Journal of Chemical Engineering of Japan, Vol. 37, No. 3, pp.

436–442, 2004 Research Paper

Size Distribution of Needle-Shape Crystals of Monosodium

L-Glutamate Obtained by Seeded Batch Cooling Crystallization

Norihito DOKI , Masaaki YOKOTA, Shigeko SASAKI

and Noriaki KUBOTA
Department of Chemical Engineering, Iwate University,
4-3-5 Ueda, Morioka-shi, Iwate, 020-8551, Japan

Keywords: Batch Crystallization, Monosodium L-Glutamate, Needle-Shape Crystal, Crystal Size Distribu-
tion, Breakage

Monosodium L-glutamate crystals, which are of fragile needle, were obtained by batch crystallization
with a natural cooling mode from aqueous solution. The effect of seeding on the product size was exam-
ined over a wide range of seed-loadings. The seed-loading ratio Cs, defined as the mass ratio of the added
seeds to the theoretical yield per batch, had basically the same effect on the product crystal size as ob-
served previously in cooling crystallization of mechanically strong granular crystals such as potassium
alum. At high seed-loading ratios as C s ≥ C s*, where C s* is a critical value of C s, seed crystals grew with
practically no secondary nucleation. Crystal breakage due to mechanical impacts brought by an agitator
occurred only slightly for the small products. For the large crystals the breakage was significant. The
breakage also depended on the type of stirrers used; the anchor stirrer induced less breakage than the
turbine stirrer. The transient supersaturation was measured on-line by an electro-conductivity method.

Introduction a seeding condition was easily controlled and predicted

Batch crystallization is widely used in the chemi-
cal and pharmaceutical industries, where the demand
is increasing for the crystals with precisely controlled
size and shape and with high purity. A lot of papers
dealing with batch crystallization have been published
as seen in recent review papers (Heffels and Kind,
1999; Kubota et al., 2002), books (Mullin, 2001; Wey
and Karpinski, 2002) and in the proceedings of a re-
cent international symposium on industrial crystalli-
zation. However, the methodology for the production
of crystals with controlled size and shape does not yet
seem to be established.
Recently, we have studied extensively on the ef-
fect of seeding on the product crystal size in batch cool-
ing crystallization. In these studies, the amount of seeds
was shown to play a decisive role in determining the
product size for the potassium alum–water system
(Jagadesh et al., 1996; Doki et al., 1999, 2001, 2002a;
Kubota et al., 2001) and the potassium sulfate–water
system (Jagadesh et al., 1999). In the range of high
seed-loadings, the seed crystals, added at the begin-
ning of a batch, grow to the product with practically
no secondary nucleation. Therefore, the size of the
product crystals or the grown seeds obtained under such
Received on July 24, 2003. Correspondence concerning this
article should be addressed to N. Doki (E-mail address:
doki@iwate-u.ac.jp).
Partly presented at the 68th Annual Meeting of The Society of
Chemical Engineers, Japan, at Tokyo, March 2003.
by a simple mass balance assuming the constant
number of crystals with no change in crystal shape.
This finding on the seeding effect was shown to be
useful in design and operation of an actual batch cool-
ing crystallizer (Jagadesh et al., 1999; Doki et al., 1999,
2002a). Further, the same seeding effect was also ob-
served for the dilution (or anti-solvent) crystallization
of sodium chloride from aqueous solution with the
addition of ethanol or ethanol aqueous solution as a
diluent (Doki et al., 2002b). See a review paper (Kubota
et al., 2002) for a general view of this seeding tech-
nique.
By the way, previous experiments of our group
were performed only for the granular inorganic crys-
tals, which are non-fragile or unbreakable by agitation
in ordinary suspension crystallization. However, there
are a large number of fragile organic compounds in
high-value added materials or pharmaceuticals, which
often crystallize as thin needles. These crystals are
easily broken in a mechanical action induced by agita-
tion during crystallization, because molecules in these
crystals are connected rather weakly by hydrogen bond-
ing and/or the van der Waals force. It is worth to ex-
amine whether the same seeding effect is observed for
these fragile needle-like crystalline materials.
The aim of this paper is to study the effect of
seeding on the product size of needle-like breakable
crystals in batch cooling crystallization. Monosodium
L -glutamate was chosen as a model compound, which
crystallizes as thin needles.

