Chemical Engineering Science 61 (2006) 3951 – 3961

www.elsevier.com/locate/ces

A fed-batch design approach of struvite system in controlled supersaturation

Md. Imtiaj Ali ∗,1 , Philip Andrew Schneider
School of Engineering, James Cook University, Townsville, Queensland, QLD-4811, Australia

Received 25 November 2004; received in revised form 23 August 2005; accepted 20 January 2006
Available online 20 March 2006

Abstract
This paper focuses on struvite (MgNH4 PO4 · 6H2 O) crystallization in controlled supersaturation. Struvite can be used as a slow-release
fertilizer. Crystallization experiments were conducted using supersaturated solutions. The secondary focus of this paper is the design of a
struvite recovery system in fed-batch-controlled supersaturation mode. The design and commissioning of fed-batch struvite crystallization
included the determination of operating supersaturation of struvite crystallization, suitable seed materials and the composition of feed solution.
Determination of operating supersaturation of struvite crystallization was conducted by two steps including thermodynamic simulation using
gPROMS2 (process simulation software) along with a set of batch experiments. Investigation of suitable seed materials was also conducted
using set of batch experiments. Two types of seed materials including quartz sand and struvite seeds were used in the investigation of seed
materials. Composition of feed solution included the investigation of struvite solution chemistry using PHREEQC3 thermodynamic modeling
package. Based on the previously investigated design approach, struvite crystallization in fed-batch system was conducted using a 44-L of
reactor with 15-L of initial reactant volume.
䉷 2006 Elsevier Ltd. All rights reserved.

Keywords: Struvite; Control; Supersaturation; Reactor; Design; Thermodynamics

1. Introduction a need of slow-release fertilizer and has many uses in horticul-

Magnesium ammonium phosphate hexa-hydrate (Mg
NH4 PO4 · 6H2 O), commonly known as struvite, is a threat for
nutrient-rich wastewater systems when the nutrient composi-
tion exceeds stable saturation limit (Muramatsu et al., 2000).
Crystalline deposits of struvite characteristically form in the
wastewater treatment infrastructure in high turbulence zone.
The very sensitive zones of forming struvite are valves, bends
in pipe, separating screens, pumps, etc. The mass of crystalline
deposits formed can be extensive and can lead to operational
failure by clogging water distribution pipes. Struvite satisfies
∗ Corresponding author. Tel.:+61 07 4781 43463; fax: +61 07 4775 1184.
E-mail address: Md.Ali@jcu.edu.au (Md.I. Ali).
1 After December 2006, corresponding email is phil.schneider@jcu.edu.au
(Dr. Philip A. Schneider), Tel.: +61 07 4781 5427.
2 gPROMS process simulation software, Process System Enterprise,
London, UK.
3 US Geological Survey, Hydrologic Analysis Software Support Program,
437 National Centre, Reston VA 20192, E-mail: h2osoft@usgs.gov.
0009-2509/$ - see front matter 䉷 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.ces.2006.01.028
ture such as in nurseries, golf course, etc. as boutique fertilizers
(Nelson et al., 2000).
The basic technique of growth type crystallizer was derived
from mixed suspension mixed product removal (MSMPR). The
key endeavor of this paper is to design a crystallization pro-
cess capable of reducing spontaneous precipitation and allow-
ing crystals to grow. Pilot scale-controlled crystallization, in the
presence of suspended seeds, has been investigated in this paper.
Thermodynamically, the metastable zone is defined as the
critical zone of supersaturation of solution where crystalliza-
tion is not governed by nucleation and thus avoids rapid and/or
spontaneous precipitation. Hirasawa (1996) documented an ex-
perimental approach to determine metastable zone width for
hydroxyapatite crystallization, relating to solution supersatura-
tion, pH value, and minimum solubility limit of crystallization.
Crystallization in the metastable zone is heterogeneous. In in-
dustrial crystallization, the metastable zone technique is widely
practiced due to smoother continuous operation in controlled
supersaturation (Thaller et al., 1981; McPherson, 1988; Srini-
vasakannan et al., 2002).
3952 Md.I. Ali, P.A. Schneider / Chemical Engineering Science 61 (2006) 3951 – 3961

