ARTICLE IN PRESS

Journal of Crystal Growth 267 (2004) 372379

Crystallization of calcium sulfate dihydrate under simulated

conditions of phosphoric acid production in the presence of
aluminum and magnesium ions
M.M. Rashad*, M.H.H. Mahmoud, I.A. Ibrahim, E.A. Abdel-Aal
Material Science Department, Central Metallurgical Research & Development Institute, P.O. Box 87, Helwan, Cairo 11421 Egypt
Received 15 March 2004; accepted 27 March 2004
Communicated by T.F. Kuech

Abstract
The effect of Al3+ and Mg2+ ions, as additives, on the crystallization of gypsum was studied under simulated
conditions of the phosphoric acid production. Calcium hydrogen phosphate and sulfuric acid were mixed with dilute
phosphoric acid at 80
C, and the turbidity of the reaction mixture was measured at different time periods to calculate
the induction time of gypsum crystals formation. Addition of Al3+ ions up to 2% decreased the induction time and
increased the growth efciency while addition of Mg2+ increased the induction time and decreased the growth efciency
compared with in absence of additives. Interestingly, the crystals mean and median diameters were found to increase in
the presence of Al3+ and decrease in the presence of Mg2+. The surface energy increased with Al3+ and decreased with
Mg2+ compared to the baseline (without additives). Gypsum morphology changed from needle-like type in absence of
additives to thick-rhombic in the presence of Al3+ ions.
r 2004 Elsevier B.V. All rights reserved.
Keywords: A1. Crystallization; A1. Impurities; A1. Induction time; B1. Gypsum; B1. Phosphoric acid

1. Introduction
Crystallization of calcium sulfate dihydrate
plays a very important role in phosphoric acid
production by the wet process. The increase of
gypsum crystals growth means increase in the
ltration rate of gypsum, i.e., increase in the
*Corresponding
author.
Tel.:
+2025010642;
fax:
+2025010639.
E-mail address: rashad133@yahoo.com (M.M. Rashad).

productivity of phosphoric acid. The phosphate

rocks contain some aluminum but the content
varies widely from 1% to 3% as Al2O3. On the
other hand, most phosphate rocks contains about
0.20.6% of magnesium expressed as MgO but
high dolomitic phosphate rocks up these values to
2%. The effect of aluminum and magnesium ions
on the crystallization of gypsum is not clear. The
presence of aluminum in phosphoric acid has a
positive inuence on the crystal habits, size and
consequently lterability [1,2]. Aluminum is said

0022-0248/$ - see front matter r 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.jcrysgro.2004.03.060

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M.M. Rashad et al. / Journal of Crystal Growth 267 (2004) 372379

to promote regular crystal growth in all directions

by yielding much thicker crystals. This reduces the
surface to volume ratio of the crystals and hence
improving the ltration rate [35]. Budz et al. [6]
showed that aluminum reduces the nucleation and
growth rates of gypsum but promoted the agglomeration of the smaller crystals.
In case of magnesium, It is believed that
magnesium ions hinder the gypsum ltration by
either increasing the viscosity of the ltrate or
affecting the gypsum crystal size [1,2]. However,
wet process phosphoric acid could be produced
from high MgO phosphate rock by accepting a
weaker lter acid, higher ltration temperature
and thinner gypsum cake thickness [7,8]. Li et al.
[9] showed that the presence of magnesium ions
alone decreased the crystal length of gypsum
crystals. On the other hand, Lin et al. [10] showed
that the presence of Mg and Fe together during the
reaction of calcium monohydrogen phosphate
with sulfuric acid at 60
C increased the width of
gypsum crystals.
The present research aims at study the primary
nucleation of gypsum under conditions simulating
the production of phosphoric acid with and
without addition of Al2O3 and MgO using pure
chemicals (calcium hydrogen phosphate and sulfuric acid in phosphoric acid medium).

