant processing high quality
lateritic bauxite, to at least twice that quantity for Bayer refineries using
diasporic bauxites (Arıkan et al. 2019; Chaplin, 1971).
Caustic soda, i.e. sodium hydroxide (NaOH), is the key reagent used
in alkaline digestion of bauxite ore (Whittington et al. 1997) which re­
lies on the dissolution of solid aluminium hydroxide and oxy-hydroxide
minerals to form aluminate ions in solution, i.e. Al(OH)-4 (Sipos, 2009).
In addition to the mineral digestion reaction (Eq. (1)), NaOH also reacts
with organic matter contained in bauxite, and to a minor extent with
atmospheric CO2, resulting in the formation of soluble sodium carbonate
(Power et al. 2012) illustrated in simplified form in Eq. (2):
Al(OH)3 + NaOH → NaAl(OH)4 (1)
Organic matter + NaOH → Organic acid anions + Na2CO3 (2)
This presence of sodium carbonate reduces the effectiveness of the
liquor to digest alumina minerals from the bauxite. Bayer process liquors
are maintained at a controlled maximum level of soluble anions, so
removal of soluble carbonate is essential to the maintenance of an
acceptable concentration of NaOH. The only known way to economi­
cally remove the soluble sodium carbonate is by causticisation with lime

* Corresponding author.
E-mail address: chris.duplessis@lhoist.com (C.A. du Plessis).

