Light Metals 2005 Edited by Halvor Kvande TMS (The Minerals, Metals & Materials Society), 2005
BOEHMITE vs. GIBBSITE PRECIPITATION
Joanne Loh, Chris Vernon, Melissa Loan, Greta Brodie
AJ Parker CRC for Hydrometallurgy (CSIRO Minerals); P.O. Box 90; Bentley, Western Australia, 6982, Australia
Keywords: Gibbsite, Boehmite, Growth Mechanism, Organic Impurities
Abstract
Boehmite (monohydrate) precipitation, in place of gibbsite
(trihydrate), has been discussed in the literature as a possible
energy-saving step in alumina refining. Indeed, the calcination of
monohydrate rather than trihydrate would save approximately
12% of the energy consumed in an alumina refinery. These
previous investigations have not focused on the economic and
technical feasibility of the process. The current investigation takes
a pragmatic approach, measuring precipitation rates, determining
product phase and particle size distribution, and assessing the
impact of impurities and probe species in an attempt to determine
the viability and possible improvements to such a process. The
present work indicates that boehmite precipitation rates are
approximately 2 orders of magnitude slower than for gibbsite
under identical conditions. Agglomeration seems not to occur.
The particle size distribution is too fine and the product is
unsuitable for calcination. However, the work has further
improved the fundamental understanding of gibbsite precipitation
and a hypothesis for the mechanism will be presented.
Introduction
Gibbsite (Al(OH)3) is the usual precipitation product from Bayer
alumina refineries. Gibbsite undergoes calcination to produce the
final product alumina (Al2O3) (1). It has been estimated that the
energy required to calcine gibbsite to alumina is ~ 2 GJ t-1 Al2O3
[1]. This represents ~ 18 % of the total energy consumption of an
alumina refinery (based on an average total energy consumption
of ~ 11 GJ t-1 Al2O3 [2]).
2Al(OH)3 o Al2O3(s)  3H 2O(g) (1)
Substantial energy savings achieved through the precipitation and
calcination of boehmite (AlOOH), in place of gibbsite, was
proposed by Filippou and Paspaliaris [3]. Calculated from
standard thermodynamic data, the energy required to convert
boehmite to alumina is ~ 34 % of the energy required for gibbsite
conversion. This translates to an energy saving of 12 % of the
total energy consumption equating to a saving of AUS$60 M per
annum in Australia alone (based on average cost and energy
consumption of Australian refineries).
On the basis of this preliminary analysis, the prospect of replacing
gibbsite precipitation with boehmite precipitation in the Bayer
process is clearly worth exploring. While much research into
boehmite precipitation has been carried out in the last decade, the
focus was not on the economic viability of boehmite precipitation,
comparative precipitation rates, nor on the product quality
required by smelters as end users of alumina.
The present work was undertaken to replicate previous work and
to provide a more commercially focused assessment (kinetics,
product characteristics and product phase) of boehmite
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precipitation in comparison with gibbsite precipitation. The effect
of common refinery variables (such as caustic concentration,
initial supersaturation, inorganic impurities), solution cations and
model organic compounds were also investigated.
Experimental
Seed Material and Experimental Conditions
Table I lists the median particle size and surface areas of the seed
material used in the present work.
Table I. Median Particle Size (D[v, 0.5]) and Surface Area of
Boehmite and Gibbsite Seed Material
Seed Material D[v, 0.5] (Pm) Surface Area (m2 g-1)a
Boehmite 6.02 3.9
Gibbsite 86 0.11
a
measured by 5 point N2 BET
Boehmite seed material was prepared by a hydrothermal reaction
of gibbsite with water at 200 °C (4 h) in an autoclave. The
product was pressure filtered through 0.45 Pm Supor membrane,
washed with hot deionised water and dried overnight (60 °C).
Boehmite was the only phase as determined by powder X-ray
diffraction. Scanning electron microscopy (SEM) revealed large
hollow particles, artefacts of the hydrothermal reaction consisting
of diamond shaped particles (Figure 1a) with smaller aggregates
of diamond shaped particles (Figure 1b).
In order to make valid comparisons between phases, gibbsite-
seeded experiments were performed under corresponding
conditions for boehmite precipitation. Gibbsite (C31 hydrate,
Alcoa World Alumina) was used as gibbsite seed (Table I). Due
to the very low surface area, matching the total boehmite seed
surface area at a seed loading of 230 g L-1 required a
corresponding gibbsite seed loading of 8150 g L-1. The resulting
gibbsite precipitation rate would be too fast for a sensible
comparison thus, gibbsite was also used at a seed loading of
230 g L-1 and appropriate allowances made when comparing rates.
