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# Institution of Chemical Engineers
Trans IChemE, Vol 80, Part A, October 2002
www.catchword.com=titles=02638762.htm
INTRODUCTION
General Introduction
A solute will remain in solution until a suf ciently high
level of supersaturation has been developed to induce
spontaneous nucleation. The extent of this supersaturation
is referred to as the metastable zone width. It will typically
be in uenced by a variety of process parameters including
saturation temperature, rate of supersaturation generation,
impurity level, mixing, and solution history1 . It is therefore
important to characterize the metastable zone width under a
speci c set of operating conditions, which relate closely to
the conditions of the nal scale crystallization. There are a
variety of correlations available in the literature, which can
be applied to help indicate the dominant nucleation mechanisms and can be used to predict the metastable zone width2 4 .
An excellent overview of published metastable zone
width experiments is available in the literature5 . The polythermal technique6 is perhaps the most widely used technique for determining the metastable zone width. This
methodology involves cooling a saturated solution at a
xed rate until nucleation occurs. This process is repeated
for a variety of cooling rates and saturation temperatures,
with the recorded nucleation temperature allowing the
calculation of the metastable zone width for a given cooling
rate, which in turn allows an estimation of the nucleation
kinetics6 . A wide variety of measurement techniques have
been applied to detect the onset of nucleation including
visualization7 , electrozone sensing8 , and optical turbidity9 .
The method of detection frequently has an in uence on the
success of the kinetics estimation, as often there is a time lag
following nucleation as the material grows to a detectable
size range1 0 1 2 .
799
800
dDc
dc
r1
2
dt
dT
With knowledge of the solubility curve, the temperature
coef cient of solubility is simply the slope for a given
saturation temperature.
When nucleation occurs, the maximum possible undercooling is given as
DTmax T Tnuc
dc
4
dT
At the point of nucleation it is assumed that the rate of
formation of new crystals equals the rate of supersaturation
generation. The mass of nuclei formed relates directly to the
number of crystals formed6 :
Dcmax DTmax
dM
k0 arr3 Dcm kN Dcm
dt
Combining equations (2), (4) and (5) yields,
m
dc
dc
m
DTmax r1
e
kN D c kN
dT
dT
100R
100 cR 12
801
802
Nucleation temperature ( C)
26.07
26.06
26.35
27.06
29.12
26.22
26.58
26.42
Figure 4. PVM images taken within 2 minutes of the point of nucleation for
a typical batch.
12:10
10:47 lnT 65:73
T
EXPERIMENTAL RESULTS
Applying the technique described in the previous section
to solutions of varying concentrations, the metastable zone
width and solubility curve over a wide temperature range
can be generated. It is often useful to t a solubility curve to
measured solubility points and extrapolate the curve over a
wide range of temperatures. There are many relationships
803
804
kN
1.86
1.83
1.78
2.03
1.97
1.57
10.39 10 6
11.79 10 6
12.58 10 6
8.87 10 6
7.53 10 6
7.28 10 6
A1 , A2 , A3
c
c
Dc
Dcmax
dM =dt
dN =dt
constants
solvent) 1
nucleation rate, m 3 s 1
constant
nucleation rate constants
apparent nucleation order
nucleation order
cooling rate, K s 1
nuclei size, m
ratio of molecular weight of hydrate: anhydrou s
temperature, K
saturation temperature, K
nucleation temperature, K
maximum undercooling, K
solute mole fraction
temperature coef cient of solubility, g solute (100 g
solvent K) 1
Greek symbols
a
e
r
density, kg m 3
J
k
kN , k0
m
n
r1
r
R
T
T
Tnuc
DTmax
x
dc =dT
REFERENCES
1. Nyvlt, J., Sohnel, O., Matuchova, M. and Broul, M., 1985, The Kinetics
of Industrial Crystallization (Elsevier, Amsterdam, The Netherlands).
2. Mersmann, A., 1996, Supersaturation and nucleation, Trans IChemE,
74: 812820.
20.
21.
22.
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25.
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27.
28.
805
ADDRESS
Correspondence concerning this paper should be addressed to
Dr B. Glennon, Department of Chemical Engineering, University College
Dublin, Bel eld, Dublin 4, Ireland.
E-mail: brian.glennon@ucd.i e
The manuscript was received 19 March 2002 and accepted for publication
after revision 6 August 2002.