436 Copyright © 2004 The Society of Chemical Engineers, Japan


Fig. 1 The crystallizer equipped with a disk turbine stir-
rer coupled with a draft tube. An anchor stirrer with-
out a draft tube was also used
1. Experimental
1.1 Crystallization
A 12.2-L jacketed crystallizer, made of glass and
fitted with a thermocouple, an electrical conductivity
cell and a sampling tube, was used. Agitation was made
by either a disk turbine stirrer coupled with a draft tube
or an anchor stirrer without the draft tube. The experi-
mental apparatus is shown in Figure 1, where the
crystallizer equipped with the disk turbine stirrer is
depicted.
Crystallization was conducted similarly as in the
previous work (Jagadesh et al., 1996, 1999; Doki et
al., 1999, 2001, 2002a; Kubota et al., 2001). Typically,
the solution of monosodium L-glutamate, saturated at
55°C, was cooled to 25°C from a temperature above
the saturation point (55°C) by circulating a cooling
water of 25°C through the jacket. The temperature fell
down in an exponential manner. A known quantity of
seed crystals was introduced just at the time when the
solution temperature passed the saturation point. Just
prior to the introduction, the seed crystals were washed
with de-ionized water. The temperature and the elec-
trical conductivity were measured on-line and these
data were put into a computer through a multi-logging
meter and recorded. From these data, the transient con-
centration of the solution was calculated on-line by the
method of Hlozny et al. (1992) as described bellow.
The batch operation time was fixed at 25 h. The agita-
tion speed was fixed at 400 min–1 for the disk turbine
stirrer, while at 300 min–1 for the anchor stirrer. These
agitation speeds were lowest levels needed to keep
homogeneous suspension.
At the end of a run, a volume of crystal suspen-
sion was taken out through the sampling tube under
suction. Crystal length and width were measured on
photographs. Volume of each needle crystal was cal-
culated as a column by assuming a circular cross sec-
tion with a diameter of the measured width. The size
measurement was made for about 5000 crystals for
each group of product crystals. From these data, the
size distribution on a volume (or mass) basis was
calculated with respect to the length. The monosodium
L -glutamate used was supplied from Ajinomoto Co.,
Inc. It was used without further purification. De-ion-
ized water was used as solvent. The seed crystals were
prepared by sieving the crystals obtained from solu-
tions by cooling crystallization and then by removing
irregular crystals manually under an optical micro-
scope.
1.2 Electrical conductivity versus temperature
The electrical conductivity V was measured over
a wide range from undersaturation to supersaturation
as a function of temperature for monosodium L-gluta-
mate aqueous solutions of different concentrations (or
saturation temperatures). The measured conductivity
was correlated with temperature T and the saturation
temperature Ts (a measure of concentration) by the fol-
lowing equation according to Hlozny et al., (1992).
V = f(Ts) + (T – Ts)·g(Ts) (1)
where f(Ts) and g(Ts) are constants governed solely by
Ts, a measure of the solution concentration. The first
term of the right-hand side of Eq. (1) represents the
conductivity at a saturation temperature and the sec-
ond term takes into account the extent of deviation of
the conductivity from that of the saturated condition.
The functions f(Ts) and g(Ts) were determined respec-
tively as best fit curves to the measured data as fol-
lows with a least squares method.
f(Ts) = 71.76 × 10–4Ts2 + 23.63 × 10 –2Ts + 21.41 (2)
g(Ts) = 11.83 × 10–5Ts2 – 30.36 × 10–5Ts + 90.6 × 10–2
(3)
The electrical conductivity data seemed to be reason-
ably correlated by Eq. (1) along with Eqs. (2) and (3)
(see Figure 2). The calibration curve of Eq. (1) thus
obtained was used to calculate on-line the transient
saturation temperature T s of the solution during crys-
tallization using a transient data set of temperature T
and electrical conductivity V. The saturation tempera-
ture T s thus calculated was then converted automati-
cally to the transient solution concentration using the
solubility-versus-temperature relationship (Ogawa and
Fujii, 1949).
437

