Effect of Agitation on the Metastable Zone, Nucleation and Growth of

Struvite Crystals in a Batch Crystallizer

Eko Ariyantoa,b,*, H. M. Anga, Tushar Kanti Sena

a
Department of Chemical Engineering, Curtin University, Perth, GPO Box U 1987, 6845
Western Australia-Australia
b
Departement of Chemical Engineering, Muhammadiyah University of Palembang, Palembang 30263
Indonesia
*
Corresponding author, Email: eko.ariyanto@postgrad.curtin.edu.au;
ekochemump2002@yahoo.com

Abstract

Nucleation and crystal growth are the fundamental processes for MgNH4PO4.6H2O (magnesium
ammonium phosphate hexahydrate or struvite) precipitation. An understanding of the nucleation and
growth of struvite crystals is essential for the effective design and operation of wastewater treatment
plants. An agitated batch crystallizer was used to study the effect of stirrer speed on the metastable
zone width and the growth of struvite crystals. Supersaturation was varied by changing concentration
of the Mg2+, NH4+, and PO33- with stoichiometric molar ratio of 1:1:1 by PhreeqC model calculation.
The higher speed can influences turbulences of the system which causes the metastable zone width to
be narrower. The precipitation of struvite was followed by monitoring the PO43- ion concentration in
the solution and crystal size distribution during the precipitation. Removal of PO43- ion concentration
increased with increasing stirrer speed. The increasing PO43- removal influenced the rate of struvite
precipitation. The kinetics was calculated by fitting first kinetic model to the experiment data
obtained. Overall, the rate of reaction followed first-order kinetic model. Struvite crystals were
analysed for their crystal size distribution (CSD) and optical images were obtained at different stirrer
speeds and supersaturations. The CSD analyses were examined by using Melvern Analyser. And
images of struvite crystals were analysed by an optical microscope.

Keyword: Struvite; Metastable Zone Width; Supersaturation; Crystals Growth

1. Introduction
Struvite formation results from the general reaction as below:
6 .6
In general, struvite formation can be divided into stages: attainment of supersaturation, nucleation and
growth. Crystal formation primarily occurs in a supersaturated solution followed by nucleation from
combination of constituent ions called embryos and nuclei growth in sequence (Jones, 2002, Myerson,
2002, Shnel and Garside, 1992, Mersmann, 2001). The presence of nuclei in the solution would
depend on mixing intensity while mixing duration can also influence its growth (Jones, 2002)
(Mersmann, 2001).
Solubility is a very important thermodynamic parameter to determine the crystallization mode
(Akrap et al., 2010) as it is essential to know solubilities before supersaturation for crystallization can
be determined for crystallization studies. For batch crystallization, the solubility and metastable zone
width must be known to understand the mechanism of crystallization. The metastable zone width is
predicted as the difference between the solubility curve and the measured curve of supersaturation
limit where nucleation occurs spontaneously. The metastable zone width depends on many operating
conditions such as supersaturation, temperature, impurities, stirring rate, cooling mode, and pH.
Several articles have been published with respect to the kinetics of struvite crystallization
process. The rate constant found was based on fitting first order kinetic model of phosphorous
concentration. The first order rate constants on preferential struvite accumulation in wastewater
conducted by Ohlinger et al. (2000), Quintana et al. (2008) and Nelson et al. (2003) were estimated
to be 4.2 h-1, 1.2 h-1 and 3.7 h-1, respectively.

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The first kinetic model for struvite precipitation was applied to the experimental data obtained
by Core et al., (2005), Pastor et al., (2008), Ohlinger et al., (1999). The equation can be written simply
as follows;
(1)
where C is the reactant concentration at time t, Ceq is the reactant concentration at equilibrium,
is the decrease in the reactant concentration over time.
By integrating Eq. 1 and assuming reaction order (n) equal to 1, Eq. 2 can be obtained
(2)
where k is the rate constant. The rate constant can be estimated by a plot of ln (C Ceq) versus time.
Higher crystal growth is can usually results with achievement of solution homogeneity by
higher agitation rates (Akrap et al., 2010). On the other hand, the higher mixing speeds can cause
crystal breakage. Breakage can be caused by collisions amongst crystals, with the wall of the
crystallizer, baffle, impeller surface or other crystals (Akrap et al., 2010). Moreover, at lower mixing
intensity a homogeneous suspension is difficult to attain. This condition will influence struvite
formation kinetics (Shimamura et al., 2003).
Struvite precipitation have been studied in different crystallizers such as agitated vessel
(Matynia et al., 2006, Pastor et al., 2008, Wilsenach et al., 2007), agitation with circulating liquid
(Corre et al., 2007), continuous Draft Tube (Koralewska et al., 2009), fluidized bed reactor (Bhuiyan
et al., 2008) and aeration reactor (Suzuki et al., 2007). In this study, the experiment was conducted in
agitated batch crystallizer. The standard equipment configuration is an agitated reactor where an
impeller was placed centrally in the vessel and to prevent swirling flow, four baffles were also added.
Moreover, the baffles not only serve to improve mass transfer and suspend crystals more effectively,
but also produced more uniform size crystals and reduced batch time (Jones, 2002).
However, comprehensive understanding of the growth of struvite on the effect of stirrer speed
is still limited to a few studies. This study, therefore, attempts to explore the effect of mixing on the
precipitation characteristic especially on rate of struvite precipitation. For this propose, the
experiments were designed to identify the mixing effect on metastable zone width, rate of struvite
precipitation and crystal size distribution.

