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 inuence 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 nd 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
In the study of the kinetics of desilication in the Bayer process, it is common to use the following equation: d[SiO2]/dt = k([SiO2]t [SiO2]eq)
n

and show that the data can be explained not only by a growth mechanism but also by a secondary nucleation mechanism. Methods and Materials Spent renery Bayer liquor (from an unidentied renery) was obtained courtesy of CSIRO and ltered prior to use through a 0.45m membrane. Two solids were used for seeding experiments, they were characterised according to their phase (XRD) and size (Malvern Mastersizer) and surface area (BET isotherm, N2 as carrier gas). They are labelled DSP 1 and DSP 2 throughout this paper. DSP 1 was a laboratory made DSP produced from kaolin in synthetic liquor, while DSP 2 was a ground heater scale - Table 1. Table 1. Seed characteristics
Phase DSP 1 Sodalite with some muscovite left over from kaolin dissolution Heater scale hydroxycancrinite sulfated alumino-silicate sodalite DSP produced from experiments sulfated alumino-silicate and mixed phase sodium aluminium silicate ~10 m Not assessed Size d50(m) 5 m Surface area (m2/g) 5.03

(1)

where t is time, [SiO2] is the concentration of silicate in solution expressed as gL-1 SiO2, k is the rate constant and n is the order (also a constant). Different studies have found the need to use different values of n ranging from 1 through to 3 (1-7). However, let us take a closer look at this equation. It is essentially the classic rate equation when one species reacts with another to form a product, where it is assumed that the reaction is only dependant on the remaining silicate in solution. While the difference in the silicate concentration to the equilibrium value is a measure of the driving force for precipitation, this is not the relative supersaturation nor supersaturation ratio commonly used in crystallization theory. This equation is purely empirical and gives no mechanistic information other than whether the reaction is diffusion limited (8). Since desilication products are crystalline, zeolite-like compounds that crystallize during the predigestion (desilication step) stage of the Bayer process, it would be useful to have more fundamental information regarding the crystallization mechanism for these solids. A better description of the desilication process would, therefore, incorporate these more fundamental forms of supersaturation. One possibility is a modication of the semi-empirical kinetic equation for growth, such that: d[SiO2]/dt = kg(SR-1)n (2)

DSP 2

200 m

2.38

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 1 consisted mainly of sodalite while DSP 2 also contained 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 ask at 90C using a bottle roller. Sodium silicate solution, equilibrated to temperature, was added to the liquor (t=0) to obtain the desired nal 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, ltered 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 rst 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 tting residuals, there are some other interesting aspects to the t 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 tted 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 condence 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 t, the rate constant calculated for rate equation 1 and the sum of squares of the residual for each t
seed added (g/100 mL) DSP 1, 1 DSP 1, 3 DSP 1, 5 DSP 1, 7 DSP 1, 10 DSP 2, 1 DSP 2, 3 DSP 2, 5 DSP 2, 7 Order, n 2 3 3 3 3 2 3 3 3 k value 0.3760 0.1516 0.2574 0.1280 0.4179 0.1637 0.0865 0.0880 0.0916 residual2 0.137

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 = kA(SR-1)n (3)

There was no overall improvement nor deterioration in the residuals, with some ts 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 = kAj(SR-1)n 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 at 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 approximate equation 2, thus the similarity to Figure 1b.
1
1

(5)

0.285 0.248 0.234 0.183 0.307 0.594 2.337 1.214

0.1

0.1

0.01 DSP 2 DSP 1 0.001

0.01 DSP 2 DSP 1 0.001

0.0001

0.0001

0.00001 0 100 200 300 400 500 600 Seed added (m2/L)

0.00001 0 100 200 300 400 500 600 Seed added (m2/L)

Figure 2. a) k values when the data is tted according to equation 3 and b) k values when the data is tted according to equation 5

Equation 1 can be modied to incorporate the surface area added, since this might affect the value of k. However, the results, 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 the driving force for precipitation is used we re-analysed this data using equation 2.
4 3.5 3 2.5 2 1.5 1 0.5 0 0 2 4 Time (hours) 6 8
0.0001 0 100 200 300 400 500 600 Seed added (m2/L) 0.001 0.1 1

The decrease in growth rate with increasing surface area when the data is analysed using equation 3 has several possibilities: i) ii) iii) the silicate used was ageing and polymerising, making nucleation and/or growth easier with time the mechanism is not growth exclusively and is a combination of other processes as more solids are present, at the same supersaturation, growth is distributed amongst the higher solids loading leading to a smaller growth rate once surface area has been taken into account.

SiO2 (g/L) SiO2 fit

0.01

DSP 2 DSP 1

Figure 1. a) SiO2 concentration in solution versus time for a spent Bayer liquor (no solids added) and b) kg values when data is tted using equation 2

If i) were true then the values for k should increase the later the experiment was performed, and given the overlap of DSP 1 and 2 results this possibility can be excluded since the experiments were run sequentially. This leaves only possibility ii) and iii).

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There is little to separate the two possible mechanisms; growth or secondary nucleation. While it seems intuitive that the desilication process probably involves an initial secondary nucleation phase followed by a growth phase, actual data to conrm this mechanism is, however, lacking and is the subject of ongoing investigations. What is clear is that the SEM images of DSP solids do not show an obvious core seed particle with new DSP growth (c/f Figure 3a and 3b). This is despite the initial DSP 1 and 2 having a different size and morphology to the resulting DSP produced. Indeed, the particle size distribution of the DSP produced from the seed shows a particle size fraction below 1 m (Figure 3d). When this is compared to the original seed 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 ts 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).

Summary and Conclusions

To summarize, it is important when investigating the desilication kinetics to understand that use of equation 1 is purely empirical. In this regard, n can take any value and alter with both the driving force of precipitation and with seed charge. While growth is a possible mechanism, the mere fact that the order of equation 1 is dependant on seed charge suggests a secondary nucleation event. The physical appearance of the solids produced both with and without seed particles and their similarity support this hypothesis. Ultimately, though, given the importance of the desilication process, it is time to re-investigate this system more rigorously.

a
10
10 9 100

b
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% by Volume Passing size

8 7 6 5 4 3 2 1 0 0.01 0.1 1 10 Size (m) 100 1000

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

60

40

20

0 10000

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. 2. 3. 4. 5. 6. 7. 8. 9. A. Duncan, H. Mller-Steinhagen, B. Verity, B. Welch, Light Metals 1995, 37-44. T. Oku and K. Yamada, Light Metals 1971, 31-45. P. G. Cousineau and G. D. Fulford, Light Metals 1987, 11-17. G. A. ONeill, Light Metals 1986, 133-140. M. G. Leiteizen, Tsvet. Metall., 1972, 45, 37-40. 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. P. J. Cresswell, CHEMECA 84, 1984, 285-292. J. W. Mullin in Crystallization, 3rd edition, Butterworth-Heinemann, Oxford UK. 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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