https://doi.org/10.1016/j.mineng.2020.106664
Received 10 July 2020; Accepted 5 October 2020
Available online 26 October 2020
0892-6875/© 2020 The Author(s). Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
C.A. du Plessis et al.
Fig. 1. Simplified Bayer process diagram, indicating causticisation location and other lime addition points.
(sometimes also referred to as re-causticisation), which precipitates
solid calcium carbonate and proportionately returns (i.e. regenerates)
hydroxide ions (in the form of NaOH) to the solution. The basic reaction
(Eq. (3)) is preceded by a hydration reaction (Eq. (4)) in scenarios where
dry quicklime is used directly in the causticisation reaction (Xu et al.
1998).
Ca(OH)2 + Na2CO3 → 2NaOH + CaCO3 (3)
CaO + H2O → Ca(OH)2 (4)
These equations are sufficient for the prediction of reaction rates and
efficiencies of causticisation of alkaline sodium carbonate solutions in
the paper pulp industry (Wang et al. 1994). However, in processing
bauxite to alumina by the Bayer process, the situation is complicated by
the presence of sodium aluminate, NaAl(OH)4, and several impurity
anions including phosphate, titanate, oxalate and fluoride (Chaplin,
1971) that can form a range of compounds with lime. The most
important (and unproductive) side-reaction with lime (Fig. 2) is the
reaction with aluminate to form TCA, tri-calcium aluminate, Ca3[Al
(OH)6]2 (Eq.5).
3Ca(OH)2 + 2NaAl(OH)4 → Ca3[Al(OH)6]2 + 2NaOH (5)
Previous studies have suggested that TCA exists in equilibrium with
CaCO3, and that the degree of causticisation under given conditions can
be predicted thermodynamically (Whittington, 1996; Roach, 2000). The
equilibrium conditions are, however, complex due to the described
formation of intermediate layered double hydroxide precipitates (LDHs,
also referred to as hydrocalumite as a generic term for compounds with
the formula Ca2Al(OH)6.X⋅nH2O that are based on repeating [Ca2Al
(OH)6]+ units), and the reported metastability of these LDHs (Rosenberg
et al. 2001). Anions such as carbonate are intercalated into the interlayer
Fig. 2. Simplified diagrammatic illustration of lime reactions into productive
and unproductive products, TCA (tri-calcium aluminate) and LDHs (layered
double hydroxides).
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Minerals Engineering 160 (2021) 106664
space of the LDH (Tóth et al. 2014). The extent of carbonate incorpo­
ration, i.e. normally 0.5 or 1 carbonate for each [Ca2Al(OH)6]+ unit,
results either in a hemicarbonate (Eq. (6)), or monocarbonate (Eq. (7))
(Runčevski et al. 2012; Smith 2017). The hemicarbonate has been re­
ported as the most likely product from the reaction of lime with indus­
trial Bayer liquors, while the use of synthetic liquor typically results in
monocarbonate as the main LDH in laboratory studies (Rosenberg et al.
1999).
4Ca(OH)2 + 2NaAl(OH)4 + 0.5Na2CO3 + 5.5H2O →
[Ca2Al(OH)6]2.(CO3)0.5.OH.(5.5H2O) + 3NaOH (6)
4Ca(OH)2 + 2NaAl(OH)4 + Na2CO3 + 5H2O →
[Ca2Al(OH)6]2.CO3⋅5H2O + 4NaOH (7)
Depending on the complex set of prevailing equilibrium conditions,
the LDH intermediates may decompose into either TCA or CaCO3
(Buttery et al. 2002; Sizyakov and Tikhonova 2012; Smith 2017). The
reactions producing TCA or LDHs (e.g. Eq. (5), 6 and 7) are detrimental
for two reasons: (1) the precipitated alumina species are lost to residue
and (2) lime is inefficiently used for low productivity reactions, i.e. less
Na2CO3 is converted per mol of Ca(OH)2 consumed. Based on these two
criteria, TCA is the most undesirable precipitate product, followed by
hemicarbonate and then monocarbonate. The equilibrium between the
most desired reaction product of lime use (CaCO3) and aluminium-
containing precipitates (TCA and LDHs) is influenced by a number of
factors including the solution aluminate concentration, combined
caustic and sodium carbonate concentration, and temperature (de Witt
et al. 2000; Roach, 2000; Rosenberg et al. 2001). Other strategies that
have successfully been employed to shift the equilibrium towards the
desired product include the use of additives such as gluconate to inhibit
the formation of TCA and facilitate the formation of calcite (Eq. (3))
Fig. 3. Diagrammatic illustration of the links between the three operational
causticisation process objectives.
C.A. du Plessis et al.
(Rosenberg et al. 1999; Rosenberg 2008).
1.3. Operational context
In an alumina refinery the objectives of causticisation are to: (1)
convert as much of the sodium carbonate as possible to caustic while (2)
minimising the loss of soluble alumina in the form of precipitates that
normally deport to residue disposal and (3) using lime reagent as effi­
ciently as possible (Fig. 3). The primary objective is to convert sodium
carbonate, although this cannot be independently optimised without
impacting the other two parameters, due to their intrinsic linkage. For
example, the extent of causticisation can be increased by increasing the
lime dose, but that would lead to inefficient lime use and alumina losses
due to unproductive side-reactions, as outlined earlier. Similarly, lime
efficiency and alumina losses can be optimised (by using small lime dose
or very dilute liquors, for example), but at the expense of reduced
Na2CO3 conversion. Operationally, it is important to balance these ob­
jectives for an economically optimal overall plant outcome. The opera­
tional setpoints to achieve such optimisation are influenced by the
specific lime reagent properties, the lime dose response and the pre­
vailing causticisation process conditions.
To optimise performance, causticisation in most modern Bayer re­
fineries occurs in so-called “side-steam” or “outside” causticisation,
which has largely replaced the original “inside causticisation” process
due to inherent inefficiencies of the latter, i.e. high lime consumption
and limited carbonate removal capability (Chaplin, 1971). Much
research has been undertaken to optimise the side-stream causticisation
process (Roach, 2000; Rosenberg et al. 2001; Whittington, 1996;
Whittington and Cardile, 1996; Xu et al. 1997; Xu et al. 1998; Young,
1982) described in early patents (Cagnolatti et al. 1965; Cundiff, 1950).
Generally, best causticisation with least TCA formation is achieved with
a more dilute aluminate liquor at close-to-boiling temperature (Chaplin,
1971). The liquor concentration used as causticisation feed is a
compromise between the causticisation process efficiency and the
amount of carbonate available for removal (Roach, 2000). At the initial
washer stages, the solution temperature is high and sodium carbonate
very concentrated, whereas further down the washer train (Fig. 1) the
temperature is generally lower and the solution more dilute due to the
counter-current wash water. In side-stream causticisation practice, this
generally means that the causticiser feed is derived from the overflow of
the first or second mud washer (Fig. 1). The causticiser solids residue,
which is a mixture of calcium compounds of carbonate, aluminate,
alumino-carbonates and lime impurities (i.e. grits comprising mainly
quartz, MgO, and minerals containing iron and other trace impurities)
reports to the bauxite residue. Hence improvements to lime efficiency
(which reduce the amount of causticiser residue produced and
aluminium lost) also contribute to the process and environmental out­
comes related to bauxite residue production and storage. Efforts to
improve efficiency have included separating the causticisation process
into two stages, the use of additives such as sodium gluconate (Rosen­
berg et al. 1999; Rosenberg 2008) and high temperature conditions up to
170◦ C (de Witt et al., 2000).
1.4. Influence of lime properties on causticisation – Current state of
knowledge
Most of the technical and patent literature on Bayer causticisation
focuses on the effects of process conditions (such as temperature, con­
centration, and mixing), but little attention has been given to the in­
fluence of the properties of lime. The main quicklime properties of
relevance are: reactivity (measured by exothermic reaction rate with
water), CaO content (measured by XRF) and availability (measured by
titration), and impurities (Australian Standard AS 1672.1, 1997; Euro­
pean Standard EN 12485, 2017). The limited literature on the influence
of lime properties also reflects conflicting views. For example, some
studies concluded that low reactivity quicklime (typically associated
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Minerals Engineering 160 (2021) 106664
with low purity lime) was the best reagent for causticisation (Young,
1982; Libby, 1983) and that slaking, prior to or during causticisation, is
detrimental to both the extent of causticisation and the efficiency of lime
use, suggesting that a layer of Ca(OH)2 coating on CaO may inhibit
causticisation. Conversely, other studies found that a high purity lime
sample performed better in causticisation than a less pure industrial lime
(Wellington and Valcin, 2007). Fundamental studies have demonstrated
that it is highly unlikely that Ca(OH)2 coating formation on CaO parti­
cles could inhibit causticisation. Explanations for inhibition are more