2. Experimental methods
2.1 Materials
Chemical used for struvite precipitation studies were magnesium chloride hexahydrate
(MgCl2.6H2O), and ammonium dihydrogen phosphate (NH4H2PO4). Stock solution of MgCl2.6H2O, as
Mg2+ source, was made by dissolving crystals of MgCl2 in distilled water. The stock solution of
NH4H2PO4, as NH4+ and H2PO4- source, was prepared in the same manner. Sodium hydroxide
(NaOH) solution was used as the means for solution pH adjustment.
2.2 Methods
2.2.3 Determination of metastable zone width
Metastable zone width can be determined form supersaturation. To avoid primary nucleation of
struvite in growth experiments, the supersaturation must be in the area between supersolubility and
solubility called as metastable zone width. The experiment was conducted in Erlenmeyer flask under
constant temperature of 25OC at different stirrer speed and pH. The MgCl2.6H2O and NH4H2PO4
solution known molarities were mixed and stirred at different constant speeds. The nucleation was
identified by change in pH. The time elapsed between pH adjustment and the first pH changes were
defined as induction time. The pH drop and visually detectable precipitation took place
simultaneously.
2.2.4 Crystal growth and determination
The experimental setup is shown schematically in Fig. 1. All experiments were performed in
the laboratory-scale agitated batch crystallizer with a working volume of 1 liter. Temperature control
within the crystallizer was achieved by pumping water from a water bath enclosed in a cryothermostat
with PID regulator for temperature control. All experiments were carried out at temperature 25OC and
pH 8 and stirrer speeds used were from 50 120 rpm
After the solution reached a desired temperature and pH, it was allowed to settle at constant
temperature and pH with no visible turbidity for another 20 minutes. Seed crystals of struvite of 4 g
and mean diameters of 19.0 m were added into the crystallizer. The kinetic studies were conducted
for 2 hour, during period of time the solution was taken from crystallizer to analysis PO4

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concentration. For CSD analysis, the crystallizer was agitated further operated for periods of 20, 40
and 60 min to analysis. After crystallization for a definite time, the crystals were filtered from the
residual solution, and were dried overnight in an oven at temperature 35OC in order to measure the
CSD. The particle size distributions were measured by laser diffraction with a Malvern Master Sizer
2000. And images of struvite crystals were analysed by an optical microscope.

Figure 1. Laboratory Batch Crystallizer

3. Results and Discussions

3.1 Solubility and metastable zone
The solubility data, measured over the initial concentration of Mg, PO4 and NH4 range between
0.001 and 0.006, are plotted in Fig. 2. The solubility curve was calculated by PhreeQC model.
Supersaturation curves of 50, 100 and 120 rpm was predicted when primary nucleation was occurred
rapidly. As shown in Fig. 2, the solubility of struvite depends strongly on solution pH. At lower
solution pH, the solubility of struvite needs more initial concentration of Mg, PO4 and NH4.
The variations of metastable zone width with initial concentration for all the stirrer speed
examined are also presented in Fig. 2. It can be seen that at higher speed, 120 rpm, struvite was found
to occur primary nucleation rapidly. The experimental results confirm the well-known effects of
stirrer speed on metastable zone width. It is evident that the higher speed can influences turbulences
of the system which causes the metastable zone width to be narrower.

10
Intial Solution pH

5
0.001 0.002 0.003 0.004 0.005 0.006 0.007
Molar Concentration of [Mg]=[PO4]=[NH4] (mol/l)

Figure 2. Metastable zone width measured as an initial concentration of Mg, PO4 and NH4 at
different stirrer speeds and 25OC.

3.2 Kinetic study

In Fig. 3 shows the desupersaturation curve for PO4 concentration with respect to time for three
different stirrer speeds (50, 100 and 120 rpm). The results indicate that stirrer speeds has a significant
influence on the desupersaturation rate of PO4 concentration. Nucleation of struvite in this study was
secondary as seed crystals were used for the study. The secondary nucleation was investigated by
observing the induction time when concentration of PO4 decreased for the first time. In Fig. 3 show

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that the stirrer speed influences induction time for secondary nucleation. Higher secondary nucleation
results from lower induction time were observed at higher agitator speeds. At lower agitator speed of
50 and 100 rpm shown that induction time was occurred in 10 and 5 min, respectively, after seed
crystal introduces in the solution (see Fig. 3). It can be seen that the concentration of PO4 reached
steady state 30, 40, and 60 min after the addition of seed crystals at 120, 100 and 50 rpm, respectively.
195
50rpm
190
PO4 Concentration,mg/L 100rpm
185
120rpm
180
175
170
165
160
0 10 20 30 40 50 60 70 80 90 100 110 120 130
Time,min
Figure 3. Measured kinetic data with first-order model prediction for struvite precipitation
from initial concentration of Mg, PO4 and NH4 = 2 mMol/l with solution pH 8.0

4
ln(Ci Ceq)

2 50rpm
1 100rpm
120rpm
0
0 10 20 30 40 50 60 70
Time,min
Figure 4. Fit of PO4 concentration to the linear form of first-order kinetic (Eq. 2) model
at different agitator speeds.

