Chemical Engineering and Processing 43 (2004) 803–810

Kinetics of Methenamine crystallization in industrial scale

A. Alamdari , F. Tabkhi
∗
Department of Chemical Engineering, School of Engineering, Shiraz University, 71345 Shiraz, Iran
−
Received 9 December 2002; received in revised form 13 January 2003; accepted 18 April 2003

Abstract

The values of kinetic parameters for Methenamine crystallization from aqueous solution, necessary for control of industrial crystallizers were
calculated in this study. Methenamine is an intermediate chemical mainly used in pharmaceutical and resin industries. In Meissner process, the
major industrial method of Methenamine production, formaldehyde and ammonia in gaseous states are introduced into the reaction vessel, and
crystalline Methenamine 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 Methenamine 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 Methenamine crystallization in industrial scale were calculated as

0 .74 0.551
.
◦
S , respectively. The growth and nucleation rate equations obtained in this study can be used to simulate
G =−0.7S 1 47 and B =−9138M
the crystallization stage of
T
hexamine plants.
−
© 2003 Elsevier B.V. All rights reserved.

Keywords: Hexamine; Crystallization; Kinetics

1. Introduction producing soluble Methenamine followed by Methenamine crystal-

lization is presented by the overall equation of
Methenamine (CH2)6N4, or hexamethylenetetramine is used
in pharmaceutical industries as a primary feed material, and (1)
in chemical industries as an intermediate material. It is well 6CH2O (g ) +−4NH3 g( →−C) ( )
6H12N4 s +−6H2O l +−q
( )
soluble in water and, like some other tertiary amines, has an 1
where q is 744.8 kJ mol of hexamine [3].
inverse solubility at low temperatures [1]. −
An optimum method to produce hexamine from formalde-
The most common production method of Methenamine in in- hyde and gaseous ammonia−is the Meissner process in which
dustrial scale is the reaction of formaldehyde with ammonia the reaction and crystallization stages take place simulta-
or ammonium salts [2]. This reaction in aqueous solution neously to produce crystalline hexamine. Due to a high
dissolution rate of ammonia and formaldehyde in the aque-
at room temperature is very fast and produces considerable
ous solution and a high reaction rate of hexamine produc-
amount of heat and water. The temperature at which the tion, the crystallization stage controls the Meissner process
reaction can take place with a high efficiency has been re- [3].
ported as between 0 and 90 C [1,3]. Side reactions due to The overall growth rates of spheres of compressed poly-
temperature rise may be prevented by cooling. The reaction crystalline hexamine with diameters of 10 and 16 mm
◦ in aqueous solutions were studied by Bomio et al. at a
− temperature of 30 C and in a supersaturation range of

◦ 1
0.0006–0.002 kg kg solution [4]. They observed a linear de-
∗−
Corresponding author. Tel.: +98-911-718-4316; −−
pendency of growth on supersaturation for a relative solu-
− 1 and a slightly higher
+98-711-628-7294.
fax:E-mail address: alamdari44@yahoo.com (A. Alamdari). tion/sphere velocity under 84 mm s
−

0255-2701/$ – see front matter © 2003 Elsevier B.V. All rights reserved. −
doi:10.1016/S0255-2701(03)00085-0
804 A. Alamdari, F. Tabkhi / Chemical Engineering and Processing 43 (2004) 803–810

1.
order dependency as the velocity exceeded 84 mm s
−
Therefore, they concluded that at lower velocities the diffu-
sion is controlling and at higher velocities both the diffusion −
and surface reaction are controlling the growth process.
For different solution/sphere velocities, they calculated the
growth rate coefficient as in the range 0.0025–0.0493 kg
2
m s 1 and the growth order in the range 0.95–1.16. They
−− −
also calculated the activation energy for Methenamine growth
−
as 50.2 kJ mol 1 for the temperature range 24.5–35 C.
−
The growth kinetics of Methenamine crystallizing from◦ pure
−
ethanol at 25 C were studied by Bourne and Davey [5]. They −
used a fluidized◦ bed, a rotating disk, and a single crystal sys-
tem and found− an independent growth rate of crystal size.
They reported that the growth rates attainable from ethano-
lic solutions are much higher than those from the aqueous
solutions at the same absolute supersaturations. They also
noted that measurements made at 25 C on the two different
experimental systems of their study suggested no influence Fig. 1. Flow diagram of the industrial process of hexamine production.
of hydrodynamics on the growth rates. However,
◦
secondary
nucleation which substantially affects the CSD of product Table 1
strongly depends on hydrodynamics and−hence on the scale The composition of the stream containing formaldehyde
of equipments.
Component N2 H 2O CH2O CH 3 OH CO2
Mass fraction 0.3985 0.2816 0.2589 0.021 0.0249