likely to be found in the formation of surface coatings of calcium car­
bonate and/or calcium aluminate/alumino-carbonate solid species. Xu
et al. (1998) demonstrated that, for CaO and Ca(OH)2, the rate of
causticisation of sodium carbonate solutions is controlled by the diffu­
sion of CO2–3 ions to the solid surface. In both cases it is the formation of
CaCO3 that progressively blocks the surface and inhibits the reaction,
thereby occluding and rendering unreacted a portion of the Ca(OH)2.
With aluminate solutions the situation is further complicated by the
formation of surface deposits of calcium aluminates (Xu et al. 1997). It is
possible to form TCA in this way (Whittington et al. 1997), but in Bayer
causticisation the intermediate is generally a calcium alumino-
carbonate, variously identified as a hemicarbonate or monocarbonate
depending on conditions (Buttery et al. 2002; Roach, 2000; Rosenberg
et al. 2001). Nevertheless, it has been suggested that direct formation of
CaCO3 from Ca(OH)2 is possible in Bayer causticisation (de Witt et al.
2000; Libby, 1983). Surface deposits and coatings influence overall
causticisation rates by blocking the reacting surface from the liquor.
Differences in reaction rates between types of lime are therefore likely to
be related to the propensity of their solid surfaces to attach and grow
layers of calcium carbonate and calcium aluminate/alumino-
carbonates. There appears to be a scarcity of published studies that
have systematically evaluated lime properties in the context of deter­
mining the impacts of lime dose on the extent of causticisation and lime
efficiency.
1.5. Slaked lime versus dry lime trade-off
Simplicity of reagent sourcing and operation generally mean that
Bayer refineries use a single source of lime, even though the optimal
lime reagent performance parameters may be different for different
process units within the Bayer process circuit (Suss et al. 2008). Lime is
commonly used in the form of slaked lime or milk of lime (MoL). The
advantages of this practice are that slaked lime can be readily distrib­
uted around the plant, typically in a ring-main, with off-take points at
the various process locations and the dose accurately controlled in
response to process requirement. The disadvantage of using slaked lime
is the associated water (typically 80 wt%) injected into the plant liquor
circuit. To overcome the dilution effect of this water, evaporation is
required elsewhere in the circuit (Fig. 1), with significant associated
energy requirements. The option of using a higher Ca(OH)2 solids con­
tent in the slaked lime (i.e. reduced water content) is constrained
because slaked lime pumpability is significantly reduced as solids con­
tent increases above 20 wt%, due to viscosity and shear-thinning effects
(Ruiz-Agudo and Rodriguez-Navarro, 2010). To overcome the high en­
ergy cost associated with evaporation, some Bayer refineries opt to use
dry quicklime dosing in some locations within the plant circuit. Using
dry quicklime, however, may be sub-optimal, depending on the lime
source and process conditions (de Witt et al. 2000) and conventional
agitator reactors may not provide optimal dispersion and mixing of dry
quicklime into process liquors.
1.6. Objectives and experimental rationale
Alumina Bayer refineries often use the available CaO % content of
quicklime as the basis for calculating lime performance. It is important
to note that this metric is determined via an acid titration method that
does not account for slaking, particle size, or reactivity effects and may
C.A. du Plessis et al.
Fig. 4. Sample preparation summary with red dotted lines indicating the comparison pairs for evaluating various lime properties.
therefore be a poor predictor of performance in the target reaction(s), as
has been demonstrated for other lime applications (Ineich et al. 2017).
The purpose of this study is therefore to use a standardised causticisation
dose–response test, with a view to meeting the need for information
beyond simple CaO content to enable more informed process and eco­
nomic decision-making on lime sourcing for the Bayer process. In
developing the test, the influences of lime properties and dose on extent
of causticisation and lime efficiency are evaluated. The results highlight
the effects of individual lime properties, including lime purity, and ad­
ditions such as dry quicklime, dry hydrated lime and MoL. The condi­
tions of the test simulate conditions typical of current side-stream
causticisation practice. The examples shown are for causticisation of
synthetic Bayer liquor using a limited range of lime samples, but the test
is equally applicable to actual plant liquors and all types of lime.
1.7. Definitions used
Lime is the generic term used to describe various forms of calcium
oxide, including: quicklime - a dry reagent of mainly CaO, produced
from the calcination of limestone of which CaCO3 is the main compo­
nent; hydrate or hydrated lime - a dry reagent of mainly Ca(OH)2,
produced from the stoichiometric hydration of quicklime with water;
and slaked lime or milk of lime (MoL) – a slurry of Ca(OH)2 particles
typically in the range of 10-22 wt% solids content, produced from
slaking quicklime in a stoichiometric excess of water.
Soluble sodium carbonate and sodium hydroxide concentrations are
important processing parameters. In this regard A, C and S in this work
have the meanings accepted as standard in the alumina industry: A =
aluminium concentration in units of g/L Al2O3, C = total caustic soda
concentration in units of g/L Na2CO3 equivalent, and S = (C + Na2CO3)
in units of g/L Na2CO3 equivalent.
Causticisation process performance in this study was assessed by
evaluating the extent of causticisation (EC, %), lime efficiency (LE,
%), and alumina losses via unproductive reactions. Extent of caustici­
sation (EC, %), in this study, is defined by the proportion of soluble
carbonate removed from solution by causticisation, expressed as a per­
centage, as determined by solution titration. The nature of solids,
including the precipitates formed, is determined separately by various
analyses. This definition of EC is preferred to the more commonly used
equivalent term “causticisation efficiency” to avoid confusion with LE.
Importantly, EC does not consider the amount of lime used to achieve
the conversion reaction. LE in this study is defined as the molar ratio of
soluble carbonate removed from solution relative to Ca added (total CaO
% as determined by XRF), expressed as a percentage. The advantage of
4
Minerals Engineering 160 (2021) 106664
this metric is that it is readily determined by solution assay (titration
methods) and standard lime analyses methods. LE only determines the
lime efficiency inherent in its properties as a reagent. It does not give an
indication of the productive versus unproductive use of lime (in terms of
the formation of precipitated products: CaCO3, TCA or LDHs), which is
predominantly a consequence of operational process conditions (such as
lime dosage, liquor composition and temperature). The relative forma­
tion of productive versus low productivity precipitation products is
determined by solid analyses, such as quantitative X-ray diffraction.
Maximum extent of causticisation (MEC, %) is defined as the
plateau in EC % as a function of CaO equivalent dose. Maximum
effective dose (MED, %) is defined as the CaO equivalent dose (in g/L)
above which no further increase in EC % occurs. The CaO equivalent
dose is the mass of lime, adjusted for the total CaO% content as
measured by XRF.
2. Materials and methods
2.1. Lime samples
The quicklime and hydrated lime samples used in this study were
from two different carbonate sources. The designated label for each
sample and preparation pathway are summarised in Fig. 4. In each test,
comparison pairs were used, indicated by the red dotted lines. The
interpretation of results was mainly confined within a comparison pair,
rather than between pairs. Most of the lime property comparisons were
conducted using subsamples of carbonate source 1, thereby enabling a
comparison of effects of physical characteristics and slaking on samples
of identical chemistry. Quicklime sample B2 was compared to quicklime
sample D, originating from a different source (carbonate source 2), to
facilitate a comparison of different quicklime chemical compositions.
The key chemical and physical characteristics of all the samples are
summarised in Table 1.
Quicklime sample B2 was prepared from industrial lime manufac­
tured from limestone Carbonate Source 1 (Fig. 4) using conventional
methods (Boynton 1980). The calcination product, with a particle size
range of + 10/-60 mm, was crushed to 100% <5 mm. The < 2 mm
fraction was discarded to yield a + 2/-5 mm fraction, which was then
further crushed to 100% <2 mm to produce B2.
Quicklime samples C1 and C3 were also prepared from Carbonate
Source 1 under laboratory conditions, to produce quicklime samples
with the same chemistry but with different reactivities. These were
achieved by calcining under different temperature conditions (Zanin
et al. 2019) resulting in a high reactivity (C1) and low reactivity (C3)
C.A. du Plessis et al. Minerals Engineering 160 (2021) 106664

