WHAT IS THE KINETIC ORDER OF DESILICATION?

Jones F1* and Smith P2

1
AJ Parker CRC for Integrated Hydrometallurgy Solutions, Nanochemistry Research Institute,
School of Applied Chemistry, Curtin University of Technology, Perth, WA, Australia
2
AJ Parker CRC for Integrated Hydrometallurgy Solutions, CSIRO Minerals, WA, Australia
Abstract
Desilication of liquor is an important process in the digestion of bauxite, particularly with respect to its ability to influence the
silica remaining in the liquor to precipitation and, ultimately, in the gibbsite product. Not surprisingly therefore, desilication
kinetics is an area of considerable interest. A common desilication rate equation from the literature is:
d[SiO2]/dt = k([SiO2]t – [SiO2]eq)n
in which the order (n) has various values ranging from 1 through to 3. Can all these values be correct and why, as some
authors have found, is n a function of the seed added?
This paper tries to shed some light on the inconsistencies found in the literature and presents new desilication data at low
and moderate seed charges. We find that use of this equation does lead to the situation where n is a function of surface
area added. However, how can this be physically interpreted? In this paper we discuss the kinetic equation, where its use
is valid and whether it is suitable to describe the desilication reaction at all. In addition, we present results of DSP seeding
on desilication and show that the behaviour is challenging our understanding of the desilication process.

Keywords: desilication, kinetics, growth, secondary nucleation, DSPs

Introduction and show that the data can be explained not only by a growth
mechanism but also by a secondary nucleation mechanism.
In the study of the kinetics of desilication in the Bayer process, it
is common to use the following equation: Methods and Materials
d[SiO2]/dt = k([SiO2]t – [SiO2]eq)n (1) Spent refinery Bayer liquor (from an unidentified refinery) was
obtained courtesy of CSIRO and filtered prior to use through
where t is time, [SiO2] is the concentration of silicate in solution a 0.45μm membrane. Two solids were used for seeding
expressed as gL-1 SiO2, k is the rate constant and n is the order experiments, they were characterised according to their phase
(also a constant). Different studies have found the need to use (XRD) and size (Malvern Mastersizer) and surface area (BET
different values of n ranging from 1 through to 3 (1-7). However, isotherm, N2 as carrier gas). They are labelled DSP 1 and DSP
let us take a closer look at this equation. It is essentially the 2 throughout this paper. DSP 1 was a laboratory made DSP
classic rate equation when one species reacts with another to produced from kaolin in synthetic liquor, while DSP 2 was a
form a product, where it is assumed that the reaction is only ground heater scale - Table 1.
dependant on the remaining silicate in solution. While the
difference in the silicate concentration to the equilibrium value Table 1. Seed characteristics
is a measure of the driving force for precipitation, this is not the Phase Size Surface area
relative supersaturation nor supersaturation ratio commonly d50(μm) (m2/g)
used in crystallization theory. This equation is purely empirical DSP 1 Sodalite with some 5 μm 5.03
and gives no mechanistic information other than whether the muscovite left over from
kaolin dissolution
reaction is diffusion limited (8). Since desilication products are
crystalline, zeolite-like compounds that crystallize during the pre- DSP 2 Heater scale 200 μm 2.38
hydroxycancrinite
digestion (desilication step) stage of the Bayer process, it would
be useful to have more fundamental information regarding the sulfated alumino-silicate
crystallization mechanism for these solids. sodalite

A better description of the desilication process would, therefore,
incorporate these more fundamental forms of supersaturation.
One possibility is a modification of the semi-empirical kinetic
equation for growth, such that:
d[SiO2]/dt = kg(SR-1)n
Here, kg is the rate constant for growth, SR is the supersaturation
ratio and n is the growth order. The important difference here is
the use of SR=[SiO2]t/[SiO2]eq rather than to the simple difference
in the two values as is found in equation 1. In this semi-empirical
growth rate equation, n=1 suggests diffusion controlled growth,
n=1-2 growth via screw dislocations and polynuclear growth
gives n>2.
In the following paper we analyse the results of two sets of data,
one at moderate seed charge and the other at low seed charges
DSP produced sulfated alumino-silicate ~10 μm Not assessed
from
experiments and mixed phase sodium
aluminium silicate
DSP 1 consisted mainly of sodalite while DSP 2 also contained
(2) cancrinite as would be expected from heater scale. All samples
showed DSP products known to form under various Bayer
conditions.
A seeding experiment involved equilibrating 80 mL spent liquor
in a Nalgene flask at 90°C using a bottle roller. Sodium silicate
solution, equilibrated to temperature, was added to the liquor
(t=0) to obtain the desired final silicate concentration and 1
minute later seed material was added to the mixture. At known
intervals, a 3 mL sample was taken from the liquor, filtered and
a known volume diluted by 10 into caustic at the same TC value
(Total Caustic in g/L equivalent Na2CO3). Analysis of Si and Al