2. Industrial crystallizer of Methenamine

◦−
absence of diffusional effects as:
1.41
M A =− 0.383(w −−w i
) s
where M is the mass transfer rate of hexamine (kg m
1 A
s ), w is the interfacial solution concentration, and w
− i 1 −s
is the saturation concentration (kghexamine kg solution
−
). They
−
also calculated the activation energies for the growth of
−
hexamine as in the range 28.9–60.7 kJ mol −1 depending on
the rotational rate of discs. They reported that the values of
activation energy were influenced by mass transfer.−
The growth and nucleation rates of Methenamine crystalliz-
ing from methanol and from an aqueous solution containing
76% 2-propanol in a bench scale MSMPR crystallizer at
steady state were studied by Myerson et al. [7]. Rohani and
Bourne used experimental data of Methenamine crystallizing
from alcoholic solutions in the literature to develop a gen-
eral model for a seeded cooling batch crystallizer based on
population and mass balances [8].
However, the values of kinetic parameters used in the rate
equations of growth and nucleation for hexamine crystalliz-
ing from water in industrial scale, have not been reported.
These parameters are necessary for simulation of crystalliza-
tion process and control of crystal size distribution (CSD)
of product.
A stream containing formaldehyde, water vapor, and inert
1
(2) gases with a flow rate of 0.344 kg s is injected to a 15.5
−
m 3crystallizer at 100–120 C( Fig. 1). The composition of
◦ −
2 the stream is reported in Table 1. In another stream ammonia
− −
gas with a purity of 99.8 mass percent in stoichiometric
proportion to formaldehyde, enters the crystallizer where
these reactants dissolve in aqueous solution and react with
each other to produce hexamine. The operating conditions
are listed in Table 2.
A double propeller mixer suspends the crystals in the so-
lution. The high flow rate of gases entering at mid-height
of the body of the reaction vessel also enhances mixing.
Therefore, the vessel behaves as an MSMPR crystallizer. A
side stream continuously leaves the crystallizer and enters
an evaporator under a pressure lower than that of the crys-
tallizer. The stream, after being concentrated sufficiently in
the evaporator, returns to the crystallizer to complete the cy-
cle. This concentration is necessary to vaporize the water
produced by the reaction, and to create supersaturation as a
driving force for nucleation and growth of hexamine crystals
in the solution. The product stream from the crystallizer is
sent to a centrifuge filter by a positive displacement pump.
The filtrate, containing very fine particles passed through
the meshes of the centrifuge basket, is sent to a dissolution

Table 2
The operating conditions of the Methenamine plant

Crystallizer pressure (bar) Evaporator pressure (bar) Crystallizer temperature ( C)