Table 1
Compositions of lime samples (% w/w dry). Av CaO = available lime.
Sample label CaO % MgO % SiO2 % Al2O3 % Fe2O3 % SO3 % CO2 % Av CaO % t60 min Size

B2 95.1 1.5 0.3 0.1 0.1 0.1 0.7 93.1 2.2 − 2 mm

D 81.5 4.9 8.3 0.5 0.3 0.8 1.1 80.6 11.3 P80 310 µm
H1 74.6 0.2 0.2 <0.1 <0.1 <0.1 2.4 N/A N/A P50 3 µm
H2 73.0 0.26 1.4 <0.1 <0.1 <0.1 2.9 N/A N/A P50 54 µm
C1 96.9 0.8 0.5 0.1 0.1 <0.1 0.2 95.1 0.2 − 2 mm
C3 96.9 0.8 0.5 0.1 0.1 <0.1 0.1 96.4 8.7 − 2 mm

quicklime sample, respectively. Quicklime reactivity was determined by
the European standard t60 reactivity test, in which t60 is the time in
minutes to reach 60◦ C from a starting temperature of 20◦ C in a slaking
test (Ineich et al. 2017; Zanin et al. 2019).
Quicklime D was prepared from Carbonate Source 2, to yield
quicklime with a different chemical composition and higher levels of
impurities compared to the other quicklime samples. Carbonate Source
2 was crushed to < 1 mm and calcined. The final product was used as is,
with a measured granulometry of 80% passing 310 µm.
Hydrated lime samples H1 and H2 were prepared using conven­
tional hydration methods (Boynton, 1980), also originating from Car­
bonate Source 1. Sub-samples were separated using a laboratory air
classifier to produce a fine Ca(OH)2 particle size sample (H1, 50% <3
µm), and a coarse particle size sample (H2, 50% <54 µm).
2.2. Procedures
2.2.1. Lime dose
Comparisons were conducted as batches of individual test bottles
containing incrementally increasing lime doses. Lime dose increments
were based on a mass equivalent basis, but expressed as CaO equivalent
content (based on the CaO % content as determined by XRF, Table 1), to
normalise for the effect of different chemical compositions of samples
used (Table 1) and to compared slaked and unslaked formats as well as
hydrates on an equivalent basis.
2.2.2. Synthetic Bayer liquor
The synthetic Bayer liquor (SBL) was prepared as a pure sodium
aluminate/sodium carbonate solution by dissolving pure aluminium
hydroxide (Alcan Superwhite) and AR sodium hydroxide in hot deion­
ised water at 90◦ C, followed by the addition of pure sodium carbonate
solution. A 5 L 18/10 stainless steel reactor was used with a magnetic
stirrer hotplate and Teflon stirrer bar. The solution was made up to a
fixed weight (estimated to give the required concentration) prior to use.
The hot mixture was passed through a 0.45 µm membrane filter and
diluted to the required concentration. The target concentrations in the
liquor were: A = 62 g/L, C = 96 g/L, S = 120 g/L, to give target ratios for
A/C = 0.65 and C/S = 0.80.
2.2.3. Slaked lime
Slaked lime (milk of lime) was prepared as a 20wt% solids slurry
(after slaking) by adding deionised water to the dry lime solids in a
stirred vessel and heating to approximately 90◦ C under nitrogen. The
mixture was stirred at temperature until fully slaked. The dilution effect
of water added via the slaking process was taken into consideration in
the interpretation of the results.
2.2.4. Bottle roll batch test
A standard bottle roll batch test (BRBT) was used for dose–response
studies. These tests were conducted in wide-necked Nalgene high-
density polyethylene bottles mounted in a custom-made rotating
carousel positioned within a water bath heated to 95◦ C (Fig. 5). A batch
of bottles was freshly prepared for each test run, with each batch con­
taining a series of increment doses for a selected lime. Each experiment
was therefore a comparison of two batches. This setup enabled indi­
vidual batches with a range of incrementally increased doses and
different lime sample comparison pairs (red dotted lines in Fig. 4) to be
run simultaneously under identical conditions (i.e. with the same
starting SBL and at the same temperature) and the results interpreted as
a function of lime dose. Lime (dry or pre-slaked) was added to each pre-
heated bottle, which was then topped up with synthetic liquor at tem­
perature. The bottles were sealed, shaken and secured in the carousel.
These were then rotated in the water bath at 95◦ C. A standard time of
two hours was chosen to be consistent with common industrial practice
(Roach, 2000). After removal from the carousel, samples of liquor and
solids were taken, and analysed as described below.
2.3. Analysis of samples
A, C & S titrations - A, C and S concentrations were determined by
liquor titration (Connop, 1996), using Metrohm autotitration equipment
and software. Special care was taken to minimise carbon dioxide uptake
by the liquor prior to titration. C and S titrations data were used to
calculate EC and LE respectively. Titration A was monitored but not
reported because it is a relatively insensitive metric. Rather, the loss of
aluminium from the SBL was monitored by XRF analysis of the solids,
while quantitative x-ray diffraction (QXRD) methods were used to
indicate its speciation in the solids.
Elemental and TIC analyses - Diluted liquor samples were analysed
for Al, Ca and Na by ICP-OES. Solids were analysed for Al, Ca, S, Fe, Mg,
Na and Si by borate-fusion wavelength dispersive x-ray fluorescence.
Total inorganic carbon (TIC) analyses were determined for solids using a
LabFit CS-2000 Carbon and Sulphur Analyzer, and for liquors with a