2. Materials and methods Table 1

Thermodynamic equilibria of struvite solution chemistry (Childs, 1970; Smith
and Martell, 1976; Martell and Smith, 1989; Morel and Hering, 1993)
This paper describes the fed-batch struvite crystallization in
controlled supersaturation mode. Prior to the main experiment, Thermodynamic equations Value of K
preliminary experimental observations in batch scale along with
{MgOH+ } ⇔ {Mg2+ } + {OH− } 10−2.56
thermodynamic simulation of struvite were required, which in- {NH+ + 10−0.45
4 } ⇔ {NH3 (aq)} + {H }
cluded the following investigations: 2− +
{HPO4 } ⇔ {H } + {PO4 } 3−
10−12.35
{H2 PO− +
4 } ⇔ {H } + {HPO4 }
2−
10−7.20
• Determination of the metastable zone. {H3 PO4 } ⇔ {H+ } + {H2 PO− 10−2.15
4}
• Determination of the suitable seed materials. {MgH2 PO+ 4 } ⇔ {Mg 2+ } + {H PO− }
2 4 10−0.45
• Determination of suitable composition of feed solutions. {MgHPO4 } ⇔ {Mg2+ } + {HPO2− 4 } 10−2.91
{MgPO− 2+
4 } ⇔ {Mg } + {PO4 }
3−
10−4.80
2.1. Determination of metastable zone

The determination of the metastable zone includes the ther- pH Controller

modynamic modeling along with a set of experimental obser-
vations. The determination of the metastable zone incorporates
(i) determination of minimum struvite solubility limit (satu-
ration) by thermodynamic modeling, (ii) determination of the
minimum limit of spontaneous precipitation using a set of batch
experiments.
pH probe

