Cryst. Res. Technol. 39, No. 2, 123 – 130 (2004) / DOI 10.1002/crat.

200310159

Crystallization of phosphogypsum in continuous phosphoric acid

industrial plant

E. A. Abdel-Aal*
Central Metallurgical Research and Development Institute, P.O. Box: 87 Helwan, Cairo, Egypt
Current Address: Particle Engineering Research Center, Department of Materials Science and Engineering,
University of Florida, Gainesville, FL 32611-6400, USA

Received 26 June 2003, revised 1 August 2003, accepted 7 August 2003

Published online 15 February 2004

Key words calcium sulfate dihydrate, phosphogypsum, primary nucleation, secondary nucleation,
crystallization, Abu-Tartur phosphat concentrate.
PACS 81.10.-h

Understanding crystallization of phosphogypsum is generally of basic importance for industrial wet-process

phosphoric acid production. In this paper, measuring the phosphogypsum crystal size distribution during
primary and secondary nucleation is reported. The results show that, secondary nucleation was occurred at 5
hr run time (12.5% solid content). Crystal growth rates were about 18.4 µm/hr at 2.5% solid content and
about 4.5 µm at 30% solid content. At steady state (16 hr run time and 30% solid content), the mean diameter
of the crystals and the average specific surface area are about 25 µm and 0.69 m2/g, respectively.

© 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

1 Introduction
Phosphoric acid is an important intermediate for production of phosphate fertilizers. It is mainly produced by
wet-process in which phosphate concentrate leached with sulfuric and weak phosphoric acids to produce
phosphoric acid (Fig. 1). Calcium sulfate crystallization occurs in parallel with leaching. According to the
process adopted, calcium sulfate dihydrate (gypsum) (CaSO4.2H2O) or calcium sulfate hemihydrate
(CaSO4.0.5H2O) is crystallized. The primary reaction for the dihydrate process is as follows [1]:

Ca10F2(PO4)6 + 14H3PO4 → 10Ca(H2PO4)2 + 2HF

10Ca(H2PO4)2 + 10H2SO4 + 20H2O → 20H3PO4+10CaSO4·2H2O

_________________________________________________________
Ca10F2(PO4)6 + 10H2SO4 + 20H2O → 6H3PO4 + 10CaSO4·2H2O + 2HF

Primary (spontaneous) nucleation of calcium sulfate dihydrate was studied using pure chemicals at room
temperature and in aqueous solutions [2 - 4]. Secondary nucleation and crystal growth of gypsum are also
studied [5 – 10]. Most of published papers describe crystallization of calcium sulfate from dilute solutions of
sodium, potassium or ammonium sulfate with calcium chloride or nitrate in equal molar ratios at relatively low
super-saturation. In addition nucleation of calcium sulfate dihydrate using pure chemicals and under industrial
simulated conditions with and without additives are also studied [11 – 14]. However, to date there are no data
for the case of primary nucleation of calcium sulfate dihydrate in industrial phosphoric acid plant [1]. The
____________________

* Corresponding author: e-mail: eabde@yahoo.com

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124 E. A. Abdel-Aal: Crystallization of phosphogypsum

primary nucleation occurs when no solids in the medium and it continues until the solids content increased up
to 10% by volume [1]. The secondary nucleation is known as a spontaneous appearance of new crystals in the
solution where another primary crystal (or crystals) is already growing [15]. It can be happened at relatively
lower super-saturation when the solids content approaches 10% by volume (about 14% by wt.) [1].
In the present work, we have measured the crystal size distribution of phosphogypsum during processing of
Abu-Tatur phosphate concentrate (Egypt) at Abu-Zaabal Fertilizer and Chemical Company (Egypt). The
reactor capacity is 500 m3 and volume of the filter feed tank is 100 m3.

2 Materials and experimental methods

2.1 Materials
Phosphate concentrate used in this study is Abu-Tartur phosphate from Egypt. Characterization of Abu-Tartur
phosphate concentrate including chemical and sieve analyses weas given elsewhere [16, 17] in details.
Chemical analysis is given in Table (1). The sulfuric acid used is commercial 98% acid and has 1.84 g/ml
specific gravity.

Table 1 Chemical analysis of Abu-Tartur phosphate concentrate.

Constituent % Constituent %
P2O5 30.1 SO3 1.50
CaO 44.4 MgO 0.90
Fe2O3 3.8 Al2O3 0.46
F 2.8 Na2O 0.28
SiO2 2.3 K2O 0.04

2.2 Operating conditions

Processing of the phosphate was carried out under typical dihydrate process conditions [17] and summarized
below:
Reaction temperature, oC: 78
Retention time (first day operation), hr: 12
Retention time (normal operation), hr: 6
Free sulfate, %: 1.6 – 2.4
P2O5 in filter acid, %: 26 – 28
Solid content (first day operation), %: increases from 0% to 30%
Solid content (normal operation), %: 30% ± 1.5%

2.3 Procedure
During start-up of the plant, the nucleation and crystal growth of phosphogypsum was followed by crystal size
distribution measurement at the required time intervals. A representative slurry sample was taken for process
control of the plant and 5 ml from this slurry was taken and dispersed with 50 ml methanol. Then, the crystal
size distribution was measured using Coulter Laser Size Analyzer Model LS230. Also, specific surface areas of
gypsum samples are obtained using Coulter Laser Analyzer.