Table 2
Standard deviation values (expressed in %) of the various parameters measured
in experimental reproducibility tests.
Solids addition

Parameter 15 g/L 21 g/L

A 0.18 0.23
C 0.15 0.30
S 0.06 0.10
EC 1.1 1.4
Fig. 5. Diagrammatic representation of bottle roll batch test in a temperature-
LE 1.1 1.5
controlled water bath with rotating carousel.

5
C.A. du Plessis et al. Minerals Engineering 160 (2021) 106664

Fig. 6. Causticisation dose–response curves comparing quicklime samples B2 (a highly reactive, high purity sample) and D (a lower reactivity, lower purity sample)
in slaked (milk of lime) and dry quicklime formats in terms of (a) extent of causticisation (EC) and (b) lime efficiency (LE).

Shimadzu TOC-VCSH Total Organic Carbon Analyzer. plateau, are relevant features of the dose–response curve. To facilitate
Quantitative x-ray diffraction (QXRD) analyses - Dried solids visualisation and interpretation, experimental data (both for EC and LE)
were analysed by x-ray diffraction (XRD) using a Panalytical high- were fitted with an empirical five-parameter logistic equation (Cum­
resolution multi-purpose powder diffractometer (Empyrean) using co­ berland et al. 2015; Gadagkar and Call, 2015; Ineich et al. 2017),
balt-Kα radiation at 40 kV and 40 mA, a Bragg-Brentano high-definition (Eq.10), where: y = extent of causticisation (EC %) or lime efficiency (LE
incident monochromator and PIXcel3D photon counting x-ray detector. %); x = lime dose; d = initial value of y; a = plateau (maximum value of
Data were collected for two hours over an angular range of 5–130◦ 2θ in y); c = inflection point; b = curve sharpness (negative for LE plots); m =
continuous scan mode. The Rietveld method with Bruker TOPAS 5 curve skewness.
software was used for QXRD. The predominant phases detected in the ⎛ ⎞
causticisation products corresponded to the published diffraction pat­ ⎜ ⎟
a− d
terns for calcite, CaCO3 (Markgraf and Reeder, 1985), TCA (katoite), y=⎜
⎝[ ( )− b ]m ⎟
⎠+d (10)
Ca3Al2(OH)12 (Lager et al. 2002), monocarbonate Ca4Al2(OH)12.CO3. 1+ cx

(5.5H2O), (François et al. 1998), and portlandite, Ca(OH)2 (Chaix-

Pluchery et al. 1987). The XRD diffractograms were not consistent with
2.4.1. Experimental reproducibility
the formation of hemicarbonate (Runčevski et al. 2012), which was
Quicklime sample B2 was selected to investigate the test reproduc­
expected based upon previous work (Rosenberg et al. 1999). The QXRD
ibility. Five tests each with dry solids additions of 15 g/L and 21 g/L
data were normalised to give optimum correlation between the calcu­
equivalent CaO to SBL were run as described previously. The standard
lated and analysed element contents.
deviations (%) for the liquor titration values, extent of causticisation,
and lime efficiency were calculated from the results and are shown in
2.4. Dose-response curves for EC and LE Table 2. It is apparent that as the dose increases, so does the standard
deviation. The standard deviation values, however, are excellent and
The EC (Eq. (8)) and LE (Eq. (9)) were calculated from S and C confirm that the test procedure can be applied with confidence and
titration data and CaO equivalent dose (in g/L). provide context for the interpretation and comparison of the results in
subsequent tests.
100 × [1 − (S − C)]
EC(%) = (8)
(S0 − C0 ) 3. Results and discussion
( )
S∙ C
S
− C0
S0
3.1. Quicklime origin and chemical composition – Comparing B2 and D in
56.1
LE(%) = 100 × × (9) dry and slaked formats
CaO equivalent dose (g/L) 106
The dose–response curves for EC % generally follow a pattern of an The influence of lime type (reflected by differences in chemical
increased response relative to dose, up to a plateau, corresponding to composition and reactivity) was investigated using the BRBT described in
pseudo-equilibrium conditions (Roach, 2000; Whittington, 1996). The the experimental section. The extent of causticisation (EC, %) achieved by
dose at which such a plateau is reached and the maximum EC % of the adding dry quicklime to synthetic Bayer liquor (SBL) is shown in Fig. 6a as
a function of lime dose for quicklimes B2 and D, compared in dry
Table 3 quicklime and in slaked dosage formats. Quicklime B2 is high purity, high
Summary of causticisation dose performance parameters for B2 and D. reactivity (i.e. rapid-slaking) quicklime, whereas quicklime D is a lower
reactivity (i.e. slower-slaking), lower purity quicklime containing signif­
Parameter Lime B2 Lime D
icant magnesium and silicon (Table 3). Maximum effective dose (MED) is
Slaked Dry Slaked Dry
defined as the lime dose required to reach 99% of the maximum (plateau)
Maximum extent of causticisation (MEC) 71% 65% 66% 64% value. Lime efficiency (LE, %) is similarly shown as a function of dose in
Maximum effective dose (MED) 15 g/L 17 g/L >24 g/L 22 g/L Fig. 6b. The key performance parameters for these two limes are shown in
Lime efficiency (LE) at MED 62% 49% 31%
Table 3. The relative mass proportions of precipitated mineral phases in
<27%