Gibbsite seed consists of large aggregates of hexagonal crystals
(Figure 1c).
Synthetic sodium aluminate liquors were prepared by dissolving
gibbsite (C31 hydrate) into a heated NaOH solution (~ C600) at
atmospheric pressure. The solution was pressure filtered through
0.45 Pm Supor membrane and the organic additives (as required)
were added to the cooled solution prior to the volume being made
up (to C200 g L-1 as Na2CO3). The solution was pressure filtered
again prior to use.
Bayer plant liquor was also used in the present work. The liquor
was redigested at atmospheric pressure to increase the A/C ratio to
match the synthetic liquor initial concentrations. Redigestion
occurred at temperature just above boiling (~ 110 °C, 1 h) to
reduce the further degradation of the organic material present in
the liquor. The plant liquor was pressure filtered through 0.45 Pm
Supor membrane and diluted to the required volume and C.
20 Pm 2 Pm
a b
20 Pm
c seed. The hexagonal and blocky shape suggests that the seed
Figure 1. SEM images of (a) large and (b) small particles of
Boehmite seed and (c) Gibbsite seed.
Boehmite precipitation leads to a very high apparent solubility.
The alumina concentration in a boehmite-seeded solution, left to
precipitate for 216 hours, was approximately 2.3 times higher than
the measured boehmite solubility [4]. In general, gibbsite exhibits
only a slight increase in apparent solubility, approximately 2 %
higher than measured gibbsite solubility after 264 hours of
precipitation. This metastability has been noted previously by
Panias [5].
Due to the length of the experiments falling around 216 hours, the
apparent boehmite solubility (A*Boehmite apparent = 79 g Al2O3 L-1,
estimated from experimental results), was used to calculate the
initial supersaturation (E=A/A*) rather than the equilibrium
boehmite solubility that is normally used. The experimental
conditions which promote boehmite precipitation were as
follows:Eapparent = 1.67, A/C 0.71, C205 at 90 °C. The sodium
aluminate solutions used for gibbsite precipitation were prepared
to this supersaturation for comparison. The solubility of boehmite
in potassium hydroxide solutions was measured and there was no
significant difference to the reported boehmite solubility in
sodium hydroxide [4]. Model organic compounds were also
added to the liquor to determine their effect on boehmite
precipitation in comparison to their known effects on gibbsite
precipitation. It was assumed that the low concentration of the
organics (mmol L-1) would have no significant effect on the
solubility of gibbsite or boehmite. These compounds were used
without further purification.
Experimental Procedure
50 mL aliquots of the liquor were pipetted into a number of
250 mL Nalgene polypropylene bottles and equilibrated to the
desired temperature for 15 minutes in an end-over-end tumbling
bottle roller. Seed was then added to the liquor and the bottle
resealed. The bottles were then returned into the bottle roller for
the required time. Sampling consisted of the removal of one
bottle and the whole contents constituted the sample for that time
interval. The sample was vacuumed filtered (0.45 mm Supor
membrane) and the solids washed and dried.
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Analytical Techniques
The liquor filtrate was analysed for alumina, caustic and total
caustic concentrations using the Worsley titration method [6].
The solids were characterized by X-ray diffraction (XRD),
scanning electron microscopy (SEM) and particle size distribution
(PSD, laser diffraction).
Results and Discussion
Previous Work
The majority of the previous investigations into boehmite
precipitation have been carried out by a research group led by
Paspaliaris and Panias. Very few descriptions of the seed source
or general characteristics of the seed used in those experiments
were given. The few SEM images published recently [5, 7] show
very large ‘seed crystals’ with nuclei on the surface. The size of
the ‘seed crystals’ ranged from ~50 to 100 Pm (based on the scale
bar provided) which is much larger than the reported size of the
crystals could be gibbsite. The presence of gibbsite in the product
was not reported by those authors.
While high efficiencies (72 g Al2O3 L-1) have been reported for
boehmite precipitation [8], they were calculated over 48 hours of
precipitation at a seed loading of 1200 g L-1. The median
diameter of the products was 10 Pm. The transfer of these
precipitation conditions to industry would significantly decrease
both productivity and product quality.
In the present work, repetition of standard boehmite precipitation
experiments initially produced only boehmite, however after 24
hours, the product contained significant amounts of gibbsite.
