www.elsevier.com/locate/ces
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.
illumination of light depended on the reflection of light onto media and enhances crystal growth by layering of newly born
suspended particles present in solution. A distinct sharp red crystallites onto the surface of the seeds.
line in reactive supersaturated solution was formed due to the Sets of preliminary batch experiments were conducted us-
formation of spontaneous precipitation, which was visible from ing 3, 4 and 7mM concentration of solution with size classified
few meters distance in a dark room. This limit of pH is the (45–63 m) quartz sand and struvite seeds. Each experiment
apparent minimum pH for spontaneous precipitation. was conducted at previously investigated optimal supersatura-
tion (close to saturation as previously investigated by thermody-
2.2. Preparation of seed materials namic simulation) with 12 h operational time. Sieving of seeds
was conducted using ASTM standard sieve. The crystal size
This paper incorporates two types of experiments, which in- distribution (CSD) of seeds as well as growing struvite crystals
clude batch scale and fed-batch pilot scale experiments. Batch was measured using Malvern particle-sizer.
experiments (in the presence of seeds) were conducted to de-
termine the suitable seed materials for struvite crystallization. 2.4. Determination of feed composition
Fed-batch scale crystallization was conducted in controlled su-
persaturation mode in the presence of previously investigated To determine the concentration of different species of mag-
suitable seed materials. nesium, ammonium and phosphate, concentration of requisite
species along with the range of pH values were utilized as
2.2.1. Preparation of seed materials for batch experiments model input. All PHREEQC calculations were performed at
Preparation of seed (for batch experiment) was conducted 25 ◦ C temperature. Using the default database file, PHREEQC
in batch scale homogeneous struvite crystallization. In this cir- model calculated the concentrations of different complexes in-
cumstance, equimolar initial solution of 0.007 M of magnesium, cluding free Mg2+ , NH+ 4 and PO4 .
3−
ammonium and phosphate was used along with constant oper- To determine the saturation state of feed solution, concentra-
ating pH of 7.75. Generated struvite crystals were then used tion of the feed solution along with the range of pH value was
as seed to perform another experiment in heterogeneous crys- utilized as model input. The default database of PHREEQC
tallization mode (in the presence of seeds) until the desirable does not contain the equilibrium solid phase data of struvite;
growth of struvite. This technique of seed preparation is called hence, it was necessary to code the equilibrium state of stru-
as serial seeding. Produced struvite crystal was then collected vite together with the equilibrium constant. The thermodynamic
and sieved using 45–63 m of ASTM standard sieve. 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
2.2.2. Preparation of seed materials for fed-batch experiments
illustrated in Section 3.2. It is worthwhile pointing out that the
Seed crystals for use in pilot scale experiments were prepared
input data of heat transfer due to the reaction of struvite for-
in fed-batch pilot scale crystallization using serial seeding tech-
mation (H ) is used zero, since no such data are available in
nique (Section 2.2.1), as described in the previous paragraph.
the available literature
Size classified struvite seeds were prepared using 63–150 m
of ASTM standard sieve. MgNH4 PO4 · 6H2 O ⇔ 6H2 O + Mg2+ + NH+ 3−
4 + PO4 ,
(2)
2.2.3. Sieving technique of crystals Log K = −13.27, (3)
Wet sieving was employed to prepare size classified struvite
seeds. Subsequent to the separation of crystals from crystal H = 0. (4)
slurry, further separation of fines was employed using mild The saturation index (SI) identifies the saturation stage of so-
alkaline water (pH = 8.5) to avoid any dissolution of crystal lution, which is defined as
(struvite) during sieving. Size classified crystal, obtained from
wet sieving, was then air dried for 7-days to remove surface SI = Log(IAP) − Log Ks , (5)
moisture. It is recommended to use the drying temperature of where Ks is the temperature corrected solubility constant. IAP
struvite in the range of 40–50 ◦ C. Experimental observations the ion activity product of struvite.
show that over drying (above 50 ◦ C) of struvite produces fragile If SI > 0, supersaturation is indicated. When SI < 0, the so-
crystals. Fragile seeds used in the fed-batch experiment may lution is undersaturated with respect to the solid. When SI = 0,
cause breakage of crystals due to recirculation of parent solution there is an apparent equilibrium with respect to the solid.
during crystallization.