6
C.A. du Plessis et al.
Fig. 7. Residue composition obtained by QXRD analysis for tests dosed with (a) slaked B2, (b) dry quicklime B2, (c) slaked D, and (d) dry quicklime D, with the
vertical dotted line indicating the Maximum Effective Dose (MED) as determined based on extent of causticisation (EC).
the residues, as determined by QXRD are shown in Fig. 7.
Slaked format comparison - Slaked lime sample B2 reaches a MED of
71% at a dose of 15 g/L CaO, with an LE of 62%. In contrast, the
causticisation curve for slaked lime D does not reach a plateau within
the studied conditions, and at a dose of 24.5 g/L CaO only achieves
65.8% causticisation. LE is also substantially lower for slaked lime D
throughout the dosing range. Based on these dose–response curves, a
substantially lower dose of slaked lime B2 would be required, compared
to slaked lime sample D, to achieve the same causticisation outcome.
The superior performance of slaked lime B2 correlates with the higher
purity and/or greater reactivity, as measured by the temperature rise
during slaking, t60 (Table 1). The finer particle size of lime sample D is
unlikely to be relevant as finer particle size generally favours reactivity,
a factor that did not sufficiently favour lime sample D in this scenario.
The corresponding mineral phases (in Fig. 7a and 7b) are significantly
different between the two lime reagents, with the most striking differ­
ence in the predominance of monocarbonate precipitation at higher
dose levels for slaked lime B2. Calcite is the predominant product at
doses below the MED, while overdosing (i.e. beyond the MED) results in
predominance of monocarbonate, due to depletion of carbonate in
7
Minerals Engineering 160 (2021) 106664
solution. Under these conditions monocarbonate appears to be a stable
reaction product, rather than an intermediate metastable product, at
least within the timeframe of these experiments (i.e. two hours) (De
Silva et al. 2012). The most relevant evaluation of the proportional
solids composition is, however, at the respective MED (vertical dotted
line) dose concentration for each sample, where the proportion of pro­
ductive (calcite) versus low productivity (monocarbonate and TCA)
products, are more favourable (at the MED) when using slaked B2
compared to slaked D. Consistent with other performance parameters,
slaked lime D shows detectable amounts of unreacted lime (portlandite)
throughout the dose range, and a significant higher proportion of TCA
formation at equivalent doses above 9 g/L CaO. These results suggest
that coarse Ca(OH)2 particles become coated with TCA, which prevents
further reaction with carbonate in solution (Xu et al. 1997). It may also
be due in part to the fact that lime D contains a higher MgO content than
lime B2, although the specific effect of MgO on TCA formation is un­
known. The effect of dose on alumina loss from solution is shown in
Fig. 8a, indicating a substantially greater extent of alumina loss at the
MED dose level when using lime D, compared to B2. The effect of lime
dose optimisation on alumina losses can be contextualised by
C.A. du Plessis et al. Minerals Engineering 160 (2021) 106664

Fig. 8. Extent of alumina lost from solution, as a function of CaO equivalent dose for samples B2 and D under (a) slaked and (b) dry quicklime addition regimes.

considering an indicative industrial causticiser feed flow rate of 1700
m3/h and alumina concentration of 62 g/L. Under these conditions, each
1% delta in alumina loss represents 9,200 tonnes of alumina per year.
Dry quicklime comparison – The EC and LE performances of the two
limes are less pronounced when dosed as dry quicklime; dry quicklime
B2 is only marginally better than dry quicklime D (Fig. 6), although dry
quicklime B2 performed substantially better than dry quicklime D in
terms of alumina loss from solution (Fig. 8b). Comparing each lime
sample in dry versus slaked format, the following observations are
made: Lime D performs better as dry quicklime compared to its slaked
form, in terms of EC and LE but worse when considering alumina loss
(comparing Fig. 8a and 8b). Lime B2 performs substantially better when
slaked in comparison metrics (i.e. EC, LE and alumina loss). Greater
alumina loss from solution occurred for lime samples when used in dry
compared to slaked format. This demonstrates that reported observa­
tions of superior performance of dry lime dosage over slaked (or the
converse) might not be generally applicable, and highlights the impor­
tance of explicitly determining the lime dose–response for each appli­
cation scenario and lime type. A comparison of Fig. 7a with 7c illustrates
that, for dry lime dosage, monocarbonate is present throughout the dose
range, even at low dosages, but is not present at similar dosages when
slaked lime is used. This suggests that the hydration reaction of CaO into
Ca(OH)2 and monocarbonate formation can occur in parallel, and that
calcite most likely forms via Ca(OH)2 in preference to directly from CaO.
Comparing the same figures also shows TCA formation even at very low
dosages in the case of dry quicklime. This suggests that dry-added CaO
may be a better substrate for initial TCA nucleation than Ca(OH)2,
whereas Ca(OH)2 preferentially nucleates calcite or monocarbonate.
TCA formation is known to form by secondary nucleation, requiring a
suitable substrate to trigger the nucleation (Salimi and Vaughan, 2016).
3.2. Ca(OH)2 particle size – Hydrated lime H1 vs. H2
Hydrated limes H1 and H2 were produced from the same source to
have a similar chemical composition. H1 is finer (50% − 3 µm) than H2
(50% –54 µm). The EC and LE curves are shown in Fig. 9 and Fig. 10, and
the overall performance results are summarised in Table 4.
The effects of Ca(OH)2 particle size were investigated using hydrated
lime so that samples with identical chemistry could be prepared with
different, quantifiable particle size distributions. The fact that hydrates

Fig. 9. Causticisation dose–response curves comparing Ca(OH)2 hydrate sample H1 (an ultra-fine hydrate) and H2 (a coarser hydrate) in terms of (a) extent of
causticisation (EC) and (b) lime efficiency (LE), where both hydrates were used in dry format.