Boehmite was reported as the only product in the literature. A
doubling of the median particle size through seed recycling (5
cycles of 24 hours, 1200 g L-1 seed loading) was reported [5].
However, this was not observed in the present work, where the
final size of the product observed was only 1.3 times that of the
original seed. Using a coarser boehmite seed (D[v, 0.5]=32.7 Pm)
[9], particles > 80 Pm in size were produced. Agglomeration was
reported for small particles as well as the larger particles, although
no conclusive data was reported and no SEM or XRD evidence
was presented.
Precipitation Kinetics
While the literature contains no quantitative comparisons between
the rates of precipitation of gibbsite and boehmite, kinetic rate
equations for boehmite precipitation have been reported [7, 10].
Boehmite precipitation has been reported to be up to one to
several hundred times slower than gibbsite for the same
supersaturation [10], although no information about the
experimental conditions was given.
Boehmite and gibbsite seeded precipitation experiments were
carried out under identical conditions (except for total seed
surface areas and seed size, see Seed Material and Experimental
Conditions). The gibbsite precipitation rate was significantly
faster than the boehmite precipitation rate (Figure 2). Indeed, the
majority of the precipitation of gibbsite had already occurred by
24 hours. In addition, the surface area of the gibbsite seed is
approximately 3 % of the total surface area of the boehmite seed.
Using standard expressions for the precipitation rate for gibbsite, a As expected, a high initial supersaturation (E=4.2 based on
calculated rate constant for gibbsite precipitation is approximately equilibrium boehmite solubility or Eapparent=1.8, A/C 0.7)
200 times higher than for boehmite. increased the initial boehmite precipitation rate. However, the
1.7 increased rate can be attributed to gibbsite formation (gibbsite
Gibbsite accounted for 60 % of the sample at 100 g L-1 seed charge, while
*
1.6 Eapparent=A/A apparent 16 % of the sample was identified as gibbsite at 230 g L-1 seed
Boehmite
Supersaturation E
1.5

1.4
1.3
1.2
1.1 *
E=A/A
1.0
0 25 50 75 100 125 150 175 200 225 250
Time (h)
Figure 2. The comparison of desupersaturation rates in boehmite
and gibbsite seeded experiments under identical experimental
conditions.
Gibbsite was the dominant phase from the gibbsite-seeded
experiment with very small amounts of boehmite (< 1 %).
Gibbsite nuclei agglomerated to form large aggregates (> 20 Pm).
The product from boehmite precipitation experiments was
predominantly boehmite with trace amounts of gibbsite (< 1 %).
Effect of Caustic Concentration
Increasing the caustic concentration (at constant supersaturation
and temperature) from 100 to 300 g Na2CO3 L-1 decreased the rate
of boehmite precipitation, similar to the effect on gibbsite
precipitation [11, 12].
Significant changes in the crystal morphology of the gibbsite
products precipitated from these solutions were observed [12]. At
low caustic concentration (~100 g Na2CO3 L-1) acicular
(elongated) crystals are produced. At higher caustic
concentrations (~300 g Na2CO3 L-1) gibbsite crystals tend to be
more blocky. No significant morphological changes occurred in
the boehmite products with changes in caustic concentrations.
At all the investigated caustic concentrations, only gibbsite was
observed from gibbsite-seeded experiments. Increasing the
caustic concentration from 100 to 300 g Na2CO3 L-1 increased the
amount of gibbsite present in the product from boehmite-seeded
experiments from 0 to 8 % (as estimated from XRD). This
implies that higher caustic (or sodium ion) concentration favours
gibbsite precipitation in a boehmite-seeded experiment.
Effect of Initial Supersaturation
It is well established that by changing the initial supersaturation of
the liquor, the different growth processes (nucleation,
agglomeration, slow growth) observed in gibbsite precipitation
may be separated and investigated individually to some extent
[13-15]. The effect of supersaturation (at constant caustic
concentration and temperature) on boehmite precipitation was
investigated to firstly determine if similar growth processes
occurred in boehmite precipitation and secondly, whether they
could be separated and investigated individually.
205
charge after 24 hours). The high initial supersaturation promoted
gibbsite nucleation.
SEM images revealed boehmite crystals adhering onto the surface
of gibbsite crystals (Figure 3a). Further adhesion of boehmite
crystals onto those already attached did not occur. Further growth
of the gibbsite occurred around the boehmite particles such that
while boehmite is further incorporated into the gibbsite crystal, it
is never completely grown over (Figure 3b). These observations
indicated that with a high initial supersaturation, boehmite, having
a different crystal structure to gibbsite, could adhere onto gibbsite.