2. Experimental procedure
2.1. Materials
Calcium
hydrogen
phosphate
CaHPO4
(ADWIC, Egypt), sulfuric acid H2SO4 (MERCK,
Germany) and phosphoric acid H3PO4 (BDH,
England) were chemical reagent grade. Aluminum
hydroxide Al(OH)3 and magnesium oxide MgO
purchased from El-Nasr Pharmaceutical chemicals
(ADWIC), Egypt were used as a source of
aluminum and magnesium ions, respectively.
2.2. Procedure
The main steps are reaction and crystallization,
ltration and washing, drying and characterization
of gypsum.

373

Reaction and crystallization: The following

solutions were prepared:
Solution (1): 27.5% P2O5/2.5% H2SO4.
Solution (2): 20% P2O5.
Solution (3): 32.5% H2SO4.
A 500 ml of solution [1] was heated to 80
C in a
1000 ml Pyrex three-neck bottle, using a thermostatically controlled water bath. The calculated
amount of calcium hydrogen phosphate was
dissolved in a 100 ml of solution [2] which added
to the heated solutions. The desired amounts of
solution [3] and a 50 ml of deionized water
containing aluminum and magnesium were also
added. The reaction was maintained at 80
C with
constant agitation at 550 rpm. These conditions
simulate the DH process for phosphoric acid
production.
Turbidity measurements: Samples of the reaction
mixture were withdrawn at different time intervals
to measure the turbidity during the course of the
reaction using a digital direct reading turbidimeter
(Orbeco-Hellige, USA). Average two readings of
two samples are taken and plotted.
Crystal size distribution: At the end of the
experiment (when the turbidity of the solution
rst exceeded 1000 NTU), about 5 ml of the
reaction mixture was taken and dispersed with
about 50 ml of methanol. Then, size distribution of
the formed crystals was determined using a
Coulter laser size analyzer (Analysete 22,
FRITCH, Germany).
Gypsum morphology: Scanning Electron Microscope (S-7200, Hitachi, Japan) was employed for
investigation of crystal morphology.
2.3. Correlation between induction time and
supersaturation
The surface energy (interfacial tension) between
the crystals and the aqueous solution is a fundamental parameter for understanding the rate of
both nucleation and crystal growth.
Based on the classic homogeneous nucleation theory, the induction time can be related
to the supersaturation using the following

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M.M. Rashad et al. / Journal of Crystal Growth 267 (2004) 372379

374

correlation [11,12]:
B
;
Logtind A
3
T log2 S

% CaHPO4

where A is an empirical constant (dimensionless)

and B depends on the number of variables, and is
given by Eq. (2):
B

bg3 Vm2 NA f y
;
2:3RT3

where b is a geometric (shape) factor of 16p=3 for

the spherical nucleus, f y is a correction factor,
when purely homogeneous nucleation takes place,
it is f y 1 and when heterogeneous nucleation
occurs it is f y 0:01; Vm is the molar volume
(74.69 cm3/mol for gypsum), T is the absolute
temperature K and R is the gas constant
(J/mol K), g is the surface energy (J/m2), NA is
the Avogadro number (mol1). Plotting of log tind
against 1=log2 S over a relatively high range of
supersaturations (1.6181.979) for a xed temperature gives a straight line with slope B=T 3 ;
related to homogeneous nucleation.
The nucleation rate, i.e. the number of nuclei
formed per unit time per volume is given by
Eq. (3):
Js

F expfbg3 Vm2 NA f yg
;
RT 3 ln2 S

where F is a frequency constant and is known as

the pre-exponential factor and has a theoretical
value of 1030 nuclei/cm3 s [13].

3. Results and discussion

Calcium sulfate dihydrate can be formed by
reaction of calcium hydrogen phosphate with
sulfuric acid in which phosphoric acid is produced
as follows:
CaHPO4 H2 SO4 2H2 O-H3 PO4
CaSO4  2H2 O:

Supersaturation ratio S of the solution was

calculated as shown below:

This reaction was carried out at conditions

simulating the industrial production of phosphoric
acid and the crystallization of gypsum was
followed up in the absence and in the presence of
Al3+ and Mg2+ ions.