8
C.A. du Plessis et al.
Fig. 10. Residue composition obtained from QXRD analysis for tests dosed with (a) hydrate sample H1 (an ultra-fine hydrate) and (b) H2 (a coarser hydrate).
were used meant that the influence of Ca(OH)2 particle size could be
evaluated independent of any slaking effects. The results (Figs. 9 & 10
and Table 4) show that finer Ca(OH)2 particles (H1, 50% <3 µm)
perform somewhat better than the coarser H2 (50% <54 µm) Ca(OH)2
particles at intermediate doses, but there is no significant difference at
higher dose levels. The similarity of the EC performance curves (Fig. 9a),
make the mathematically determined MED less relevant for interpreta­
tion purposes, and is therefore not plotted as vertical lines in Fig. 10. An
interesting observation of the solids assay (Fig. 10) is the higher pro­
portion of the precipitated monocarbonate phase generated using finer
particles (H1) at the same dose levels, or even when comparing at the
calculated MEDs. Monocarbonate overtakes TCA precipitation at a dose
of 15 g/L, and overtakes calcite precipitation at 21 g/L in the case of the
fine H1 particles, while for the coarser H2, monocarbonate is signifi­
cantly less pronounced while more unreacted portlandite remains. This
indicates that at dose levels where causticisation reaction demand for
lime is exceeded, finer Ca(OH)2 particles stimulate monocarbonate
formation, compared with coarser Ca(OH)2 particles. There are a range
of factors that may influence Ca(OH)2 particle size in industrial appli­
cations (Ineich et al. 2017). However with all other factors being equal,
slaking conditions influence Ca(OH)2 particle size and hence also, the
subsequent causticisation effects.
3.3. Reactivity of quicklime – C1 and C3
Quicklime samples C1 and C3 are both high purity quicklimes with
an identical chemical composition, but have different reactivities
because of differing calcination conditions, as reflected by different t60
values (Table 1). C1 is an ultra-reactive (t60 = 0.2 min) quicklime, while
C3 is a moderately reactive quicklime (t60 = 8.7 min). These were
evaluated in a comparison pair BRBT, both in slaked and dry quicklime
addition formats to evaluate their dose-responses.
The data in Fig. 11 and Table 5 show a minor difference in the
causticisation performances of slaked limes prepared from these two
quicklime samples with different reactivities. A larger, but still small
Table 4
Summary of causticisation dose performance parameters for H1 and H2.
Parameter H1 H2
Maximum extent of causticisation (MEC) 67% 68%
Maximum effective dose (MED) 24 g/L 27 g/L
Lime efficiency (LE) at MED 35% 31%
9
Minerals Engineering 160 (2021) 106664
difference is, however, observable between the dry quicklime dose for­
mats, with somewhat better performance shown by the lower reactivity
quicklime C3. The relative insensitivity of causticisation performance to
lime reactivity is consistent with the observation that causticisation is
diffusion controlled (Xu et al. 1998) prior to the formation of TCA on Ca
(OH)2 particle surfaces (Salimi and Vaughan, 2016). These results sug­
gest that, for high purity lime in the normal range of reactivity (t60
ranging between 0.5 and 9 min) (Zanin et al. 2019), there is no signif­
icant effect of lime reactivity on causticisation performance. This also
indicates that the differences observed between sample B2 and D, as
described earlier, cannot be attributed only to reactivity differences,
rather highlighting the effect of composition differences, while
acknowledging that chemical composition and reactivity may be
related. For both samples C1 and C3, slaking resulted in a slightly
improved performance compared to unslaked dry quicklime addition,
mirroring the effect observed for sample B2.
4. Industrial implications
The results presented throughout were expressed as CaO equivalent.
The actual quicklime dosage required would be higher, based on the
CaO content of the lime, and might amplify the differences between
quicklime sources when comparing a quicklime dose requirement basis
rather than CaO equivalent content.
The influence of lime dose and properties on the nature of products
in the residues suggests potential future avenues of investigation,
particularly in relation to LDH generation and use. The very high pro­
portion of seemingly stable LDH formation demonstrated using lime B2
(Fig. 7a) with increasing lime dosage, may be of particular interest. If
these findings are confirmed under actual plant conditions, the forma­
tion of LDH may be explicitly targeted and utilised in the Bayer pro­
cesses. The LDH properties that facilitate impurity removal from
alkaline leaching solutions are well known (Perotta and Williams, 1996;
Rosenberg and Armstrong, 2005; Nguyen and Lee, 2019). Deliberate
LDH generation could be promoted for impurity removal. It may also
enable flow sheet modification and optimisation, as suggested by
Rosenberg and Armstrong (2005), in which a portion of the spent liquor
(after alumina precipitation but containing residual sodium aluminate
and sodium carbonate, Vind et al. 2018) is reacted with lime to generate
LDH (Eq. (6) and (7)) resulting in hemicarbonate and monocarbonate,
respectively. Hence, the LDH could then be recovered and used instead
of lime in the causticisation reactor (Eq. 11 or 12). These reactions also
enable the recovery of aluminium.
C.A. du Plessis et al. Minerals Engineering 160 (2021) 106664

Fig. 11. Causticisation dose–response curves comparing an ultra-reactive lime (C1) with a moderately reactive lime (C3) in terms of extent of causticisation (EC) (a,
b) and lime efficiency (LE) (c, d) in slaked (a, c) and dry quicklime (b, d) formats.

