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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.
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E-mail address: rashad133@yahoo.com (M.M. Rashad).
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
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
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374
correlation [11,12]:
B
;
Logtind A
3
T log2 S
% CaHPO4
bg3 Vm2 NA f y
;
2:3RT3
F expfbg3 Vm2 NA f yg
;
RT 3 ln2 S
wt: CaHPO4
100;
Total soln: wt
C
;
C
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
0
0
GE
T0 T1
100:
T0
3
4
Time, min.
1200
1000
800
600
400
without
1.00%
2.00%
200
Turbidity, NTU
0
0
100
200
300
Time, Sec.
400
500
600
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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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
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
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5
15
20
30
45
60
75
100
150
250
300
500
Mesh
635
325
200
100
60
50
36
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
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%
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378
References
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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