wt: CaHPO4
 100;
Total soln: wt

C%CaSO4  2H2 O %CaHPO4

Mwt: CaSO4  2H2 O

;
Mwt: CAHPO4
S

C
;
C

where C  is the value of calcium sulfate dihydrate

solubility at 80
C and 27.5% P2O5=0.83 [1].
Crystallization experiments were carried out at
different S values where these values were calculated at different added amounts of CaHPO4 and
H2SO4 as shown in Table 1.
3.1. Determination of the induction time and
growth efficiency
Induction time tind is dened as the time
elapsed between achievement of supersaturation
by addition of reactants and appearance of nuclei.
Generally the value of tind can be determined by
monitoring the turbidity of the supersaturated
solution. The turbidity is plotted against time of
crystallization, and this plot was used to obtain the
induction time. Fig. 1 shows an example of the
obtained plots at S 1:88 in absence of additives.
It can be seen that, the turbidity increases very
slowly up to 3.3 min and then sudden increased.
The time corresponds to this inection is referred
as induction time, (tind 3:3 min in this case).
To study the effect of Al3+ or Mg2+ ions on the
crystal growth of gypsum, experiments were

Table 1
Calculated values of supersaturation ratios at different amounts
of CaHPO4
Wt. CaHPO4 (g)

C

5.3968
6.4762
8.0952
9.4444
9.9417

0.921
1.103
1.380
1.612
1.643

0.83
0.83
0.83
0.83
0.83

1.088
1.301
1.618
1.880
1.979

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1200

375

1200
1000

800
600
400

800

Turbidity, NTU

Turbidity, NTU

1000

Induction time

200

600

4
3
Time,min.

without
1.00%
1.50%
2.00%
3.00%

400

0
7

200

Fig. 1. Induction time of gypsum crystals without additives at

supersaturation 1.880.

0
0

GE

T0  T1
 100:
T0

3
4
Time, min.

1200
1000
800
600
400

without
1.00%
2.00%

200

3.2. Effect of Al3+ and Mg2+ ions on the induction

time and growth efficiency
The effects of Al3+ and Mg2+ ions as Al2O3 and
MgO% from 0.0% to 3.0%, on gypsum crystallization were studied at different supersaturation
ratios from 1.088 to 1.979. A sample of the
obtained turbidity plots at S 1:880 is shown in
Figs. 2 and 3 for Al3+ and Mg2+, respectively.
Addition of 1% Al2O3 shifted the plots towards
shorter time whereas addition of 1% MgO shifted
the plots towards longer time compared with the
plot without additives. The induction time and the
growth efciency were estimated and presented in
Table 2. In addition, increasing aluminum ions up
to 2% as Al2O3 decreases the induction time.
Further increase in Al3+ ions up to 3% increases
the induction time and then decreases the growth
efciency of gypsum (GE 8.30%). From literature [3], Al3+ ions adsorb on [1 0 1] faces formed

Fig. 2. Effect of Al2O3, % on the gypsum turbidity at

supersaturation ratio 1.880.

Turbidity, NTU

carried out at different percentages of ions and

different supersaturation ratios under simulated
conditions of phosphoric acid production. The tind
was calculated as described above and the crystal
growth efciency GE was calculated from values
of the tind with and without each metal ions T1
and T0 ; respectively, as follows in Eq. (9), [14
16]:

0
0

100

200

300
Time, Sec.

400

500

600

Fig. 3. Effect of MgO, % on the gypsum turbidity at

supersaturation 1.880.

Table 2
Induction time and growth efciency of gypsum crystals in the
presence of Al2O3 and MgO at supersaturation ratio 1.880
%

Al2O3

00.0
1.00
1.50
2.00
3.00
a

MgO
a

tind

GE (%)

tind

GE (%)

3.31
1.95
1.97
2.60
3.50

41.09
40.48
21.45
5.74

3.31
4.12

4.71

24.47

42.29

GE=Growth efciency.