2.1.1. Determination of minimum struvite solubility limit

The constituent chemicals of struvite are magnesium, am-
monium and phosphate. Solution chemistry plays an impor-
tant role in struvite formation. In supersaturated solution, stru-
vite forms by chemical reaction of Mg2+ , NH4+ and PO3− 4 as
demonstrated
Mg2+ + NH+ 3−
4 + PO4 + 6H2 O ⇔ MgNH4 PO4 · 6H2 O.
(1)
The key parameters involved in struvite solution chemistry are
solution supersaturation, pH, and concentration of reactants.
Solution, consists of Mg2+ , NH4+ and PO3− 4 , remains in com-
plex forms of Mg2+ , MgOH+ , MgH2 PO+ 4 , MgHPO4 , H3 PO4 ,
H2 PO− 4 , HPO 2−
4 , PO 3−
4 , MgPO −
4 , NH 3 (Bouropoulos and Kout-
soukos, 2000). The basic thermodynamic relations of chemi-
cal complexes are listed in Table 1. The detailed description of
struvite chemistry is previously published by Ali and Schneider
(2005).
Coding of thermodynamic equilibria in gPROMS determines
the minimum pH limit of struvite saturation at the given range of
concentrations of magnesium, ammonium and phosphate. The
result of gPROMS thermodynamic simulation was then vali-
dated by the simple thermodynamic modeling using PHREEQC
and the derived data from the Ohlinger (Ohlinger, 1999) solu-
bility limit curve.
2.1.2. Determination of minimum limit of spontaneous
precipitation
The set of experiments were conducted using synthetic so-
lution of 3, 4, 5 and 7 mM solution. Synthetic solution made
up of de-ionized water was used in this experiment. Analyti-
cal grade MgCl2 and NH4 H2 PO4 was used to make up solu-
tion maintaining molar ratio of Mg : NH4 : PO4 as 1:1:1. The
metastable zone experiment was conducted in batch-scale in
Laser scattering device
Sharp red line
Fig. 1. Schematic of experimental setup.
the absence of seed to identify the minimum pH of spontaneous
precipitation at given concentrations. The schematic diagram
of experimental setup is demonstrated in Fig. 1.
Each experiment was conducted in a dark room using a laser
light scattering device (laser pointer of helium neon laser light
source) in which red color laser light passed through reactive
solution of volume 1 l. The reactive solution, contained in 1.5 l
clean glass beaker, was agitated using a rotational mechanical
agitator of agitator blade diameter 2.5 in. A uniform speed of
35 rpm was employed throughout all experiments to provide
sufficient mixing of solution. The initial pH of reactive solu-
tion (about 5.38) was slowly brought up to saturation level (in-
vestigated by thermodynamic modeling) using 0.5M of NaOH,
and afterward 0.1M of NaOH was slowly added until the first
appearance of crystal cloud in solution. In each experiment, a
30 min interval was allowed after each drop addition of NaOH
to observe any alteration of reactive solution. By careful ob-
servation, the first appearance of crystal cloud was detected by
laser light passing through the reactive solution. Scattering of
laser light was applied parallel to the bottom and perpendicu-
lar to the surface of reactive solution container. To avoid any
interference, laser light in solution must not touch the agitator
blade.
In the absence of any solid particles, undersaturated solu-
tion did not show any distinct redline of laser light, since
 Md.I. Ali, P.A. Schneider / Chemical Engineering Science 61 (2006) 3951 – 3961
illumination of light depended on the reflection of light onto
suspended particles present in solution. A distinct sharp red
line in reactive supersaturated solution was formed due to the
formation of spontaneous precipitation, which was visible from
few meters distance in a dark room. This limit of pH is the
apparent minimum pH for spontaneous precipitation.
2.2. Preparation of seed materials
This paper incorporates two types of experiments, which in-
clude batch scale and fed-batch pilot scale experiments. Batch
experiments (in the presence of seeds) were conducted to de-
termine the suitable seed materials for struvite crystallization.
Fed-batch scale crystallization was conducted in controlled su-
persaturation mode in the presence of previously investigated
suitable seed materials.
2.2.1. Preparation of seed materials for batch experiments
Preparation of seed (for batch experiment) was conducted
in batch scale homogeneous struvite crystallization. In this cir-
cumstance, equimolar initial solution of 0.007 M of magnesium,
ammonium and phosphate was used along with constant oper-
ating pH of 7.75. Generated struvite crystals were then used
as seed to perform another experiment in heterogeneous crys-
tallization mode (in the presence of seeds) until the desirable
growth of struvite. This technique of seed preparation is called
as serial seeding. Produced struvite crystal was then collected
and sieved using 45–63
m of ASTM standard sieve.
2.2.2. Preparation of seed materials for fed-batch experiments
Seed crystals for use in pilot scale experiments were prepared
in fed-batch pilot scale crystallization using serial seeding tech-
nique (Section 2.2.1), as described in the previous paragraph.
Size classified struvite seeds were prepared using 63–150
m
of ASTM standard sieve.
2.2.3. Sieving technique of crystals
Wet sieving was employed to prepare size classified struvite
seeds. Subsequent to the separation of crystals from crystal
slurry, further separation of fines was employed using mild
alkaline water (pH = 8.5) to avoid any dissolution of crystal
(struvite) during sieving. Size classified crystal, obtained from
wet sieving, was then air dried for 7-days to remove surface
moisture. It is recommended to use the drying temperature of
struvite in the range of 40–50 ◦ C. Experimental observations
show that over drying (above 50 ◦ C) of struvite produces fragile
crystals. Fragile seeds used in the fed-batch experiment may
cause breakage of crystals due to recirculation of parent solution
during crystallization.
2.3. Experiments on suitable seed materials
As part of the design of the struvite reactor, it is necessary
to determine suitable seed materials, which have positive influ-
ence on struvite growth. It is worthwhile pointing out that the
presence of suitable seeds in reactive solution acts as diffusive
3953
media and enhances crystal growth by layering of newly born
crystallites onto the surface of the seeds.
Sets of preliminary batch experiments were conducted us-
ing 3, 4 and 7mM concentration of solution with size classified
(45–63
m) quartz sand and struvite seeds. Each experiment
was conducted at previously investigated optimal supersatura-
tion (close to saturation as previously investigated by thermody-
namic simulation) with 12 h operational time. Sieving of seeds
was conducted using ASTM standard sieve. The crystal size
distribution (CSD) of seeds as well as growing struvite crystals
was measured using Malvern particle-sizer.
2.4. Determination of feed composition
To determine the concentration of different species of mag-
nesium, ammonium and phosphate, concentration of requisite
species along with the range of pH values were utilized as
model input. All PHREEQC calculations were performed at
25 ◦ C temperature. Using the default database file, PHREEQC
model calculated the concentrations of different complexes in-
cluding free Mg2+ , NH+ 4 and PO4 .
3−
To determine the saturation state of feed solution, concentra-
tion of the feed solution along with the range of pH value was
utilized as model input. The default database of PHREEQC
does not contain the equilibrium solid phase data of struvite;
hence, it was necessary to code the equilibrium state of stru-
vite together with the equilibrium constant. The thermodynamic
data of struvite are available in the literature (Taylor et al.,
1963; Ohlinger, 1999), and is shown in Eqs. (2)–(4). The de-
tailed outcome of the PHREEQC thermodynamic modeling is
illustrated in Section 3.2. It is worthwhile pointing out that the
input data of heat transfer due to the reaction of struvite for-
mation (H ) is used zero, since no such data are available in
the available literature
MgNH4 PO4 · 6H2 O ⇔ 6H2 O + Mg2+ + NH+ 3−
4 + PO4 ,
(2)
Log K = −13.27, (3)
H = 0. (4)
The saturation index (SI) identifies the saturation stage of so-
lution, which is defined as
SI = Log(IAP) − Log Ks , (5)
where Ks is the temperature corrected solubility constant. IAP
the ion activity product of struvite.
If SI > 0, supersaturation is indicated. When SI < 0, the so-
lution is undersaturated with respect to the solid. When SI = 0,
there is an apparent equilibrium with respect to the solid.
3. Results and discussion for design and commissioning of
struvite reactor
3.1. Identification of metastable zone
Thermodynamic equilibria of struvite chemistry were simu-
lated using gPROMS and the simulated response was verified
3954 Md.I. Ali, P.A. Schneider / Chemical Engineering Science 61 (2006) 3951 – 3961