However, as precipitation proceeds and supersaturation decreases,
gibbsite only precipitates onto gibbsite crystals, resulting in an
increase in size, and further boehmite adhesion ceases.
2 Pm 2 Pm
a b
Figure 3. SEM images of (a) gibbsite nuclei covered with
boehmite particles and (b) gibbsite growth around the boehmite
particles.
Co-precipitation of gibbsite significantly changed the PSD of the
product. There is a large increase in the percentage (by volume)
of particles > 10 Pm in size and this has been attributed to the
agglomeration of gibbsite crystals and the adhesion of boehmite
particles on the gibbsite agglomerates.
Decreasing the initial supersaturation (E=3.4 based on equilibrium
boehmite solubility or Eapparent=1.5, A/C 0.57) correspondingly
decreased the precipitation rate. Boehmite was the major phase in
the products with gibbsite accounting for < 1 %.
Due to the interference of gibbsite in the boehmite-seeded
experiments, no definite conclusions could be made with regards
to whether the growth processes observed in gibbsite precipitation
occur in boehmite precipitation at different initial
supersaturations. However, it has been observed that boehmite
agglomeration does not occur to any significant extent.
Effect of Solution Cation – Sodium vs. Potassium
The substitution of potassium for sodium in a gibbsite-seeded
aluminate liquor increased the gibbsite precipitation rate [16]. For
the first five hours of the precipitation experiment, the boehmite
precipitation rate in potassium aluminate liquor was significantly
faster relative to the precipitation rate from a sodium aluminate
liquor. By 168 hours, the yield had increased by 20 g L-1. Using
a common equation applicable to gibbsite growth (2), where SA is
the surface area and E is the supersaturation with respect to
boehmite, it was possible to arrive at a temperature-dependent
growth rate constant (kT) for each experiment.
dAl2O3
- kT SAE 2 (2)
dt
Where potassium was substituted for sodium, the rate constant
was approximately 5 times greater for boehmite precipitation.
Applying the same equation to gibbsite precipitation, the rate
constant was approximately three times greater from the
potassium liquor. Thus the potassium ion has had a greater effect
in increasing the precipitation rate for boehmite than for gibbsite.
Boehmite was the only phase present in the product as determined
by powder X-ray diffraction. No gibbsite formation occurred (up
to 168 hours) while gibbsite had been observed by this time in the
other boehmite precipitation experiments in sodium aluminate
liquors. This could indicate an ‘inhibitory effect’ of potassium on
gibbsite nucleation in boehmite seeded experiments under
boehmite precipitation conditions, although there is no such effect
on gibbsite precipitation where the liquor is seeded with gibbsite.
The substitution of potassium for sodium in synthetic aluminate
liquors changed the mechanism of gibbsite growth, resulting in
acicular crystals (Figure 4a). No acicular crystals were observed
from the boehmite-seeded potassium aluminate liquor. However,
changes in the crystal morphology were observed and consisted of
straight edged diamond crystals becoming more rounded (Figure
4b).
5 Pm 2 Pm
a b
Figure 4. Products from potassium aluminate liquor; (a) gibbsite
seeded and (b) boehmite seeded.
Effect of Organic Impurities
The mechanism by which organic compounds inhibit gibbsite
precipitation is commonly attributed to a surface process [17].
This occurs through the reduction of the number of active sites on
the seed surface, thereby reducing the number of available sites
where precipitation can occur. Comparing the effects of model
organic compounds on gibbsite precipitation with the effects on
boehmite precipitation will increase knowledge and understanding
of the surface properties of boehmite. Two well-known gibbsite
inhibitors (sodium gluconate and sodium tartrate) and an organic
impurity present in Bayer liquor (sodium acetate) were
investigated.
Sodium Gluconate (4 mmol L-1 concentration). Sodium gluconate
is one of the strongest known inhibitors of gibbsite precipitation in
sodium aluminate solutions [13]. From the present results,
sodium gluconate inhibits growth (presence of an induction
period, decreased precipitation rates) and suppressed secondary
nucleation (increase in the percentage by volume of particles with
sizes > 80 Pm) of gibbsite by adsorbing at the active growth sites.
While surface nucleation was still observed (Figure 5a), these
206
occurred at less energetically favourable sites, indicating that
these sites can still grow (at high supersaturations) while the more
active sites have been poisoned. The new sites create additional
adsorption and growth sites until these outweigh the poisoning
capability of the gluconate and growth then continues as per
normal. Gibbsite was the only phase detected.