Fig. 4 illustrates first-order kinetic model was applied with respect to PO4 concentration
decrease. The results of first-order kinetic model can be seen in Table 1. The constant kinetic values
in Table 1 increase with increase in stirrer speed. The results show that struvite precipitation rate
increased with increasing stirrer speed. Higher stirrer speed increases the homogeneity of the
suspension as well as increasing the collision between agitator and seed and amongst the seed
themselves, resulting in higher crystallization rates.

Table 1. Kinetic data of struvite precipitation at different stirrer speeds; 25OC and pH 8
RPM k, (/min) k, (/hr) R2
50 0.03 1.84 0.95
100 0.07 4.2 0.95
120 0.11 6.6 0.98

3.3 Crystal size distribution

In order to investigate the effect of the agitator speed on overall crystal growth rate, samples
were withdrawn and analysed by a Malvern Analyser at different time intervals during the
crystallization. The time evaluation of the crystal size distribution obtained are shown in Fig. 5.
In Fig. 5 indicates that the seed crystals (0 minute) in the batch crystallization grew to larges
crystals, as indicated by the CSD moving towards the larger sizes with time. However, the overall
crystal growth rates are different for different agitator speeds. At lower agitator speed, crystal growth
rate decreased when compared with higher stirrer speeds. During the experimental run, it was
observed that at lower agitator speeds the crystals were more located at the bottom half of the

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crystallizer. In this case, the complete suspension was not achieved, so the seed crystals were not
suspended in an environment of higher supersaturation resulting in lower growth rate.
The dominant size of CSD move toward coarser fraction as impeller speed increased. It
indicates that at higher stirrer speeds the hydrodynamic conditions are more suitable for crystals
growth. In this case, the agitation condition provided the state of complete suspension of crystals
particle and the maximum surface area of the crystals is exposed to the solution for mass transfer. On
the other hand, at higher speed it could cause crystal breakage, which is by collision between crystals
and wall of the crystallizer, impeller or other crystals.
8
t=0min
6 t=40min
t=60min
Volume(%)

4
A 2

0
1.000 10.000 100.000 1000.000 10000.000
ParticleSize(m)
8
t=0min
6 t=20min
t=40min
Volume(%)

4
B
2

0
1.000 10.000 100.000 1000.000 10000.000
ParticleSize(m)
8
t=0min
6 t=20min
t=40min
Volume(%)

4
C
2

0
1.000 10.000 100.000 1000.000 10000.000
ParticleSize(m)
Figure 5. Crystal size distribution of struvite crystals at different process times for various
stirrer speed: (A) 50 rpm; (B) 100 rpm; and (C) 120 rpm

The images of the final crystals of struvite at various stirrer speeds produced by optical
microscope are shown in Fig. 6. There is clear evidence that stirrer speed has a significant influence
on the final product size of struvite crystals. At 50 rpm (Fig. 6(A)), the image crystals appear to be
smaller, and gradually increase in size with higher stirrer speed (Fig. 6(B)(C)).

A B C
Figure 6. The images of struvite crystals obtained at various stirrer speeds
(A) 50 rpm, (B) 100 rpm, (C) 120 rpm

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Acknowledgment
This research work has been supported by the DIKTI scholarship, which is gratefully acknowledged.
The authors are also grateful to the excellent technical assistance supplied by personnel in the
Chemical Engineering Laboratory, Curtin University.

Conclusions
The study shows that stirrer speed has significant effect on the metastable zone width,
nucleation and growth of struvite crystals. Stirrer speed influences the hydrodynamics of the system
and the metastable zone width was narrower at higher speeds. The rate of reducing PO4 concentration
in bulk solution increases with increase in stirrer speed. The concentration of PO4 reached steady state
30, 40, and 60 min after the addition of seed crystals at 50, 100 and 120 rpm, respectively.
Desupersaturation of PO4 follows first-order kinetics. The rate constant increases from 1.84 hr_1 to
6.70 hr-1 with increase in stirrer speed from 50 to 120 rpm. The CSD study was investigated with
different stirrer speeds. The CSD clearly shows that the overall crystal growth rates are different for
different stirrer speeds. The higher size struvite crystals resulted at higher stirrer speed and were
confirmed by the microscopic images taken.

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