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 was performed using ICP. The initial SiO2 concentration was
either above 3 gL-1 (high supersaturation) or below 3 gL-1 (low
supersaturation).
Results and discussion
Data to be analysed was collected on the desilication of a spent
Bayer liquor under different SR and solids seeding conditions. In
the first data set, the initial SiO2 concentration was above 3 gL-1
while in the second data set the initial concentration was below
3 gL-1. In addition the two sets altered in their seeding conditions,
set 1 used seed conditions of 10-100 gL-1 while set 2 had seeding
conditions 0.5-6 gL-1.
The desilication rate in the absence of any seed was determined
for each. For both sets (see Figure 1a for data set 1, data set
2 not shown) a linear rate equation (based on Eqn 1) was
reasonable. However, the use of Eqn 1 for the seeded desilication
experiments resulted in some strange results as outlined in
Table 2. Apart from some very bad fitting residuals, there are
some other interesting aspects to the fit using Eqn 1. Firstly, the
order appears to depend on the initial silicate concentration
(not shown), where the lower SR data set only required n=1, the
higher SR dataset required n=2 and 3. However, this is not so
critical because it is well known that growth mechanisms can
and do change with changes in SR (8), thus the two data sets
may well have been on the cusp of such a mechanistic change.
It must be stressed that in the absence of solids both liquors
were reasonably fitted with n=1 and would tend to negate such
an argument. Of greater concern is that even when the initial
silicate concentration is the same, the order of the reaction is
dependent on the seed mass (or surface area) present. While
this supports the different values of n in the literature (1-7) it
does not give confidence in the use of Equation 1 as a suitable
relationship for the desilication kinetics.
Table 2. Mass of DSP 1, or DSP 2 used, order of rate equation
which gave the best fit, the rate constant calculated for
rate equation 1 and the sum of squares of the residual
for each fit
seed added
Order, n k value
(g/100 mL)
DSP 1, 1 2 0.3760
In this case, there is no change of n with solids (n=2) and the
overall rate equation shows a small steady increase with solids
charge (see Figure 1b) at the higher solids loadings. Despite
some large errors at the low solids loading this gives a slightly
decreasing rate constant when surface area is taken into
consideration (Figure 2a). That is
kg(SR-1)n = k”A(SR-1)n (3)
There was no overall improvement nor deterioration in the
residuals, with some fits being better while others were worse.
Thus, growth is a possible mechanism provided the proper SR
term is used.
There is, however, a third option; and that is secondary nucleation.
This possibility arises directly from the observation that the
desilication rate using eqn 1 is dependant on the surface area.
The rate equation for secondary nucleation is (8):
dN/dt = knMj(SR-1)n (4)
where N is the number of nuclei formed, M is the suspension
density (wt%) of seed present, n and j are constants and kn is
the rate constant for secondary nucleation. If we assume, as
per the growth rate, that the loss of silicate in solution is due to
nucleation and that a better descriptor to suspension density is
suspension surface area then the following would hold:
d[SiO2]/dt = k’Aj(SR-1)n (5)
Let us now analyse the data according to equation 5.
The data (Figure 2b), although showing different values to
Figure 1b, show a great deal of similarity. This is, however, very
susceptible to the j value. At the value shown (j=0.5) the data is
quite flat for the experiments at the higher solids loading while
the data is also reasonably constant but lower at the lower solids
loadings. This might be related to the different supersaturation
regimes. A constant k’ value is more reasonable than decreasing
or increasing values when surface area is taken into account
and similar solids are used. At j=1 the equation becomes
mathematically equivalent to Equation 3 while at low j values we
Σresidual2
approximate equation 2, thus the similarity to Figure 1b.
0.137
1 1

DSP 1, 3 3 0.1516 0.285 0.1 0.1

DSP 1, 5 3 0.2574 0.248 0.01 0.01

DSP 2 DSP 2
DSP 1 DSP 1
DSP 1, 7 3 0.1280 0.234 0.001 0.001

DSP 1, 10 3 0.4179 0.183 0.0001 0.0001

0.00001
DSP 2, 1 2 0.1637 0.307 0.00001
0 100 200 300 400 500 600 0 100 200 300 400 500 600
Seed added (m2/L) Seed added (m2/L)