◦−
Residence time (h)
60–70 12.88
−0.25 −0.59
 A. Alamdari, F. Tabkhi / Chemical Engineering and Processing 43 (2004) 803–810
tank, in which fines are dissolved by dilution and heating.
These particles are expected to be produced through the
mechanism of contact nucleation. The clear solution from
the dissolution tank is sent to a head tank, and thereafter is
returned to the crystallizer. The dissolution of fines prevents
their return to the crystallizer and maintains the MSMPR
conditions. The solution level in the crystallizer is controlled
by a simple hydrodynamic controller installed between the
head tank and the crystallizer. However, the variation of the
suspension volume is generally within the range of ±5.5%.
3. Industrial data
Dynamic information necessary for calculating the kinetic
parameters of crystallization, was obtained during the course
of start up of the industrial Methenamine crystallizer. As the
reaction progressed and evaporation continued, spontaneous
nucleation created new crystals which they began to grow.
Thus the size distribution of crystals was evolving before
the steady state conditions were reached.
Consecutive sampling from the suspension was carried out
and crystals were separated from the liquor in each sample
using a Buchner funnel under vacuum conditions. Crystals
were well washed by Methenamine saturated methanol and were
dried in a laboratory oven. The CSD was measured using
sieve analysis and the Methenamine concentration in the filtrate
from each sample was determined by gravimetric method,
after the complete water evaporation from the sample. Since
there was only one solute component in the solution, the
gravimetric method seemed to be accurate enough to mea-
sure the Methenamine concentrations. This method has been re-
ported as an accurate method for measuring concentrations
of KCl in controlled cooling crystallization operations [9].
To obtain an insight into the morphology of Methenamine
crystals, scanning electron microscopy (SEM) photomicro-
graphs were prepared using a Cambridge 360 electronic
microscope.
4. Mathematical modeling
The form of the growth rate equation was assumed as:
g (3)
G
G =− K S
where K G is the growth rate coefficient and S is the supersat-
uration. S was calculated as the difference of the liquor con-
centration and the saturation concentration. The secondary
nucleation rate equation was assumed as:
◦− M iS j (4)
B =− KN T
where K is the nucleation rate coefficient and M is the
N T
suspension density of crystals in the solution. Assuming
a size independent growth rate of crystals, the transient
population balance equation in a continuous MSMPR crys-
805
tallizer with constant volume of solution in the absence of
crystal agglomeration and breakage is [10]:
∂n ∂n n (5)
∂t +−G ∂L +−Q V =− 0
where Q is the volumetric flow rate of suspension leav-
ing 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 crys-
tallizer under study. An initial condition for the population
balance equation is:
(6)
n(0,L) =− f(L)
where f(L) is the size distribution of crystals initially cre-
ated 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:
◦− ◦− (7)
n(t, 0) =− n =− B /G
The variations in the solution temperature were recorded
over time during the course of start up. The range of vari-
ations was from 60 to 67 C. The temperature values nec-
◦−
essary for modeling were calculated by linear interpolation
between the recorded values.
The mass balance equation for hexamine component was
written as:
d T T
V dt w +M r h w +M
s T c = ˙m −+ ˙m− −−Q s T c
1/ρ +M /ρ 1/ρ +M /ρ (8)
is the rate of hexamine production by reaction
and ˙m ris the mass flow rate of hexamine returned to the
where ˙
h
crystallizer from the head tank. The last term on the right
hand
m side of Eq. (8) is the mass flow rate of Methenamine in
both solid and liquid phases taken out from the crystallizer.
are the crystal and the mother liquor densities,
ρ c and ρ s
respectively, and w is the mass fraction of hexamine in the
clear solution. The initial condition of Eq. (8) is the mass
fraction of hexamine in the initial solution at time zero, w0.
The mass flow rate of hexamine produced by reaction was
calculated from the mass flow rate of formaldehyde enter-
ing the crystallizer. The Methenamine mass flow rate entering
the crystallizer from the head tank was calculated by bal-
ancing the Methenamine mass around the centrifuge, the fines
dissolution tank, and the head tank.
The simultaneous solution of the mass and population bal-
ances predicts the CSD of product at different times. Kinetic
parameters of the crystallization process were determined
by fitting the model generated set of CSD to the measured
806 A. Alamdari, F. Tabkhi / Chemical Engineering and Processing 43 (2004) 803–810
set of CSD. The objective function, defined as the following