10.0
Labile supersaturation
9.5
9.0
8.5
Metastable Zone
8.0
Solution pH

7.5 Undersaturation

7.0
pH for minimum solubility by coded model
6.5 pH for minimum solubility using PHREEQC
6.0 pH for minimum solubility using Ohlinger's solubility curve
pH for rapid nucleation
5.5
5.0
0.001 0.002 0.003 0.004 0.005 0.006 0.007
Concentration of Magnesium, Ammonium and Phosphate (moles)

Fig. 2. Identification of the metastable zone for struvite crystallization.

with thermodynamic modeling using the PHREEQC thermody-

Reactive Solution
namics modeling package and the derived data of the Ohlinger
(1999) solubility limit curve. Together with concentrations, the (Concentration = x molar)
1
graphical presentation of experimental pH (Section 2.1.2) along
with the simulated pH (Section 2.1.1) are presented in Fig. 2.
The range of maximum and minimum pH limits (Fig. 2) is
known as the operating pH range of struvite crystallization. Titrant-1 Titrant- 2
Crystallization within that range is heterogeneous. Crystalliza-
tion beyond this range is homogeneous, influenced by labile
supersaturation. Fig. 3. Schematic diagram of feed addition.
This operating zone of the crystallization is known as
metastable zone. Crystallization, operating close to saturation,
Table 2
may intensify crystal growth by limiting nucleation. Crystal Possible composition of feed solution
growth in this zone may be governed by surface diffusion
(layering) of newly born crystallites onto seed particles. Feed Type Titrant-1 pH Titrant-2 pH

M1 MgCl2 + NaOH ≈ 10–11 NH4 H2 PO4 ≈ 3.8

M2 NH4 H2 PO4 + NaOH ≈ 9.0 MgCl2 ≈ 7.0
3.2. Composition of feed solution M3 NH4 H2 PO4 + MgCl2 ≈ 5.3 NaOH ≈ 12.5

Experimental control depends on correct stoichiometry of

feed solution based on the fundamental reaction of struvite crys-
tallization. The struvite reactor, operated at constant pH and
constant reactant concentration was employed in this experi-
mental control. Assume that the reactor is consisted of V l of
reactive solution of x1 equimolar concentration of magnesium,
ammonium and phosphate. The schematic diagram of the feed
addition system is shown in Fig. 3. It is worthwhile pointing
out that the feed solution must be split into two streams, since
the presence of magnesium, ammonium and phosphate in the
same stream may cause the formation of struvite crystal. For-
mation of struvite crystal in feed stream can adversely affect
struvite process, leading to poor control.
Fed-batch action of the process was maintained by the ad-
dition of two titrant streams, which comprised of x2 molar
reactant concentration and x3 molar concentration of NaOH.
Concentration of feed solution was maintained based on
the stoichiometric formulation described in Eqs. (6) and (7)
(Bouropoulos and Koutsoukos, 2000)
x2 = Cx 1 + 2x1 , (6)
x3 = 2Cx 1 − 2x1 , (7)
where C is an arbitrary constant and 2x1 is considered for the
dilution effect. Based on the feed addition rate in a trial fed-
batch experiment, C = 10 was considered to maintain longer
duration of experimental control.
The combination of feed solution (titrant) has significant ef-
fect on robust and long-term experimental control of struvite
crystallization. Possible compositions of feed solution using
MgCl2 , NH4 H2 PO4 and NaOH are listed in Table 2. To evalu-
ate the detailed solution chemistry of the various compositions
(Table 2) of feed solution, thermodynamic modeling was con-
ducted using PHREEQC thermodynamic modeling package.
The model input was x2 = 0.06 M (MgCl2 and/or NH4 H2 PO4
 Md.I. Ali, P.A. Schneider / Chemical Engineering Science 61 (2006) 3951 – 3961 3955

concentration), x3 =0.11 M (NaOH concentration), as described 100

% Free Magnesium ion (Mg )

in Eqs. (6) and (7). It is worthwhile noting that the feed con-

2+
centration of NaOH and MgCl2 and/or NH4 H2 PO4 was cal- 80
Free Free
culated considering the average reactive solution concentration Magnesium ion Magnesium ion
of 0.006 M (x1 ) as employed in the fed-batch experiment (viz. 60 at pH value 5.3 at pH value 11
is = 100% (M3: is = 86.06%
Section 4). Titrant-2 of each feed type (Table 2) consists of Titrant-1) (M : Titrant-1)
single component, whereas titrant-1 of each feed type is multi- 40 1