Fig. 2 Calibration curves correlating electric conductiv-
ity as a function of temperature and solution con-
centration. Saturation temperature is used as a
measurement of concentration
Fig. 3 Temperature and supersaturation profiles
2. Results and Discussion
2.1 Typical temperature and supersaturation pro-
files
Figure 3 shows a typical set of temperature and
supersaturation profiles during crystallization. The
temperature falls naturally in an exponential manner,
reaching the final level of 25°C rather quickly. In re-
sponse to this temperature fall, the supersaturation is
generated rapidly and reaches the peak. After the peak
it decreases slowly due to the low growth rate of mono-
sodium L-glutamate crystals. Therefore, a long batch
operation time of 25 h was needed to consume super-
saturation completely. Two supersaturation profiles are
shown in Figure 3; one is for an experiment using the
turbine stirrer with a draft tube and the other for an-
other experiment using the anchor stirrer without draft
tube. The peak for the turbine stirrer is lower than that
for the anchor stirrer. This difference in the peak height
could be attributed to the difference in the number of
fine particles. The fine crystals were generated more
438
Fig. 4 Length versus width of the product crystals obtained
for the 45 µm seeds
Fig. 5 Size distributions of the product crystals obtained
for the 45 µm seeds at different seed loading ratios
by the turbine stirrer with secondary nucleation mecha-
nisms and/or breakage of seed crystals and the super-
saturation started to decrease earlier by the growth of
these small crystals.
2.2 Seeding effect on the product crystal size—in
the case of the 45 µ m seeds—
Figure 4 shows typically the length versus width
data collected for about 5000 product crystals ob-
tained for the 45 µm seeds at a seed-loading ratio of
C s = 1.78 × 10 –3, where C s is defined as the mass
ratio of the added seeds to the theoretical yield per
batch. Data points in gray color in Figure 4 indicate
the 45 µm seeds themselves. The crystal size of the
product distributes over a wide range both in length
and width. The solid line passing through the origin is
a best fit to the length versus width data of the prod-
ucts, of which slope is an average aspect ratio L/W. It
was 7.8, which was the same as that measured for the
45 µm seeds. This coincidence leads to a conclusion
that the 45 µm seed crystals grew almost with no break-
age on the whole.
Figure 5 shows the size (length) distributions of
the product crystals obtained for the 45 µm seeds over
JOURNAL OF CHEMICAL ENGINEERING OF JAPAN
Fig. 6 A photograph of the product crystals obtained for Fig. 7 A photograph of the product crystals obtained
the 45 µm seeds at a seed-loading ratio of 1.78 × for the 302 µ m seeds at a seed loading ratio of
10–3 1.88 × 10–1 and with the turbine stirrer. Broken
peaces of crystals can be seen

a wide range of seed-loading ratio Cs. The distribution

depends on the amount of seeds added. At low seed-
loading ratios, the crystal size distribution spreads
widely and has two peaks. The distribution changes
from bi-modal to uni-modal as the seed-loading ratio
Cs increases. The amount of particles of the smaller
part decreases with an increase in the seed amount and
most of these particles were considered to consist of
grown nuclei the same as observed in a previous study
on potassium alum (Doki et al., 1999). It must be noted
that mechanical breakage of crystals does not depend
on supersaturation and becomes likely to occur with
an increase in the amount of seeds.
As seen in Figure 5, a seed-loading ratio of Cs = Fig. 8 Length versus width of the product crystals obtained
1.78 × 10–3 is a critical one, above which the crystal for the 302 µ m seeds
size distribution becomes uni-modal without fine crys-
tals (grown nuclei). Figure 6 shows a photograph of
the product crystal obtained at this same seed-loading
breakage was not avoided completely. Therefore, we
ratio. The crystals look uniform with virtually no fine
can conclude that, at high seed-loadings, the seed crys-
crystals.
tals grow with practically no secondary nucleation and
The mean mass size of the product crystals ob-
less crystal breakage (see Figure 4 again) for the case
tained was compared with the corresponding theoreti-
of 45 µm seeds.
cal mean mass size calculated from Eq. (3) as follows.
2.3 Effect of breakage on product crystal size
This equation was obtained from a balance between
Contrary to the case of 45 µm seeds, a lot of bro-
the mass deposited on seed crystals and the mass con-
ken pieces were included in the products obtained for
sumed from the solution by assuming no change in the
the large seed crystals of 302 µ m as shown in Figure
crystal number and the crystal shape and no residual
7, in which a picture of the products obtained at a seed-
supersaturation at the end of a batch (Jagadesh et al.,
loading ratio of Cs = 1.88 × 10–1 with the turbine stir-
1996).
rer. The corresponding diagram of length versus width
is shown in Figure 8. Data of the product in Figure 8
13
Lp  1 + Cs  scatter widely than those observed for the case of
=  ( 4) 45 µm seeds (see Figure 4). This is due to breakage of
Ls  Cs 
crystals. The average aspect ratio, the slope of a best
fit line passing through the origin, became smaller to
An actual comparison was made for the product ob- 4.6 from 7.8 of the seeds. The size distribution of
tained at the critical seed-loading ratio of Cs = 1.78 × the products is shown in Figure 9 for the 302 µ m
10 –3. The experimental mean mass size, which was seeds. The distribution changes from bi-modal to uni-
359 µm, was smaller than the corresponding theoreti- modal as similarly as observed for the smaller seeds
cal value of 372 µ m. This difference suggests that of 45 µm (see Figure 5). Although the effect of the