equation, calculates the difference between these two sets of
distributions:
exp mod
5 11 (P k j (t k ,L))
fobj =− (t ,L) −−P
k =− 1 j =− 1
where P is the mass of particles smaller than size L in unit
mass of solid free solution and was calculated as:
18
L 3
−−
0 ρ ck vL ndL
P =− 10
18
The conversion factor of 10 − has been introduced to ad-
just the units of crystal size in−the equation. Optimum ki-
netic 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 pop-
ulation densities of crystals at time increments from the be-
ginning. 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 minimiza-
tion.
Since the model equations were nonlinear, they were
solved numerically. The backward finite difference method
was used to prevent divergence in calculations. The pro-
grams were written using the package of matlab and the
parameter optimization was carried out using “fminsearch”
routine in this package.
6. Results and discussion
The optimized values for kinetic parameters of hexam-
ine crystallization under the industrial conditions specified
are given in Table 3. It is pertinent to note that the hexam-
ine crystals suspended in the solution were assumed not to
stick together considerably and thus, the agglomeration was
considered negligible. This assumption was checked by vi-
sualization of crystals under the microscope. No significant
agglomeration was observed, but crystals appeared mostly
individual and unattached. This observation also showed no
significant crystal breakage. Fig. 2 shows representative pho-
Table 3
The optimized values of the kinetic parameters of Methenamine crystallization
KG g NK
0.7 1.47 9138
tomicrographs of Methenamine crystals sampled from the in-
dustrial 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:
2 (9)
j
5 0 022
(11)
−− . L )
f(L) =− 3.25 ×−10 (1 −−e
The size evolution in the industrial crystallizer, which was
followed by measuring CSD at five different times during
the transient period of operation, is shown in Fig. 3. The fig-
ure also shows the set of CSD predicted by the model using
(10)
the optimized values of the kinetic parameters. As the crys-
tallization process continues, after about 20 h, the size distri-
bution of particles in the crystallizer is expected to approach
the steady CSD suggested by the model shown in Fig. 4.
Methenamine concentrations in the solution predicted by the
model, and those measured experimentally in the industrial
unit are shown in Fig. 5. Both the model predicted and the
plant data showed a peak in concentrations of hexamine in
the solution during the transient period. The reaction of am-
monia with formaldehyde and the accompanied evaporation
taking place in the solution both continuously increase the
concentration of Methenamine. On the other hand, mass depo-
sition of Methenamine on the surface area of suspended crystals
diminishes the concentration. At the beginning of the pro-
cess, there was not enough surface area available to consume
Methenamine generated in the solution; therefore, the concen-
tration increased greatly. This led to a higher supersatura-
tion, which accordingly increased the growth and nucleation
rates. Higher rates of these mechanisms resulted in more
crystal surface area available for mass deposition of hex-
amine (Figs. 6 and 7). Therefore, as enough surface area
was generated, the mass deposition prevailed the concentra-
tion increase by reaction and evaporation, and the concen-
tration started to decrease. As the steady state condition was
reached, an equilibrium state was established between the
concentration rise of Methenamine by reaction and evaporation
and the concentration fall by mass deposition.
Comparison of the model predicted data with the plant
data in both Figs. 5 and 7 shows the consistency of the re-
sults and the accuracy of the calculated values of the kinetic
parameters. It is worth noting that the industrial data of hex-
amine concentrations in the clear solution and suspension
densities of crystals shown in these figures were not directly
used in the definition of the objective function for minimiza-
tion in Eq. (9). Therefore, a good agreement of the model
predicted data with the plant data presents the validity of the
mechanistic model.
Since the temperature in the present industrial operation
was almost constant around 65 C and the hexamine solu-
bility in water at the conditions of the operation is approx-
imately independent of temperature, a peak in supersatura-
tion values similar to that of concentration values with time
was expected. The calculated values of supersaturation are
shown in Fig. 8. The same behavior was expected for the
growth rate; however, calculations showed that the nucle-
◦−
i j
0.74 0.551
 A. Alamdari, F. Tabkhi / Chemical Engineering and Processing 43 (2004) 803–810 807