components phase. Hence, there is high possibility of forming

various complexes in titrant-1 of each feed type, leading to al- 20
teration of desired feed concentration. Therefore, the detailed
solution chemistry of titrant-1 is described in the next para- 0
4 6 8 10 12 14
graphs, since it is accountable for poorer experimental control.
pH value
Eq. (8) shows the formation of the possible chemical compo-
nents when MgCl2 and NaOH solution are mixed to make up Fig. 4. Free Mg2+ concentration in feed-type M1 and M3 of titrant-1.
titrant-1 (feed type 1 of composition types M1 and M3 ). Pos-
sible aqueous phases form in the feed solution are OH− , H+ ,
H2 O, Cl− , H2 , MgOH+ , Mg2+ , Na, NaOH and O2 , whereas 100 Free Ammonium
the possible solid phases are Brucite [Mg(OH)2 ] and Periclase ion at pH value

% Free Ammonium (NH4+ )

Free Ammonium 9.0 is = 72.91%
(MgO) 80 ion at pH value (M2: Titrant-1)
5.4 is = 100%
4MgCl2 + 8NaOH = OH− + H+ + H2 O + 8Cl− + Mg2+ 60
(M3: Titrant-1)

+ MgOH+ + 7Na+ + NaOH + O2

+ Mg(OH)2 + MgO. (8) 40

A thermodynamic modeling using PHREEQC shows that both 20

Brucite [Mg(OH)2 ] and Periclase (MgO) remains in supersatu-
rated state in solution at the specified solution concentration of
0.06 M of MgCl2 and 0.11 M of NaOH. It is worthwhile point-
ing out that the saturation indexes (SI) for Brucite are 23.09
and 37.02 at pH value of 4 and 11, respectively. Whereas, the
saturation indexes (SI) for Periclase are 27.88 and 41.82 at
pH 4 and 11, respectively, for the specified feed solution con-
centration described above. Moreover, magnesium may form
some other complexes including MgOH+ and Mg(OH)2 (ac-
tive), as computed by PHREEQC model (Eq. (8)). MgOH+
remains in dissolved form and not accountable for magnesium
loss. Mg(OH)2 (active) is a solid phase, which remains in un-
dersaturated form (SI = −40 at pH 4; SI = −22.50 at pH 14 at
the specified feed concentration, described above). Therefore,
Mg(OH)2 (active) also not accountable for magnesium loss in
feed solution. Hence, the loss of reactive magnesium is actually
caused by the solid formation (flock) of Brucite [Mg(OH)2 ]
and Periclase (MgO).
Thermodynamic prediction, using PHREEQC, demonstrates
the trend of Mg2+ in titrant-1 when composition type M1 and
M3 is maintained (Fig. 4). As described in Fig. 4, about 14%
reduction (loss due to precipitation+reduction of concentration
due to complex formation) of free magnesium occurs at pH
11, due to the formation of dissolved MgOH+ , as well as solid
formation of Brucite [Mg(OH)2 ] and Periclase (MgO).
A trial experiment showed that the precipitation of flock in
the feed solution did not take part in feed addition since it had
settled at the bottom in the static condition. At the make up
pH of titrant-1 of feed type M1 , this precipitant caused loss
of soluble magnesium in the form of Mg(OH)2 (and MgO)
precipitate in the feed (less than 14%), leading to imbalance in
reactant concentration in the system.
0
4 6 8 10 12 14
pH value
Fig. 5. Free NH+
4 and NH3 concentration in feed-type M2 and M3 of titrant-1.
Mixing of NH4 H2 PO4 and NaOH solution to make up titrant-
1 (feed type M2 ) led to imbalance control due to transformation
of NH+ +
4 to volatile NH3 . The transformation of NH4 to NH3
caused significant loss of NH+ 4 in the form of NH3 (probably
less than 27.09%) from the feed solution (viz. Fig. 5 at pH
9.0), leading to an alteration of the desired supersaturation in
the reactive solution.
Mixing of NH4 H2 PO4 and MgCl2 to make up titrant-1 of
feed type M3 could easily form struvite in feed solution, since
feed solution (titrant-1 of feed type M3 ) remained strongly con-
centrated by the feed magnesium, ammonium and phosphate.
A trial experiment conducted with 0.006 M equi-molar concen-
tration of reactive magnesium, ammonium and phosphate along
with the equimolar feed concentration of 0.06 M of (Eqs. (6)
and (7)) magnesium, ammonium and phosphate caused struvite
precipitation in feed solution at pH value of 5.52. Thermody-
namic modeling using PHREEQC indicated supersaturation of
solution in this circumstance. Precipitation of struvite in feed
solution caused the alteration of feed concentration very sub-
stantially leading to very weak experimental control. In this
circumstance, reactive solution achieved undersaturation at the
initial stage of experiment startup. Undersaturation of solu-
tion occurred due to the reduced feed concentration. Therefore,
titrant-1 of feed type M3 caused significant impact on faulty
3956 Md.I. Ali, P.A. Schneider / Chemical Engineering Science 61 (2006) 3951 – 3961

Fig. 6. Scanning electron microscopic view of: (A) struvite seeds, (B) growing struvite.