DSP 2, 3 3 0.0865 0.594

a b
DSP 2, 5 3 0.0880 2.337
Figure 2. a) k” values when the data is fitted according to equation 3 and b) k’
DSP 2, 7 3 0.0916 1.214 values when the data is fitted according to equation 5

Equation 1 can be modified to incorporate the surface area The decrease in growth rate with increasing surface area when
added, since this might affect the value of k. However, the results, the data is analysed using equation 3 has several possibilities:
in fact, suggest that n = f(A, SR) (i.e., n is a function of A and SR)
not k. In order to determine if the issue is that the wrong form of i) the silicate used was ageing and polymerising, making
the driving force for precipitation is used we re-analysed this data nucleation and/or growth easier with time
using equation 2. ii) the mechanism is not growth exclusively and is a combination
4 1 of other processes
3.5

3
iii) as more solids are present, at the same supersaturation,
0.1

2.5 growth is distributed amongst the higher solids loading

leading to a smaller growth rate once surface area has been
SiO2 (g/L) DSP 2
2 0.01
SiO2 fit DSP 1
1.5

1 0.001 taken into account.

0.5

0
0 2 4 6 8
0.0001
0 100 200 300 400 500 600
If i) were true then the values for k should increase the later the
Time (hours) Seed added (m2/L)
experiment was performed, and given the overlap of DSP 1 and
a b
2 results this possibility can be excluded since the experiments
Figure 1. a) SiO2 concentration in solution versus time for a spent Bayer liquor were run sequentially. This leaves only possibility ii) and iii).
(no solids added) and b) kg values when data is fitted using equation 2

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 There is little to separate the two possible mechanisms; Summary and Conclusions
growth or secondary nucleation. While it seems intuitive that
To summarize, it is important when investigating the desilication
the desilication process probably involves an initial secondary
kinetics to understand that use of equation 1 is purely empirical.
nucleation phase followed by a growth phase, actual data to
In this regard, n can take any value and alter with both the driving
confirm this mechanism is, however, lacking and is the subject of
force of precipitation and with seed charge. While growth is a
ongoing investigations. What is clear is that the SEM images of
possible mechanism, the mere fact that the order of equation 1
DSP solids do not show an obvious core seed particle with new
is dependant on seed charge suggests a secondary nucleation
DSP growth (c/f Figure 3a and 3b). This is despite the initial DSP
event. The physical appearance of the solids produced both
1 and 2 having a different size and morphology to the resulting
with and without seed particles and their similarity support
DSP produced. Indeed, the particle size distribution of the DSP
this hypothesis. Ultimately, though, given the importance of the
produced from the seed shows a particle size fraction below
desilication process, it is time to re-investigate this system more
1 μm (Figure 3d). When this is compared to the original seed
rigorously.
material (Figure 3c), it suggests that there is either a small size
fraction that does not grow or that secondary nuclei are formed.
The constant k’ value at higher solids loadings obtained using
the secondary nucleation equation is physically reasonable,
although here it must be cautioned that reasonable fits for this
equation can also be obtained for other j values. However, a j
value of <1 has been previously noted in the literature (9).

a b

10 100
10 100
9
9
8 80

% by Volume Passing size

8 80
% by Volume Passing size

7
7
6 60
6 60
5
5
4 40
4 40
3
3
2 20
2 20
1
1
0 0
0 0 0.01 0.1 1 10 100 1000 10000
0.01 0.1 1 10 100 1000 10000 Size (μm)
Size (μm)

c d

Figure 3. a) SEM image of a DSP formed from a liquor in the absence of seed and b) in the presence of seed c) Particle size distribution of original seed material d)
Particle size distribution of DSP produced on seeding

References
1. A. Duncan, H. Müller-Steinhagen, B. Verity, B. Welch, Light Metals 1995, 37-44.
2. T. Oku and K. Yamada, Light Metals 1971, 31-45.
3. P. G. Cousineau and G. D. Fulford, Light Metals 1987, 11-17.
4. G. A. O’Neill, Light Metals 1986, 133-140.
5. M. G. Leiteizen, Tsvet. Metall., 1972, 45, 37-40.
6. A. N. Adamson, E. J. Bloore and A. R. Carr in Extractive Metallurgy of Aluminium, Vol 1 (ed. G. Gerard and P. T. Stroup) Interscience Publishers, NY,
1963, 23-58.
7. P. J. Cresswell, CHEMECA 84, 1984, 285-292.
8. J. W. Mullin in Crystallization, 3rd edition, Butterworth-Heinemann, Oxford UK.
9. A. G. Jones, in Advances in Industrial Crystallization (eds. J. Garside, R. J. Davey, A. G. Jones) Butterworth-Heinemann, Oxford UK 1991, 213-228.

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