3. Results and discussion for design and commissioning of
2.3. Experiments on suitable seed materials struvite reactor
As part of the design of the struvite reactor, it is necessary 3.1. Identification of metastable zone
to determine suitable seed materials, which have positive influ-
ence on struvite growth. It is worthwhile pointing out that the Thermodynamic equilibria of struvite chemistry were simu-
presence of suitable seeds in reactive solution acts as diffusive 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)
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
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 3.3. Determination of suitable seeds (batch scale experiment)
solution to the undersaturated.
It is therefore imperative to use feed solutions according to Figs. 6 and 7 describe the scanning electron microscopic
M1 to minimize loss of reactants due to the formation of struvite (SEM) view of struvite growth, using struvite seeds and quartz
and NH3 in feed solution. Continuous stirring of titrant 1 (feed sand seeds, respectively. The SEM view in Fig. 6 demonstrates
type M1 ) set the feed solution in motion, thus avoiding the the similarity of typical orthorhombic shape of struvite seeds
settlement of Mg(OH)2 precipitate. This well-mixed Mg(OH)2 and growing struvite due to crystallization. Noticeable increase
in feed solution would then redissolve on entry to the reactor. of size of struvite seeds was observed after crystallization
The ionic strength of the reactive solution was altered main- (Fig. 6A and B). Quartz sand seeds did not take part in growth
taining 0.1 M of NaCl. Considering the dilution effect of the (Fig. 7); however, some struvite crystals formed due to the
combined feed addition, 0.2 M of NaCl was required in titrant-2 nucleation and subsequent growth of stable crystallites. The
of feed type M1 to maintain 0.1 M concentration of NaCl in the magnified view described in Fig. 8 shows the clear image of
reactive solution. The addition of 0.2 M of NaCl reduced the pH struvite growth in the presence of quartz sand seeds. Tiny
value of titrant-2 (feed type M1 ) to 3.60. In this circumstance dendrite-shaped struvite crystals form in the presence of quartz
“acid–base neutralization” occurred in reactive solution when seeds and they remain as separate crystal instead of layering
both titrants were added at the same flow rate to maintain con- onto the surface of quartz sand.
stant stoichiometry. A trial experiment showed that acid–base Particle size analysis using Malvern particle-sizer confirmed
neutralization caused excessive flow rate of feed solution, lead- growth of struvite of about 14 and 4 m of growth for struvite
ing to the occurrence of extreme supersaturation. Adjustment seeds and quartz sand seeds, respectively (Figs. 9 and 10). The
of pH of titrant-2 (feed type M1 ) was thus required to mini- reason is probably the similarity of lattice structure between
mize the acid–base neutralization effect. Experimental investi- struvite seeds and newly born struvite crystallites enhances the
gations showed that the pH difference between titrant-2 (type diffusion integration process (Mullin, 1993). It is worthwhile
M1 ) and reactive solution 1.0–1.25 maintained reasonably con- pointing out that the crystallite is a domain of solid-state mat-
sistent control of the process. 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
4. Fed-batch-controlled crystallization
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)
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)
15
Volume %
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
Data Logger
pH Controller
Automatic
temperature Control
System
Recirculation PVC
pipe
Cooling Coil
Recirculation Pump
• Fed-batch experiment is required to operate within previously Unfortunately, no standard design approach exists for stru-
investigated stable metastable zone to minimize spontaneous vite crystallization. However, some common techniques such
precipitation (Section 3.1). as suspension bed, seedings, feed addition are widely practiced
• The fed-batch system is required to maintain using two feed (Bouropoulos and Koutsoukos, 2000; van der Houwen and Val-
solutions. The first is a solution of NH4 H2 PO4 (the ammonia sami-Jones, 2001; Kofina and Koutsoukos, 2003, 2005; Adnan
and phosphate source) and NaCl (to maintain ionic strength), et al., 2004). A schematic diagram of struvite fed-batch system
pH adjusted to 6.0. The second is composed of NaOH (for is shown in Fig. 11.