Fig. 7. Scanning electron microscopic view of: (A) quartz sand seeds, (B) growing struvite with quartz sand.

experimental control leading to the change of supersaturated
solution to the undersaturated.
It is therefore imperative to use feed solutions according to
M1 to minimize loss of reactants due to the formation of struvite
and NH3 in feed solution. Continuous stirring of titrant 1 (feed
type M1 ) set the feed solution in motion, thus avoiding the
settlement of Mg(OH)2 precipitate. This well-mixed Mg(OH)2
in feed solution would then redissolve on entry to the reactor.
The ionic strength of the reactive solution was altered main-
taining 0.1 M of NaCl. Considering the dilution effect of the
combined feed addition, 0.2 M of NaCl was required in titrant-2
of feed type M1 to maintain 0.1 M concentration of NaCl in the
reactive solution. The addition of 0.2 M of NaCl reduced the pH
value of titrant-2 (feed type M1 ) to 3.60. In this circumstance
“acid–base neutralization” occurred in reactive solution when
both titrants were added at the same flow rate to maintain con-
stant stoichiometry. A trial experiment showed that acid–base
neutralization caused excessive flow rate of feed solution, lead-
ing to the occurrence of extreme supersaturation. Adjustment
of pH of titrant-2 (feed type M1 ) was thus required to mini-
mize the acid–base neutralization effect. Experimental investi-
gations showed that the pH difference between titrant-2 (type
M1 ) and reactive solution 1.0–1.25 maintained reasonably con-
sistent control of the process.
3.3. Determination of suitable seeds (batch scale experiment)
Figs. 6 and 7 describe the scanning electron microscopic
(SEM) view of struvite growth, using struvite seeds and quartz
sand seeds, respectively. The SEM view in Fig. 6 demonstrates
the similarity of typical orthorhombic shape of struvite seeds
and growing struvite due to crystallization. Noticeable increase
of size of struvite seeds was observed after crystallization
(Fig. 6A and B). Quartz sand seeds did not take part in growth
(Fig. 7); however, some struvite crystals formed due to the
nucleation and subsequent growth of stable crystallites. The
magnified view described in Fig. 8 shows the clear image of
struvite growth in the presence of quartz sand seeds. Tiny
dendrite-shaped struvite crystals form in the presence of quartz
seeds and they remain as separate crystal instead of layering
onto the surface of quartz sand.
Particle size analysis using Malvern particle-sizer confirmed
growth of struvite of about 14 and 4
m of growth for struvite
seeds and quartz sand seeds, respectively (Figs. 9 and 10). The
reason is probably the similarity of lattice structure between
struvite seeds and newly born struvite crystallites enhances the
diffusion integration process (Mullin, 1993). It is worthwhile
pointing out that the crystallite is a domain of solid-state mat-
ter that has the same structure as single crystal. However, the
 Md.I. Ali, P.A. Schneider / Chemical Engineering Science 61 (2006) 3951 – 3961 3957

likelihood of diffusion integration process for quartz seeds is

less effective, leading to re-dissolving of unstable crystallites. It
is worthwhile noting that the experiments relating to this section
were conducted very close to saturation region, as investigated
previously by thermodynamic modeling using PHREEQC.

4. Fed-batch-controlled crystallization

Fed-batch struvite crystallization requires some pre-requisite

observation for reasonably accurate control of supersaturation
in fed-batch crystallization.

4.1. Summary of the design and commissioning

Fig. 8. Magnified scanning electron microscopic view of struvite growth when Based on the design and commissioning of fed-batch-
quartz sand is used as seeds. controlled struvite crystallization, following conclusions can
18

16
Struvite Seeds
14
Growing struvite (0.002M)

12 Growing struvite (0.003M)

Volume %

Growing struvite (0.004M)

10
Growing struvite (0.005M)
8

0
0 50 100 150 200
Particle size in microns (1.2 to 600)

Fig. 9. Crystal size distributions (CSD) of struvite seeds and growing struvite.