The effect of sodium gluconate on boehmite precipitation is more
pronounced than for gibbsite precipitation. The induction period
for boehmite was approximately 2 to 3 times that of the induction
period of gibbsite at the same sodium gluconate dosage
concentration. Blocky crystals were observed in the product
(Figure 5b). Boehmite was identified as the only product.
2 Pm 2 Pm
a b
Figure 5. The effect of 4 mmol L-1 sodium gluconate on (a)
nucleation on the gibbsite seed surface and (b) the crystal
morphology of boehmite.
The total surface area of boehmite seed used was approximately
38 times that of the gibbsite seed. This, coupled with the
inhibitory effect of sodium gluconate being a surface process,
indicates that the boehmite seed surface has significantly fewer
active sites than gibbsite and the less active (inactive) sites do not
readily form new growth sites as is observed for gibbsite.
Sodium Tartrate (4 mmol L-1 concentration). Sodium tartrate had
a reduced inhibitory effect on both gibbsite and boehmite
precipitation than sodium gluconate at the same concentration.
This is in agreement with the observation that an organic
compound with a higher number of carbon atoms and hydroxyl
groups would have a greater extent of inhibition [18]. No
induction periods were observed for gibbsite precipitation.
Scanning electron micrographs revealed mass (elongated) nuclei
formation on the seed crystals, predominantly in areas of rough
surfaces and on prismatic faces (Figure 6a). The observed
morphology is in agreement with previously reported observations
[19, 20]. Gibbsite was the only phase detected.
The boehmite precipitation rate was only slightly reduced in the
presence of sodium tartrate and the induction period was
increased by one hour. This indicated that tartrate adsorption is
less specific on boehmite and that growth sites may not be the
preferred adsorption sites. SEM images reveal rounded diamond
shaped crystals (similar to Figure 4b) with some plate-like nuclei
and needle formation also present (Figure 6b). Boehmite was the
only phase in the product, indicating that gibbsite nucleation had
been suppressed.
Sodium Acetate (0.5 mol L-1 concentration). There was no effect
of sodium acetate on gibbsite or boehmite precipitation. No
significant changes to the crystal morphology of the seed and
nuclei were observed for either seed types. The products from
these experiments were the same as the seed type – i.e. gibbsite
from gibbsite-seeded experiment and boehmite from boehmite-
seeded experiment. While sodium acetate appears to have no
effect on gibbsite precipitation, it seems to suppress gibbsite
nucleation in boehmite-seeded experiments.
2 Pm 2 Pm
a b
Figure 6. The effect of 4 mmol L-1 sodium tartrate on nuclei
formation on (a) gibbsite and (b) boehmite seed surfaces.
Boehmite Precipitation from Plant Liquor
Boehmite precipitation tests were also carried out in plant liquor
containing native organic impurities. As expected, the
precipitation rate was lower in the plant liquor relative to a pure
synthetic Bayer liquor under the same conditions. Boehmite was
the only phase identified in the product.
Conclusions
Despite optimism in the literature, it is unlikely that boehmite
precipitation will ever compete with or replace gibbsite
precipitation in the Bayer process. The most compelling reasons
for this are:
x The precipitation rate for boehmite is approximately
200 times slower than that of gibbsite.
x Boehmite forms with a small crystallite size and does
not seem to grow any larger than 30 Pm.
x Boehmite does not tend to agglomerate to any great
extent and apparent particle aggregation processes seem
to be a consequence of nucleation on existing slow-
growing particles.
x Boehmite ‘agglomerates’ are fragile and tend to have
morphologies that would not survive handling or
calcination, resulting in fine particles.
The solutions proposed in the literature to overcome the problems
of slow kinetics and low yield of boehmite precipitation are not
economically feasible. For example, kinetic inhibition has been
described as being due to poisoning of the active surface area by
hydroxyl ions. To ‘overcome’ this inhibition, it was proposed that
neutralization of caustic would increase the precipitation rate.
This is highly unattractive to an alumina refinery, as caustic soda
will have to be replaced or regenerated.
Despite the negative findings on the economic feasibility of
boehmite precipitation as a replacement for gibbsite precipitation
in the Bayer process, the commonalities and differences between
boehmite and gibbsite precipitation still provided valuable
information about gibbsite precipitation mechanisms. A new
growth mechanism is presented, incorporating present and past
observations.