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gypsum crystals. This leads to formation as shown

in Fig. 6 using SEM. This is in consistence with
data reported by Budz et al. [6] as they stated that
aluminum ions promote the agglomeration of the
small crystals of gypsum. It is also reported that
Al3+ ions helps in formation of rhombic crystals
[17,18]. So, it is expected that Al3+ ions decrease
the induction time. However, high Al3+ ions
content (about 3% Al2O3) leads to increasing the
viscosity of the medium [17,18] that in consequent
elongates the induction time and inhibits crystallization growth rate.
In case of Mg2+ ions, The obtained results
reveal that the presence of MgO increasing the
induction time and consequently decreases the
growth efciency comparing with the control test
(without additives). Thus, the presence of MgO in
phosphate ore may retard the gypsum crystal
growth i.e., smaller crystals are formed that block
the lter cloth opening and decrease the ltration
rate.
3.3. Correlation between supersaturation ratio and
induction time
The interfacial tension (surface energy) between
the gypsum crystals and the aqueous solution is a
fundamental parameter for understanding the rate
of both nucleation and crystal growth. Relation
between tind against 1=log2 S with and without 1%
Al2O3 and MgO over a relatively high supersaturation ratios from 1.618 to 1.979 gives straight
lines (Fig 4). The surface energies are calculated
from the slopes of these lines-as shown in the
experimental sectionand given in Table 3. The
calculated surface energies are 8.39, 9.53 and
8.05 mJ/m2 without additives, with 1% Al2O3
and with 1% MgO, respectively. It is clear that
the surface energy is increased by addition of 1%
Al2O3 and slightly decreased by addition of 1%
MgO.
The nucleation rate, i.e., the number of nuclei
formed per unit time per volume can be calculated
according to the relation mentioned in the experimental section by known surface energy value. The
obtained of nucleation rates at 1.880 are given in
Table 3. The nucleation rate is relatively lower in
the presence of 1% Al2O3 compared with the

3.1
2.9
2.7
y = 0.0478x + 1.7657

2.5
Log tind

376

2.3
2.1

y = 0.0498x + 1.6468

1.9

baseline
Al2O3
MgO

y = 0.057x+1.292

1.7
1.5
10

12

14

16

18

20

22

24

1/log2 S

Fig. 4. Relation between log tind and 1/log2 supersaturation

ratio with and without 1% Al2O3 and 1% MgO.

Table 3
Surface energy and nucleation rate with 1% of Al2O3 and 1%
MgO
Item

Surface energy
(mJ/m2)

Nucleation rate
(Nuclei/
cm3 s  1028)

Without
1% Al2O3
1% MgO

8.39
9.53
8.05

71.8
58.1
74.8

control test (without additives). In contrast, in the

presence of 1% MgO, the nucleation rate is
relatively higher than the control test. Low
nucleation rate in case of 1% Al2O3 means that a
small number of nuclei are formed. These nuclei
have higher chance to grow to large crystals
compared with high number of formed nuclei in
case of MgO. This result is in consistence with
obtained increase in crystal growth efciency with
addition of 1% Al2O3 and with crystal size
distribution results as given below.
3.4. Effect of Al2O3 and MgO on crystal size
distribution
The crystal size distribution of gypsum in the
presence of 1% Al2O3, 3% Al2O3 1% MgO and

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2% MgO compared with the baseline (without

additives) at supersaturation ratio of 1.880 is given
in Tables 4 and 5. The obtained results reveal that
the percentage of ne crystals (o20 mm) without
additives is 23.0% and this was dropped to 6.40%
in the presence of 1% of Al2O3 and was increased
to 38.7% in the presence of 3% Al2O3. On the
other hand, this value was as high as 39.7% and
57.3% with addition of 1% and 2% MgO,
respectively. Table 4 shows also that the median
and mean diameter of gypsum crystals are higher
with 1% Al2O3 compared with 1% MgO. The
Table 4
Cumulative size analysis of gypsum crystals with and without
Al2O3 and MgO at supersaturation ratio 1.880
Crystal size
mm

5
15
20
30
45
60
75
100
150
250
300
500

Mesh

635

325

200

100
60
50
36

Cumulative volume % passing

Control test
(without
additives)