VOL. 37 NO. 3 2004 439


Fig. 9 Size distributions of the product crystals obtained
for the 302 µm seeds
Fig. 10 Seed chart—the normalized mean mass size of the
product crystals versus the seed-loading ratio
breakage of crystals is not observed clearly in Figure
9, a significant occurrence of breakage was suggested
from the discrepancy between the experimental mean
mass size of the products of 512 µm obtained at a value
of Cs = 1.88 × 10–1 and the corresponding theoretical
mean mass size of 558 µm. Although another potential
cause for the decreased experimental product size is
secondary nucleation, it did not seem to play a major
role at this high seed-loading ratio, because most of
the small particles in the photograph (Figure 7) were
not so thin and the seed-lording ratio was sufficient to
suppress secondary nucleaiton. It must be that, in gen-
eral, secondary nucleation cannot be distinguished
clearly from breakage. In this paper, we define sec-
ondary nucleation as a process of the formation of thin
crystals by the presence of parent crystals without
440
change in their size, and as a process which depends
on supersaturation.
2.4 Seed chart
The mean mass size of the products L p normal-
ized with that of the seeds L s is plotted in Figure 10 as
a function of the seed-loading ratio Cs. This diagram
was named the seed chart (Kubota et al., 2002). For
the case of the 45 µm seeds, it increases with an in-
crease in Cs and reaches the ideal growth line at a criti-
cal point Cs*. Then it decreases along with the ideal
growth line. The data points lie roughly on the ideal
growth line. This fact leads to a conclusion that virtu-
ally no fine particles are generated at Cs ≥ Cs* for the
45 µm seeds. For the 302 µm seeds, general behavior
of the product size on the seed chart is similar as that
for the 45 µm seeds. Namely, virtually no secondary
nucleation occurred in the seed-loading ratio range
above a critical point. However, the value of Lp/Ls for
the 302 µ m seeds does not coincide completely even
at Cs ≥ Cs*, for the turbine stirrer in particular, with the
ideal growth line. This is mainly due to the breakage
of crystals.
In the range of Cs < Cs*, the value of Lp/Ls decreases
as Cs is decreased, regardless of the seed size used.
For the 45 µm seeds, this can be mainly attributed to
the generation of fine particles by secondary nuclea-
tion mechanisms with less occurrence of breakage (see
Figures 4 and 6). This behavior is roughly the same as
that observed for granular unbreakable materials (Doki
et al., 1999). For the large seeds of 302 µ m, the
behavior of Lp/Ls is apparently the same. However, in
this case, breakage works significantly to generate new
particles (see Figures 7 and 8), causing the mean mass
size to decrease.
In Figure 10, the effect of the type of impeller can
be seen. The value of Lp/L s is lower for the disk tur-
bine impeller than that for the anchor stirrer. This means
that the generation rate of new particles by secondary
nucleation and/or breakage was higher for the disk tur-
bine impeller. It can be said, therefore, that the selec-
tion of impeller type is important to control product
crystals by suppressing secondary nucleation and/or
breakage.
The crystallization behavior of needle-shape
monosodium L-glutamate was basically the same as that
reported previously on non-fragile crystalline materi-
als (Jagadesh et al., 1996, 1999; Doki et al., 1999, 2001,
2002a; Kubota et al., 2001). Therefore, the scale-up
rule observed for the non-fragile granular materials
(Doki et al., 1999) is expected to apply on the whole
for the needle-shape monosodium L-glutamate crystals.
Namely, the critical seed-loading ratio Cs* is expected
not to depend on the scale of a crystallizer. The criti-
cal value C s * determined by using a laboratory