2.4 Crystal growth calculations

In this study, growth rate, G, is expressed in micrometers per hour and referred to d90 of the crystals (d90:
diameter of crystals passing 90% by volume, in µm). G is calculated according to McCabe’s law [1,18]:

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Cryst. Res. Technol. 39, No. 2 (2004) / www.crt-journal.org 125

W = G x T + Wo

where:
W : characteristic crystal size of age t, in this study increase in d90 of the crystals, µm
Wo: characteristic size of nucleus (negligible)
T : retention time, hr
G : growth rate, in µm/hr

3 Results and Discussion

3.1 Effect of run time and solid content on phosphogypsum crystal size
distribution
Size distribution of phosphogypsum crystals at different run time periods (1 – 24 hr) and different solid
contents (2.5 – 30.0%) were determined and given in Figs. 2 - 5. It is clear that at the early stages of
crystallization (Fig. 2), nucleation and growth of the crystals are occurred. The mean diameter of the crystals is
increased with time (shifting to the larger sizes). On the other hand, bimodal crystal size distribution is
appeared in Fig. 3 due to increase in the nucleation (formation of fine crystals less than 10 µm). This is started
at 5 hr run time and 12.5% solid content. This is mainly attributed to secondary nucleation of phosphogypsum
at that solid content [1]. However, a steady state for the crystal size distribution is achieved at 16 hr run time
(Figs. 4 and 5).
The statistics of the crystal size distribution at different run times and solid contents are given in Table 2
and Fig. 6. These data show that, the volume percentages of fine crystals (<10 µm) are almost remain constant
(60,7% to 61.2%) from 3 to 8 hr run time and at 7.5% to 20% solid content. This is related to rising fresh
secondary nuclei. In the time period (8-16 hr), the fine crystals fraction is decreased steadily. This indicates
that, the rate of crystal growth is higher than the rate of nucleation. Then, equilibrium between the nucleation
and the regular crystal growth is attained after 16 hr run time as the volume percentages of fine crystals (<10
µm) are almost remain within the range from 24% to 30%.

Table 2 Statistics of phosphogypsum crystal size distribution (at different run time and solid content).
Run Time, hr Retention Time, hr Solid Content, % Volume %
Crystal Size Diameter,
< 10 µm < 25 µm < 50 µm < 75 µm < 90 µm
1 1 2.5 71.8 95.8 99.7 100.0 100.0
2 2 5.5 68.2 93.8 99.7 100.0 100.0
3 3 7.5 60.7 89.3 98.9 100.0 100.0
4 4 10.0 58.6 87.2 98.1 100.0 100.0
5 5 12.5 59.1 84.7 97.8 100.0 100.0
6 6 15.0 59.4 82.9 97.2 99.6 99.8
7 7 17.5 59.8 80.5 96.2 98.5 98.9
8 8 20.0 61.2 79.9 95.6 98.5 99.1
10 10 25.0 53.8 83.3 96.7 99.2 99.6
12 12 30.0 49.9 81.7 96.9 99.4 99.7
14 12 30.0 43.5 76.6 95.9 99.2 99.7
16 12 30.0 28.5 61.6 87.5 96.7 98.5
18 12 30.0 26.2 60.9 88.2 96.3 98.0
20 12 30.0 29.6 61.0 85.2 94.3 97.1
22 12 30.0 23.9 56.5 85.3 94.9 97.2
24 12 30.0 25.1 56.5 83.6 94.9 97.6

© 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

126 E. A. Abdel-Aal: Crystallization of phosphogypsum

Fig. 1 Simple flow-sheet of dihydrate process.

Fig. 2 Comparative size distri-

bution of phosphogypsum crystals
(at different run time and solid
content).

Fig. 3 Comparative size distri-

bution of phosphogypsum crystals
(at different run time and solid
content).