The ‘active’ aluminium species or the composition of the ‘growth
units’ participating in gibbsite precipitation remains yet to be
identified. While precipitation may be dependent upon the
addition of ‘growth units’ from the solution onto the growing
crystal surface, interactions of the aluminium species in solution
could play an important role in influencing outcomes such as
207
nucleation and precipitation rates, crystal morphology and the
incorporation of impurities into the crystal. The majority of
results from investigations into solution speciation in caustic
aluminate liquors confirm the general consensus that aluminium is
predominantly present as a four-coordinated monomer, the
aluminate ion (Al(OH)4-). However, there is evidence that
polymeric or oligomeric aluminate species (clusters) are also
present in the solution [21-23]. Although the exact nature of their
composition is unknown, it is likely that the clusters are gibbsite-
like in structure as they are precursors to gibbsite nuclei. Cluster
formation occurs in the bulk solution and may exist also on the
crystal surface. While no distinct interfacial layer at the growing
gibbsite crystal surface has been observed spectroscopically [22],
liquor-like clusters may still be present in the interfacial layer.
Clusters having the same composition, both in the bulk solution
and in the interfacial layer, would be spectroscopically
indistinguishable from each other and a ‘distinct’ layer would not
be detectable.
Precipitation occurs through the addition of growth units onto the
surface. This may occur through the movement of the growth unit
onto the surface or through the rearrangement of a cluster near the
surface. Boehmite precipitation occurs with the addition of
boehmite growth unit onto a boehmite surface. Clusters, close to
the boehmite growing surface, could impede the movement of
boehmite growth units to the surface. Structural rearrangement of
a gibbsite-like cluster to form a boehmite growth unit is less
energetically favourable due to its high stability. Gibbsite is more
likely to form due to the existence of the pseudo-gibbsite structure
of the clusters and explains why gibbsite was a major product in
our boehmite experiments.
Disruption or the prevention of gibbsitic cluster formation would
then remove the propensity for gibbsite to form. This has been
demonstrated through the substitution of potassium ions for
sodium ions in solution. Only boehmite was precipitated from a
potassium aluminate solution while gibbsite was the major phase
from a sodium aluminate solution under conditions promoting
boehmite precipitation. Molecular dynamics modeling has
shown that less stable clusters are formed with potassium ions
than with sodium ions [14, 24]. Sodium ions appear to have a
stabilizing effect on the clusters of aluminate ions in solution.
This stabilizing effect was also observed by dynamic light
scattering measurements – sodium aluminate solutions had a
longer nucleation induction period than for potassium aluminate
solutions [14]. The substitution of potassium for sodium results
in the formation of ‘looser’ clusters (preventing gibbsitic cluster
formation), decreasing the predisposition for gibbsite nucleation
in seeded solutions.
Reduction of the initial supersaturation and caustic concentration
(at constant supersaturation) also produced boehmite as the only
product from boehmite-seeded sodium aluminate liquor. The
formation of (gibbsitic) clusters may also be reduced in less
concentrated liquors, leading to the precipitation of boehmite as
the dominant growth mechanism. In addition to changes in the
product phase, the precipitation rate for both boehmite and
gibbsite increased (7 to 8-fold) with a decrease in caustic
concentration. This may be attributed to the increased mobility
through the solution by the growth units to the growing surface.
The same magnitude of the increase in the precipitation rates in
boehmite and gibbsite most likely indicates that the cluster
formation is similar in both solutions and that cluster formation is
reacts similarly to changes in liquor concentration (speciation).
The addition of simple organic compounds and the presence of
native organic compounds in plant Bayer liquor also prevented
gibbsite precipitation in boehmite-seeded experiments. The effect
of the organic compounds appears to be through either the
disruption of the gibbsitic clusters (preventing the cluster
formation) or the stabilization of the clusters (such that the energy
advantage for gibbsite to precipitation is decreased) rather than
through the promotion of boehmite precipitation. This is evident
in the lack of morphological changes to boehmite in the presence
of these additives while there are significant changes to gibbsite.
This indicates fewer interactions between boehmite and the
organic additives. These observations also indicate that boehmite
growth may occur through a different intermediate species to
gibbsite growth.
Acknowledgements
The authors gratefully acknowledge Phan Khanh for particle size
distribution measurements and Ian Davies for powder X-ray
diffraction spectra collection. The authors also gratefully
acknowledge the Light Metals Flagship Program (CSIRO) for its
generous sponsorship of this work.
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