crystallizer could be directly applied for the design of
an industrial scale crystallizer, as done for non-fragile
JOURNAL OF CHEMICAL ENGINEERING OF JAPAN
materials (Doki et al., 2002a).
2.5 Comments on recent publications
Recently, Borrissova et al. (2002) reported a study
on non-seeded batch cooling crystallization of the
same material used in the present study, monosodium
L -glutamate, where the transient supersaturation was
measured by using ATR-FTIR spectroscopy and con-
trolled by manipulating the temperature. The supersatu-
ration had a large effect on the crystal size and aspect
ratio of the products. The lower supersaturation gave
larger crystals with low aspect ratios. A typical exam-
ple of the large product crystals they obtained was
300 µm in length with an aspect ratio of 10. These crys-
tals were thinner than those obtained in the present
study.
Borrissova et al. (2002) also produced small crys-
tals ranging from 25 to 30 µm in length by the non-
controlled cooling method or by the natural cooling
method as employed in the present study. The fine prod-
uct crystals thus produced were used as seed crystals
for a subsequent cooling crystallization. But, this at-
tempt was not successful in growing the crystals fur-
ther, probably because of an insufficient amount of
crystals. However, these fine crystals will be success-
fully used as inner seeds as suggested by Doki et al.
(2002b) if their number is controlled to satisfy the seed-
ing condition of Cs ≥ Cs*.
Roberts (2002) gave a lecture in a recent sympo-
sium on the application of process analytical techniques
to monitoring the crystallization of organic crystals,
in which ATR-FTIR for measurement of solution su-
persaturation, ultrasonic spectroscopy for monitoring
particle size, X-ray diffraction for assessing the poly-
morphic form of crystallized materials and video
microscopy for measurement of crystal shape and crys-
tal habit are introduced. These analytical techniques
will be effectively coupled with the seeding method
presented in our recent studies.
Conclusions
Monosodium L -glutamate was crystallized in
batches from aqueous solutions, which was obtained
as fragile thin needles. The followings were drawn as
concluding remarks.
(1) The 45 µm seed crystals were grown with
suppressed secondary nucleation at the seeding condi-
tion of Cs ≥ Cs* similarly as observed for non-fragile
crystals. The aspect ratio of the product crystals was
the same as that of the seed crystals. However, break-
age was not avoided completely.
(2) The 302 µm seed crystals were grown basi-
cally in the same manner, but crystal breakage occurred
significantly even at Cs ≥ Cs*. The aspect ratio of the
product was smaller than that of the seeds.
(3) The stirrer type had an effect of the product
size. The disk turbine stirrer with a draft tube gave
VOL. 37 NO. 3 2004
smaller crystals at a low range of Cs. This means that
the disk turbine gave a larger amount of fine crystals
by secondary nucleation and/or crystal breakage.
Acknowledgment
This study was conducted as part of the Research Project of
the Intelligent Manufacturing System in Japan in 2002 (title: Intel-
ligent Design and Control of Batch Crystallization Processes. Do-
mestic Code No. 0134, Common name: SINC-PRO). The monoso-
dium L-glutamate used in this study was supplied from Ajinomoto
Co., Inc.
Nomenclature
Cs = seed-loading ratio defined by W s/Wth [—]
C s* = critical seed-loading ratio [—]
Lp = mean mass length of product crystals [µ m]
Ls = mean mass length of seed crystals [µ m]
T = temperature [°C]
Ts = saturation temperature of a solution [°C]
V = electrical conductivity [mS/cm]
Ws = mass of seed crystals [kg]
Wth = theoretical crystal yield calculated from solubility
with no residual supersaturation at the end of a
batch [kg]
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