3.2 Effect of run time and solid content on crystal mean diameter and average
specific surface area
The mean diameter of the crystals and the average specific surface area at different run times and along with
the solid contents are given in Table 3 and Figs 7, 8. These results show two main stages:
The first stage from 1- 12 hr run time (2.5 - 30.0% solid content), there is rapid increase in the crystals
mean diameter and decrease in the average specific surface area. This means that the rate of crystal growth is

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Cryst. Res. Technol. 39, No. 2 (2004) / www.crt-journal.org 127

higher than the rate of nucleation. The decrease in average specific surface area continues to 16 hr run time.
The second stage from 12 to 16 hr run time (30.0 % solid content), there is slight increase in the crystals mean
diameter and slight decrease in the average specific surface area. The third stage from 16 - 24 hr run time
(30.0% solid content), more or less the same crystals mean diameter and the same average specific surface
areas are achieved. Again, steady state of phosphogypsum crystallization is happened at 16 hr run time.

Fig. 4 Comparative size distri-

bution of phosphogypsum
crystals (at different run time
and solid content).

Fig. 5 Comparative size distri-

bution of phosphogypsum
crystals (at different run time).

Fig. 6 Volume percentage of <10 µm fine crystals at

different run time and solid content.

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128 E. A. Abdel-Aal: Crystallization of phosphogypsum

Table 3 Effect of run time and solid content on mean diameter and specific surface area of phosphogypsum
crystals.
Run Time, hr Solid Content, % Mean Diameter, µm Specific Surface Area, cm2/g
1 2.5 8.32 9063
2 5.0 9.11 8902
3 7.5 11.25 7896
4 10.0 12.20 8006
5 12.5 12.70 7983
6 15.0 13.50 7958
7 17.5 14.53 7937
8 20.0 17.39 7882
10 25.0 20.06 7646
12 30.0 23.72 7409
14 30.0 23.74 7215
16 30.0 24.67 6908
18 30.0 25.11 6730
20 30.0 26.04 7011
22 30.0 27.57 6777
24 30.0 27.71 7001

3.3 Effect of run time and solid content on d90 of the crystals and growth rate
According to McCabe’s law [1,18], crystal growth in homogeneous supersaturated media (regular feeding rates
and good dispersion of the reactants) is linear. On the other hand phosphogypsum crystallization shows
relatively low growth rates compared to other industrial crystallization products. This is related to mass transfer
kinetics from liquid phase to solid phase. However, high growth rate can be achieved at low solid content
(start-up of crystallization). This is attributed to increase of average specific crystal surface area available for
crystallization rather than formation of new nuclei [1]. At 1 hr run time and 2.5% solid content, a growth rate
as high as 18 µm/hr was obtained (Table 4 and Fig. 9). After 16 hr run time (30% solid content), the growth
rate achieved was ranged from 4.4 to 5.1 µm/hr. Similar results were reported [1] using South California
phosphate concentrate (20 µm/hr at low solid content and 4.7 µm/hr at high solid content). It is reported [20]
that the supersaturation must be much higher for sparingly soluble substances in order to obtain an industrially
advantageous growth rate of 3.6 µm/hr < G > 360 µm/hr. It is worth of mention that higher growth rate results
in small mean diameter of crystals at low retention time.

Fig. 7 Crystals mean diameter at different run time and Fig. 8 Average specific surface area of phosphogypsum
solid content. crystals at different run time and solid content.

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Cryst. Res. Technol. 39, No. 2 (2004) / www.crt-journal.org 129

Table 4 Effect of run time and solid content on d90 and growth rate of phosphogypsum crystals.

Run Time, hr Solid Content, % d90, µm Growth Rate, µm/hr

1 2.5 18.38 18.38
2 5.0 20.91 10.46
3 7.5 25.80 8.60
4 10.0 28.10 7.03
5 12.5 30.83 6.17
6 15.0 32.36 5.39
7 17.5 35.04 5.01
8 20.0 37.34 4.67
10 25.0 45.59 4.56
12 30.0 48.48 4.04
14 30.0 49.37 4.11
16 30.0 54.50 4.54
18 30.0 53.26 4.44
20 30.0 60.60 5.05
22 30.0 58.73 4.89
24 30.0 61.20 5.10

Fig. 9 Phosphogypsum crystal growth rates at

different run time and solid content.

4 Conclusion
Nucleation of phosphogypsum crystals was studied during start-up of phosphoric acid plant. At the early stages
of crystallization, the primary nucleation was predominant. On the other hand, the secondary nucleation was
occurred at 5 hr run time and 12.5% solid content. Crystal growth rates were about 18.4 µm/hr at 2.5% solid
content and about 4.5 µm at 30% solid content. At steady state (16 hr run time and 30% solid content), the
mean diameter of the crystals and the average specific surface area are about 25 µm and about 0.69 m2/g,
respectively.
Acknowledgements I would like to thank Prof. Hassan El-Shall, Associate Director for Particle Engineering Research
Center at University of Florida for the opportunity to do crystal size distribution analyses in his Center and for his guidance
during the research. Also, sincere appreciations are directed to Hydrometallurgy Division in Central Metallurgical R&D
Institute, Abu-Zabaal Fertilizers and Chemicals Co. and Abu-Tatrtur Project for their help during conducting the work.

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