Abstract
The values of kinetic parameters for hexamine crystallization from aqueous solution, necessary for control of industrial crystallizers were
calculated in this study. Hexamine is an intermediate chemical mainly used in pharmaceutical and resin industries. In Meissner process, the
major industrial method of hexamine production, formaldehyde and ammonia in gaseous states are introduced into the reaction vessel, and
crystalline hexamine is continuously produced. The reaction between formaldehyde and ammonia is very fast and thus the whole process is
controlled by the crystallization stage. However, the kinetic information reported in the literature for industrial crystallization of hexamine is
very limited. Mechanistic modeling of hexamine crystallization was performed using mass and population balance equations. These equations
were solved using the backward difference method. Kinetic parameters in the growth and nucleation rate equations were determined by fitting
the mechanistic model to the industrial data obtained in the present study from an industrial MSMPR crystallizer. To determine the population
densities and supersaturations, both the solid and liquor phases were sampled during the transient step of particle size evolution. To optimize
the parameters, the differences between the model-predicted data and the plant data were minimized using the nonlinear unconstrained method
in an optimization subroutine. The growth and nucleation rate equations for hexamine crystallization in industrial scale were calculated as
G = 0.7S1.47 and B = 9138MT0.74 S0.551 , respectively. The growth and nucleation rate equations obtained in this study can be used to simulate
the crystallization stage of hexamine plants.
2003 Elsevier B.V. All rights reserved.
Keywords: Hexamine; Crystallization; Kinetics
1. Introduction
producing soluble hexamine followed by hexamine crystallization is presented by the overall equation of
0255-2701/$ see front matter 2003 Elsevier B.V. All rights reserved.
doi:10.1016/S0255-2701(03)00085-0
(1)
804
1.41
(2)
N2
0.3985
H2 O
0.2816
CH2 O
0.2589
CH3 OH
0.021
CO2
0.0249
Table 2
The operating conditions of the hexamine plant
Crystallizer pressure (bar)
Crystallizer temperature ( C)
0.25
0.59
6070
12.88
4. Mathematical modeling
The form of the growth rate equation was assumed as:
G = KG S g
(3)
where KG is the growth rate coefficient and S is the supersaturation. S was calculated as the difference of the liquor concentration and the saturation concentration. The secondary
nucleation rate equation was assumed as:
B = KN MTi S j
(4)
(5)
where Q is the volumetric flow rate of suspension leaving the crystallizer as product and V is the volume of the
suspension in the crystallizer. Q and V remained almost
constant with time at the conditions of the industrial crystallizer under study. An initial condition for the population
balance equation is:
n(0, L) = f(L)
3. Industrial data
805
(6)
where f(L) is the size distribution of crystals initially created in the solution by spontaneous nucleation due to a
high supersaturation. f(L) was measured by sieve analysis
of crystals in a sample taken from the crystallizer contents
at time zero, after spontaneous nucleation had occurred.
During the transient period of start up, and thereafter at
steady state period, secondary nucleation creates nuclei in
the solution. The nuclei density represented by the following
equation is another boundary condition of the population
balance equation:
n(t, 0) = n = B /G
(7)
806
11
5
(9)
k =1j =1
The conversion factor of 1018 has been introduced to adjust the units of crystal size in the equation. Optimum kinetic parameters were obtained by minimizing the objective
function.
5. Solution of model
Initially, an arbitrary value for each kinetic parameter was
assumed. The solution of model equations yielded the population densities of crystals at time increments from the beginning. Using the model predicted population densities of
crystals at different times, the values of objective function
corresponding to assumed parameters were calculated. The
values of parameters for least value of objective function
were determined using unconstrained nonlinear minimization.
Since the model equations were nonlinear, they were
solved numerically. The backward finite difference method
was used to prevent divergence in calculations. The programs were written using the package of matlab and the
parameter optimization was carried out using fminsearch
routine in this package.
KN
0.7
1.47
9138
0.74
0.551
tomicrographs of hexamine crystals sampled from the industrial crystallizer under this study.
The initial CSD measured experimentally was fitted with
a smooth exponential function, f(L), in order to minimize
errors due to fluctuations in the input data to the model:
f(L) = 3.25 105 (1 e0.022L )
(11)
Fig. 2. Representative photomicrographs of hexamine crystals sampled from the industrial crystallizer.
807
808
Fig. 3. Cumulative size distribution at different times during the evolution of particle size, comparison between the model predictions and the plant data.
Fig. 4. Cumulative size distribution predicted by the model using the optimized parameters.
Fig. 5. Hexamine concentrations in the solution with time, comparison between the model predictions and the plant data.
809
Fig. 10. Variations of nucleation rate with time, predicted by model using
optimized parameters.
ation rate behaved differently (Figs. 9 and 10). Due to increasing supersaturation at the first few hours of operation,
the nucleation rate was expected to increase and approached
its maximum value. Thereafter, no considerable decline in
nucleation rate was calculated. This was due to large mass
of crystals created after about 10 h. The generation of secondary nuclei due to mass of existing crystals, compensated
the reduction of nucleation caused by lower values of supersaturation as the process approached towards the steady
state conditions.
7. Conclusions
The process of hexamine crystallization in an industrial
MSMPR crystallizer was modeled using the population and
mass balance equations. Minimizing the differences between
the model-predicted data and the plant data, the kinetic parameters of growth and nucleation rates were calculated.
These parameters may be used to optimize the quality and
the quantity of hexamine product crystallized from aqueous
solutions in industrial plants.
Appendix A. Nomenclature
AT
B
CSD
f(L)
fobj
Fig. 8. Variations of supersaturation with time, calculated by the model
using the optimized parameters.
g, i, j
G
810
KG
KN
kv
L
MSMPR
MA
MT
m
h
m
r
n
n
P
q
Q
S
SEM
t
V
w
wi
w0
ws
Greek letters
c
s
Subscripts
g
j
k
l
gas
jth sieve used in size analysis
kth set of data points
liquid
Superscripts
exp
mod
experiment
model
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