25

Quartz seeds
20
Growing struvite (0.002M)

Growing struvite (0.003M)

15
Volume %

Growing struvite (0.004M)

Growing struvite (0.005M)

10

0
0 50 100 150 200
Particle size in microns (1.2 to 600)

Fig. 10. Crystal size distributions (CSD) of quartz sand seeds and growing struvite with quartz sand.
3958 Md.I. Ali, P.A. Schneider / Chemical Engineering Science 61 (2006) 3951 – 3961
pH Controller
Automatic
temperature Control
System
Feed titrant-1
Dosing Pump
Fig. 11. Schematic of controlled struvite crystallization.
be made:
• Fed-batch experiment is required to operate within previously
investigated stable metastable zone to minimize spontaneous
precipitation (Section 3.1).
• The fed-batch system is required to maintain using two feed
solutions. The first is a solution of NH4 H2 PO4 (the ammonia
and phosphate source) and NaCl (to maintain ionic strength),
pH adjusted to 6.0. The second is composed of NaOH (for
pH maintenance) and MgCl2 (the magnesium source). Com-
position factors of the feed solutions are 12x1 (Mg2+ , NH+ 4 was used in this study (Fig. 12). The reactor was operated in
and PO3−4 ) and 18x1 (NaOH), where x1 is the equimolar re-
active solution concentration (Section 3.2).
• Struvite crystal is required to use for struvite crystallization
to enhance struvite growth rate (Section 3.3).
Fed-batch experiment was conducted based on the previous
investigation. The detailed design of fed-batch experiment is
described in Section 4.1.
Data Logger
Feed titrant-2
Dosing Pump
Recirculation PVC
pipe
Cooling Coil
Recirculation Pump
4.2. Design of struvite reactor
Unfortunately, no standard design approach exists for stru-
vite crystallization. However, some common techniques such
as suspension bed, seedings, feed addition are widely practiced
(Bouropoulos and Koutsoukos, 2000; van der Houwen and Val-
sami-Jones, 2001; Kofina and Koutsoukos, 2003, 2005; Adnan
et al., 2004). A schematic diagram of struvite fed-batch system
is shown in Fig. 11.
A struvite reactor of 44 L volume, made of clear Perspex,
suspended bed condition, allowing seeds and crystals to keep
in uniform and full suspension. A pH controller (alpha 2000W)
controlled the desired pH of solution and triggered feed ad-
dition when solution pH dropped below set point. Two dos-
ing pumps (Grundfos DME-12) were operated for titrant (feed
solution) additions based on two separate output signals sent
via the pH controller. The pH controller was operated in pulse
frequency control mode together with a proportional integral
 Md.I. Ali, P.A. Schneider / Chemical Engineering Science 61 (2006) 3951 – 3961
Fig. 12. Photographic view of struvite reactor.
control strategy. Based on the pH sensor output, the dosing
pump adjusted the flow rate of feed solution.
The pH controller monitored and controlled the desired solu-
tion pH by two automatic relays (relay A and relay B) system,
mounted in it. This system made the experimental control fully
automatic. Therefore, the feed solution must be split into two
parts as described in Section 3.2. It is worthwhile pointing out
that the split of feed solution into three parts is not adaptable
with a single pH controller due to the absence of third relay.
Nonetheless, using more than one pH controller would be one
way to maintain experimental control, which however could
make the control system more complicated and more expensive
(due to addition pH controller, dosing pump).
The mixing of the reactive solution was carried out by a re-
circulation pump (Onga pump: model 413) together with solu-
tion recirculation loop, composed of PVC pipe of 1-in diameter.
A variable transformer (variac) was used to maintain trouble
free controlled flow rate of the recirculation pump. The top por-
tion of PVC pipe was connected with an adjustable and flexible
recirculation system (Fig. 12) to avoid short circuiting of recir-
culated streams. The reactor was seeded with 30 g of previously
generated struvite crystal of size range 63–150
m. Samples
of crystal suspension were collected through pump outlet and
were filtered using 0.45
m filter paper.
Continuous operation of the recirculation pump led to ex-
cessive temperature rise in the reactor. Significant increases of
solution temperature caused offset (drift) of pH value. There-
fore, it was necessary to maintain constant operating temper-
3959
atures, enabling effective supersaturation control. A plastic-
coated cooling coil (Figs. 11 and 12) assembled with control
module was required to avoid corrosion of exposed copper and
to maintain constant experimental temperature. The fed-batch
experiment was conducted using the desired reactive concentra-
tion 0.0060 M along with the operating pH of 7.22. Previously
generated fresh struvite seeds of mean diameter 127.77
m of
weight 30 g were used in the fed-batch experiment.
5. Results and discussion from fed-batch experiment
Followed by the experimental setup, as described in Figs. 11
and 12, the conducted experiment in controlled supersaturating
showed the stability of control all through the experiment. Dur-
ing the fed-batch experiment seed crystals took part in growth.
The experimental control of pH and reactant concentrations is
shown in Section 5.1 and the growth of struvite crystals during
crystallization is shown in Section 5.2.
5.1. Control of supersaturation in fed-batch experiment
Fig. 13 illustrates the control profile of struvite system at dif-
ferent process conditions. Fig. 13(A) shows the profile of exper-
imental control relating to the concentration of magnesium and
phosphate as well as experimental pH during the experiment.
Reasonably acceptable control of reactive solution composi-
tion and the operating pH of reactive solution were achieved
in the fed-batch pilot scale experiment. Fig. 13(B) shows the
3960 Md.I. Ali, P.A. Schneider / Chemical Engineering Science 61 (2006) 3951 – 3961