23.0
30.3
36.4
40.7
44.7
51.1
63.6
86.5
93.1
99.2

Al2O3

MgO

1%

3%

1%

2%

6.40
10.44
16.39
21.88
26.39
34.87
51.50
82.20
90.74
98.81

38.71
59.76
79.88
88.81
92.14
93.06
93.17
93.19
93.26
97.31

4.99
27.09
39.74
61.04
82.48
93.28
98.06
99.75
100
100
100
100

12.01
45.01
57.27
79.64
97.71
99.80
100
100
100
100
100
100

377

lower content of ne crystals and the higher mean

diameter in the case of 1% Al2O3 may indicate
that the gypsum crystal growth is enhanced
compared with the baseline. On contrary, the
higher contents of ne crystals and lower values of
mean diameter in case of 3% Al2O3 and MgO may
imply the lower gypsum crystal growth.
3.5. Gypsum morphology
One of the most important factors affecting the
ltration rate is gypsum morphology (size and
shape of crystals). For the best ltration rates,
crystals of uniform size are most desirable. Very
large crystals co-existing with very small ones in
absence of intermediate size crystals will offer poor
ltration characteristics [1,1719]. The SEM of
gypsum crystals in absence of additives is given in
Fig. 5 which indicates that the shapes of crystals
are needle-type crystals. On the other hand, cluster
crystals are formed in the presence of 1% Al2O3
(Fig. 6). The morphology of gypsum crystals in the
presence of 1% MgO is needle type (Fig. 7).
The average length to width ratio (L/W) of 10
crystals is 12:1 without additives, 3.0:1 with 1%
Al2O3 and 12.5:1 with 1% MgO. Cluster formation together with smaller contents of ne crystals
with Al2O3 (Table 4) would be favorable for the
ow of the liquid phase through these crystals.
This will have industrial impact in phosphoric acid
industry by dihydrate process which depends

Table 5
Statistics of gypsum crystals size in the presence of Al2O3 and
MgO compared with baseline (without additives) at supersaturation ratio 1.880
Item

0.0%
Al2O3
(baseline)
1%

9.59
d10 (mm)
Median d50 (mm)
95.39
d90 (mm)
269.45
Mean diameter (mm) 121.82
Specic surface area
0.22
(m2/g)

MgO
3%

1%

2%

28.89 7.47 7.18 4.78

145.53 24.98 24.45 17.06
294.28 63.10 53.76 36.48
156.48 28.50 27.04 18.18
0.10 0.38 0.37 0.59

dx x % Fraction passing the corresponding size.

Fig. 5. SEM of gypsum crystals in absence of additives.

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M.M. Rashad et al. / Journal of Crystal Growth 267 (2004) 372379

Fig. 6. SEM of gypsum crystals in the presence of 1% Al2O3.

contrast, the presence of 12% MgO inhibited the

gypsum crystals at all supersaturation ratios.
Surface energy is increased in the presence of 1%
Al2O3 and decreased with 1% MgO compared
with the baseline. Nucleation rate is decreased in
the presence of 1% Al2O3 and increased with 1%
MgO compared with baseline. The mean diameter
of the formed crystals is increased and the
ne crystals less than 20 mm is decreased in the
presence of 1% Al2O3 and increased in the
presence of 3% Al2O3 compared with the baseline.
On the other hand, Mean diameter of the formed
crystals is decreased and the ne crystals less than
20 mm is increased the presence of MgO. Interestingly, the majority of the formed crystals are
clusters with 1% Al2O3 and needle-like type with
MgO and baseline.

References

Fig. 7. SEM of gypsum crystals in the presence of 1% MgO.

mainly on the ltration of phosphoric acid

through gypsum medium.

4. Conclusions
Effect of Al3+ and Mg2+ ions on calcium
sulfate dihydrate (gypsum) crystallization under
simulated conditions of phosphoric acid production is studied. The results showed that Al3+%
from 1% to 2% decreases the induction time at all
supersaturation ratios compared with the Mg2+
which increases the induction time at all supersaturation ratios. The growth efciency increases
with addition of 1% Al2O3 up to 41% and
decreases by increasing Al2O3 content to 3%. On

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