[Ca2Al(OH)6]2.(CO3)0.5.(OH).(5.5H2O) + 3.5Na2CO3 →
4CaCO3 + 2NaAl(OH)4 + 5NaOH + 5.5H2O
[Ca2Al(OH)6]2.CO3⋅5H2O + 3Na2CO3 →
4CaCO3 + 2NaAl(OH)4 + 4NaOH + 5H2O
The advantages of this flow sheet modification would be: (1) that the
NaOH content of the spent liquor stream to digestion is increased, (2) the
alumina concentration is reduced, and (3) water is removed from the
spent liquor by the hydration reaction (Eq. (6) and (7)) (Rosenberg and
Armstrong, 2005).
The method described in this study allows for evaluation and po­
tential optimisation of dry quicklime reagent dosing to be compared
(11) with slaked lime reagent addition. The incentive for optimisation of dry
quicklime dosing is significant. Practically, approximately 160 kg water
is injected into a typical outside causticiser process per tonne of alumina
(12) produced. An alumina plant with production capacity of 4 million
tonnes Al2O3, would thereby inject 640,000 tonnes of water into the
causticiser per annum. To overcome the dilution effect of this water,
evaporation is needed elsewhere in the circuit (Fig. 1), requiring
approximately 480,000 GJ per annum in evaporation energy. Assuming
a modest energy price of USD 5 per GJ, this represents a cost of USD 2.4
million per annum.

Table 5 4.1. CO2 emission considerations

Summary of causticisation dose performance parameters for C1 and C3 in slaked
and dry format. The efficient use of lime also warrants consideration in the context of
greenhouse gas (GHG) emissions. Reduced lime consumption will
Parameter Lime C1 Lime C3
reduce an alumina refinery’s overall GHG emissions due to the CO2
Slaked Dry Slaked Dry
footprint inherently associated with lime reagents. In addition to the
Maximum extent of causticisation (MEC) 69% 64% 71% 69% different properties of lime that influence lime utilisation efficiency, the
Maximum effective dose (MED) 20 g/L 21 g/L 16 g/L 17 g/L differences in CO2 footprint of various lime sources are also relevant and
Lime efficiency (LE) at MED 41% 37% 53% 49%
may compound the impact on CO2 emission reduction. The CO2

10
C.A. du Plessis et al.
Table 6
Indicative comparison of CO2 intensity impact, for a scenario (B) where a 20%
reduction in lime consumption is combined with a lower CO2 intensity lime
reagent.
Scenarios
A B
Lime consumption 0.047 0.038 t lime / t alumina
Lime reagent CO2 intensity 1.3 1.1 t CO2 / t lime
Lime CO2 contribution 0.061 0.041 t CO2 / t alumina
Non-lime CO2 contribution 0.503 0.503 t CO2 / t alumina
Overall plant CO2 intensity 0.564 0.544 t CO2 / t alumina
Lime contribution to CO2 intensity 10.8 7.6 %
Overall CO2 footprint reduction 3.5 %
emission intensity of lime reagents range from 0.95 to 1.4 t CO2 / t lime
and are mainly dependent upon the energy efficiency of calcination
kilns, fuel properties used as heat source and the extent of carbonate
conversion (Miner and Upton, 2002). In general, the lowest CO2 foot­
prints are achieved by lime calcined in parallel flow regenerative shaft
kilns, while rotary kilns generally result in larger CO2 intensity (Pir­
inger, 2017). The optimisation of lime utilisation efficiency combined
with CO2 intensity differences can be illustrated by way of an indicative
scenario comparison (Table 6) based on industrially relevant parameters
(Alcoa, 2003).
5. Conclusions
This study examined the influence of lime properties on causticisa­
tion performance using a synthetic Bayer liquor (SBL) in a two-hour
batch causticisation test. The indicators of performance used were the
extent of causticisation, lime efficiency, and proportions of phases in the
residues (where applicable). The lime properties investigated were: (1)
quicklime origin (reflecting different chemistries), (2) slaked versus dry
quicklime dosage regimes, (3) Ca(OH)2 particle size, and (4) quicklime
reactivity.
• Chemistry – A high purity lime performed significantly better than a
low purity lime, particularly when both were used in slaked format, i.
e. 71% extent of causticisation was achieved at 62% lime efficiency
with dose of 15 g/L CaO compared to 66% causticisation at 27% lime
efficiency with a dose of 25 g/L CaO.
• Slaking versus dry addition – Slaking generally resulted in
improved performance when using high purity quicklime, although
the contrary effect of slaking was found for the low purity quicklime.
• Particle size – Ca(OH)2 particle size distribution of reagents dosed in
hydrate format was found to have a modestly beneficial effect on
lime efficiency: dry hydrated lime with 50% <3 µm yielded 67%
causticisation and 35% lime efficiency at the maximum effective
dose, compared to 67% causticisation and 31% lime efficiency for
the same lime with 50% –54 µm.
• Reactivity – Quicklime reactivity was found to have no significant
effect when used in slaked format, and a slightly beneficial effect
when dosed in dry quicklime format.
The data demonstrate that lime properties can significantly influence
causticisation performance and optimal reagent dose in synthetic Bayer
plant liquor. It is likely that performance variations would also be found
when using actual plant liquors and under plant operating conditions.
The method demonstrated in this study may be used to assess a wider
range of processing and liquor conditions, to evaluate and compare the
performance of different lime sources, chemistries and formulations
during causticisation of alumina plant liquors.
Additionally, the method may be used to evaluate the potential
performance benefit of slaking compared with dry quicklime addition.
The data from this study indicated that the differences between quick­
limes when dosed in slaked versus dry reagent addition formats may be
11
Minerals Engineering 160 (2021) 106664
significant. Given the operational effort involved in the slaking process
and the impact of slaked lime dosing on the water balance of Bayer re­
fineries (and subsequent evaporation energy requirements), the
methods described in this study may be used to assess and compare the
relative techno-economic effectiveness of various modes of lime dosing.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgements
The research was funded by Lhoist. The authors wish to acknowledge
the valuable contributions of Fiona Benn, Tuyen Pham, Steve Peacock
and Sophia Surin at the CSIRO, and Catherine Bouchard, Stéphane
Meganck and Laurent Duvivier at the Lhoist Business Innovation Centre.
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