0.010 8
0.009 7
0.008

pH value of Solution
Concentration (M)

6
0.007
0.006 5
0.005 4
0.004 Mg Conc (M)
Average Controlled Mg (M)
3
0.003
PO4 Conc (M) 2
0.002 Average Controlled PO4 (M)
0.001 pH value 1
0.000 0
0 2 4 6 8 10
(A) Time in hours

30 8
Fig. 14. SEM view of produced struvite.
7
25

pH value of solution
6
Volume in Litre

20 25
5
15 4
Volume of reactive 3 20
10 solution (L)
pH value 2 Percent Volume
5
1 15
0 0 Seeds
0 2 4 6 8 10 10.04-hrs
10
(B) Time in hours

Fig. 13. (A) Process control of the system of expected reactive concentration 5
0.0045 M and pH 7.40. (B) Volume of reactive solution during the process
control.
0
0 50 100 150 200 250 300 350 400 450
increase of reactive volume due to the fed-batch action of Particle Size Range (microns)
experiment.
Fig. 15. CSD curve of struvite seeds and growing struvite.
After fed-batch experiment, generated struvite was separated
from mother liquor using ASTM standard sieve of aperture
63
m. Collected struvite was air dried for seven days. Fol- harvested crystal was 161.63
m. Hence, the growth of crystal
lowed by air drying, dry sieving was implemented to separate was 33.86
m. XRD analysis of the produced crystals indicates
fines of mean size smaller than 63
m. A recovery of 65–70% the crystals as struvite (Fig. 16).
of the expected struvite mass was found in this experiment. For
the perfect diffusion integration mechanism, it was expected 6. Conclusions
that 100% of the generated struvite would be larger than 63
m
(considering the lower size range of struvite seed). However, 1. The strategy described here has potential to cope with stru-
experimental observation showed that 30–35% of the generated vite crystallization at constant supersaturation, since pH and
struvite showed smaller size than was expected. Fractional gen- reactant concentration can be kept constant.
eration of smaller struvite was due to the production of fines. 2. The fed-batch system must be maintained using two feed
Some possible reasons of fines generation may be due to the solutions. The first is a solution of NH4 H2 PO4 (the ammonia
imperfect diffusion of newly born crystals, breaking of grow- and phosphate source) and NaCl (to maintain ionic strength),
ing crystals/seeds due to the impeller action of recirculation pH adjusted to about 6.0. The second is composed of NaOH
system, etc. (for pH maintenance) and MgCl2 (the magnesium source).
Composition factor of the feed solutions are 12x1 (Mg2+ ,
5.2. Produced struvite crystal in fed-batch crystallization NH+ 3−
4 and PO4 ) and 18x1 (NaOH), where x1 is the equi-
molar reactive solution concentration.
The controlled fed-batch experiment, described above, pro- 3. It is possible to identify the metastable zone when the mini-
duced struvite crystal of orthorhombic shape (Fig. 14). CSD mum struvite solubility limit (saturation limit) and the min-
curve of seeds and growing struvite crystals, during the op- imum limit of spontaneous precipitation are known. Laser
eration of pilot scale reactor operation, is shown in Fig. 15. light scattering into the reactor can detect the minimum limit
The mean diameter of struvite seeds employed in the fed- of pH for spontaneous precipitation. Minimum struvite sol-
batch experiment was 127.77
m and the mean diameter of ubility limit is identified by thermodynamic simulation and
 Md.I. Ali, P.A. Schneider / Chemical Engineering Science 61 (2006) 3951 – 3961 3961

900

800
struvite - File: 8057-01p general.raw
Operations: X Offset -0.058 | Import
700
Struvite, syn - NH4MgPO4·6H2O
Dittmarite, syn - NH4MgPO4·H2O
600
Lin (Counts)

500

400

300

200

100

0
2 10 20 30 40
2-Theta - Scale

Fig. 16. Analysis of struvite by XRD analysis.

was validated precisely by PHREEQC thermodynamic mod-
eling package and the available solubility limit curve, pro-
posed by Ohlinger (1999).
4. Uses of mother crystals (struvite as seeds) in struvite crys-
tallization provide positive influence on struvite growth.
Mother crystals provide support of efficient diffusion inte-
gration process, leading to faster growth of struvite during
crystallization.
5. Produced struvite crystals show the typical orthorhombic
shape with sharp edge.
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