pH maintenance) and MgCl2 (the magnesium source). Com- A struvite reactor of 44 L volume, made of clear Perspex,
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-
suspended bed condition, allowing seeds and crystals to keep
active solution concentration (Section 3.2). in uniform and full suspension. A pH controller (alpha 2000W)
• Struvite crystal is required to use for struvite crystallization controlled the desired pH of solution and triggered feed ad-
to enhance struvite growth rate (Section 3.3). dition when solution pH dropped below set point. Two dos-
ing pumps (Grundfos DME-12) were operated for titrant (feed
Fed-batch experiment was conducted based on the previous solution) additions based on two separate output signals sent
investigation. The detailed design of fed-batch experiment is via the pH controller. The pH controller was operated in pulse
described in Section 4.1. frequency control mode together with a proportional integral
Md.I. Ali, P.A. Schneider / Chemical Engineering Science 61 (2006) 3951 – 3961 3959
control strategy. Based on the pH sensor output, the dosing atures, enabling effective supersaturation control. A plastic-
pump adjusted the flow rate of feed solution. coated cooling coil (Figs. 11 and 12) assembled with control
The pH controller monitored and controlled the desired solu- module was required to avoid corrosion of exposed copper and
tion pH by two automatic relays (relay A and relay B) system, to maintain constant experimental temperature. The fed-batch
mounted in it. This system made the experimental control fully experiment was conducted using the desired reactive concentra-
automatic. Therefore, the feed solution must be split into two tion 0.0060 M along with the operating pH of 7.22. Previously
parts as described in Section 3.2. It is worthwhile pointing out generated fresh struvite seeds of mean diameter 127.77 m of
that the split of feed solution into three parts is not adaptable weight 30 g were used in the fed-batch experiment.
with a single pH controller due to the absence of third relay.
Nonetheless, using more than one pH controller would be one 5. Results and discussion from fed-batch experiment
way to maintain experimental control, which however could
make the control system more complicated and more expensive Followed by the experimental setup, as described in Figs. 11
(due to addition pH controller, dosing pump). and 12, the conducted experiment in controlled supersaturating
The mixing of the reactive solution was carried out by a re- showed the stability of control all through the experiment. Dur-
circulation pump (Onga pump: model 413) together with solu- ing the fed-batch experiment seed crystals took part in growth.
tion recirculation loop, composed of PVC pipe of 1-in diameter. The experimental control of pH and reactant concentrations is
A variable transformer (variac) was used to maintain trouble shown in Section 5.1 and the growth of struvite crystals during
free controlled flow rate of the recirculation pump. The top por- crystallization is shown in Section 5.2.
tion of PVC pipe was connected with an adjustable and flexible
recirculation system (Fig. 12) to avoid short circuiting of recir- 5.1. Control of supersaturation in fed-batch experiment
culated streams. The reactor was seeded with 30 g of previously
generated struvite crystal of size range 63–150 m. Samples Fig. 13 illustrates the control profile of struvite system at dif-
of crystal suspension were collected through pump outlet and ferent process conditions. Fig. 13(A) shows the profile of exper-
were filtered using 0.45 m filter paper. imental control relating to the concentration of magnesium and
Continuous operation of the recirculation pump led to ex- phosphate as well as experimental pH during the experiment.
cessive temperature rise in the reactor. Significant increases of Reasonably acceptable control of reactive solution composi-
solution temperature caused offset (drift) of pH value. There- tion and the operating pH of reactive solution were achieved
fore, it was necessary to maintain constant operating temper- 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
was validated precisely by PHREEQC thermodynamic mod- Kofina, A.N., Koutsoukos, P.G., 2005. Spontaneous precipitation of struvite
eling package and the available solubility limit curve, pro- from synthetic wastewater solutions. Crystal Growth and Design 5 (2),
posed by Ohlinger (1999). 489–496.
Martell, A.E., Smith, J.C., 1989. Critical Stability Constants.
4. Uses of mother crystals (struvite as seeds) in struvite crys- McPherson, A., 1988. The use of heterogeneous and epitaxial nucleants to
tallization provide positive influence on struvite growth. promote the growth of protein crystals. Journal of Crystal Growth 90
Mother crystals provide support of efficient diffusion inte- (1–3), 47–50.
gration process, leading to faster growth of struvite during Morel, F.M.M., Hering, J.G., 1993. Principles and Applications of Aquatic
crystallization. Chemistry. Wiley, New York.
Mullin, J.W., 1993. Crystallization. third ed. Butterworth-Heinemann
5. Produced struvite crystals show the typical orthorhombic Publications, Ipswich, UK.
shape with sharp edge. Muramatsu, K., Yasui, A., Suzuki, T., Kiuchi, K., 2000. Factors involved in
struvite formation by Natto bacilli. Biocontrol Science 51 (1), 57–60.
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