Fig. 2. Representative photomicrographs of Methenamine crystals sampled from the industrial crystallizer.
808 A. Alamdari, F. Tabkhi / Chemical Engineering and Processing 43 (2004) 803–810

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. Methenamine concentrations in the solution with time, comparison between the model predictions and the plant data.
 A. Alamdari, F. Tabkhi / Chemical Engineering and Processing 43 (2004) 803–810 809

Fig. 9. Variations of growth rate during the course of plant operation,

predicted by model using optimized parameters.
Fig. 6. Predictions of surface area available in the solution.

Fig. 7. Suspension densities in the solution with time, comparison between Fig. 10. Variations of nucleation rate with time, predicted by model using
the model predicted data and the plant data. optimized parameters.

ation rate behaved differently (Figs. 9 and 10). Due to in-

creasing 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 sec-
ondary nuclei due to mass of existing crystals, compensated
the reduction of nucleation caused by lower values of su-
persaturation as the process approached towards the steady
state conditions.
7. Conclusions
The process of Methenamine 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 pa-
rameters of growth and nucleation rates were calculated.
These parameters may be used to optimize the quality and
the quantity of Methenamine product crystallized from aqueous
solutions in industrial plants.

Appendix A. Nomenclature

A total surface area of crystals available

T 1
in solution (m 2kg solution
−
)
1
B ◦− nucleation rate (# (kgsolution s) )
− −
CSD crystal size distribution
f(L) −
the population density of initial
1
crystals (# ( mkg solution) − )
f objective function of optimization
obj 1 −
((kg kg solution )2)
−
Fig. 8. Variations of supersaturation with time, calculated by the model g, i, j orders in kinetic equations (dimensionless)
using the optimized parameters. G −
growth rate of crystals ( ms )−1
810 A. Alamdari, F. Tabkhi / Chemical Engineering and Processing 43 (2004) 803–810

1 47
K growth rate coefficient ( ms 1
kg hexamine Greek letters
G −− −− .
kg 1solution
.
47
) crystal density (kg m 3)
−
K nucleation rate coefficient (# s 1
kg−−
0 74 ρc solution density (kg m −3 )
N
0 291
−− solid
. ρs −
0 551
kg hexamine
−− .
.
kg solution )
1
k volumetric shape factor of crystals (# ) Subscripts
v −
L g gas
crystal size ( m) −
MSMPR mixed suspension mixed product j j th sieve used in size analysis
removal k k th set of data points
M mass deposition rate in surface l liquid
A
integration (kghexamine m −−2 s − 1 )
M suspension density of crystals in solution
T 1 − Superscripts
(kgsolid kg clearsolution )
− exp experiment
h mass inflow rate of hexamine from head
− 1 mod model
˙m tank to the crystallizer (kg s )
−
r production rate of hexamine by
−
˙m reaction (kg s 1 )
−
n population density of crystals References
− 1
(# ( mkg solution) − )
n population density of nuclei [1] E.M. Smolin, L. Rapoport, The Chemistry of Heterocyclic Com-
◦ −1 pounds, S-Triazines and Derivatives, Interscience Publication, New
(# ( mkg solution) − ) York, 1959.
P− mass of crystals smaller than size L [2] J. Kirk, D.F. Othmer, Encyclopedia of Chemical Technology, third
in unit mass of solid − free solution ed, vol. 2, John Wiley & Sons, New York, 1978, p. 511.
1
[3] F. Meissner, E. Schwiedessen, D.F. Othmer, Continuous production
(kg kg solution
−
) of hexamethylenetetramine, Ind. Eng. Chem. 46 (1954) 724.
q heat generation in the reaction of [4] P. Bomio, J.R. Bourne, R.J. Davey, The growth and dissolution of
− 1 hexamethylene tetramine in aqueous solution, J. Cryst. Growth 30
Methenamine production (kJ mol )
−
hexamine (1975) 77–85.
Q volume outflow rate of suspension from [5] J.R. Bourne, R.J. Davey, The growth of hexamethylene tetramine
−
the crystallizer (m s3 1 ) crystals from ethanolic solutions, J. Cryst. Growth 34 (1976) 230–
−
S 1
supersaturation (kghexamine kg solution ) 238.
SEM − − [6] J.R. Bourne, R.J. Davey, H. Gros, K. Hungerbühler, The rotating
scanning electron microscopy
t time (s) −
V 3 disk configuration in the measurement of crystal growth kinetics
volume of crystallizer and evaporator (m )
w from solution, J. Cryst. Growth 34 (1976) 221–229.
hexamine concentration
1
in solution [7] A.S. Myerson, S.E. Decker, F. Weiping, Solvent selection and batch
(kghexamine kg solution ) crystallization, Ind. Eng. Chem. Proc. Des. Dev. 25 (1986) 925–929.
− [8] S. Rohani, J.R. Bourne, A simplified approach to the operation of
w interfacial hexamine concentration between batch crystallizer, Can. J. Chem. Eng. 68 (1990) 799–806.
i − and the solution (kghexamine
the solid surface [9] H.A. Mohameed, B. Abu-Jdayil, M. Al Khateeb, Effect of cooling
1 rate on unseeded batch crystallization of KCl, Chem. Eng. Process.
kg solution
−
)
41 (2002) 297.
w0 initial concentration of hexamine in
− 1 [10] A.D. Randolph, M.A. Larson, Theory of Particulate Processes, Aca-
solution (kghexamine kg solution
−− ) demic Press, New York, 1988, p. 59.
w the saturation concentration of hexamine
s 1
(kghexamine kg solution )
−
−