Advanced Materials Research Vols.

554-556 (2012) pp 570-574

Online available since 2012/Jul/26 at www.scientific.net
© (2012) Trans Tech Publications, Switzerland
doi:10.4028/www.scientific.net/AMR.554-556.570

Preparation of α-Calcium Sulfate Hemihydrate from Phosphogypsum in

CaCl2 Solution under Atmospheric Pressure
Ma Baoguo1, a, Ru Xiaohong2,b, Lu Siwen3,c, Zou Kaibo4,d
State Key Laboratory of Silicate Materials for Architectures
(Wuhan University of Technology)
Wuhan 430070, Hubei, P. R. China
a
email:mbgjob@163.com, bemail:rxhwhut@163.com, cemail: 472548180@qq.com,
d
email: wwwzkb@163.com

Keywords: α-Calcium Sulfate Hemihydrate, Phosphogypsum , CaCl2 Solution

Abstract.With the growing demand of phosphoric fertilizer a great quantity of phosphogypsum (PG)
was produced in China.To utilization of PG in an energy-saving way,the phase transition of PG from
DH to α-HH in CaCl2 solution under atmospheric pressure was conducted, the reaction time of phase
transition was significantly shortened by higher reaction temperature and CaCl2 content of the
mixtures. The suitable temperature and CaCl2 addition of the mixture were 95 ºC and 24 wt.%
respectively, morphology of the corresponding dehydration product phase is rod-like shape.
Preparation of α-HH from PG in hot CaCl2 solution at atmospheric pressure was based on dissolution-
crystallization mechanism. The increasing addition of CaCl2 in solution makes the solubility of
CaSO4 decrease due to the common ion effect.

Introduction
Calcium sulfate hemihydrate (HH) is a very important material especially in the building industry.
There are two forms of HH: α phase and β phase , usually the two phases are distinguished according
to the method of preparation1. β phase has a longer history of application in construction and buliding
materials, yet α-HH has gained more acceptance in modern building materials, molding, special
binder systems, dental materials, and some other innovative applications due to it’s better workability
and higher strength values2. But the current commercial processes are energy-intensive and expensive
for large volume applications due to their reaction conditions of elevated temperatures and pressures.
Since 1990s, there is a growing interest in the research of phase-transition of gypsum in
autoclave-free method under atmospheric pressure in concentrated electrolyte solutions because of
its mild reaction condition and energy conservation3. Much work has been focused on the
phase-transition diagrams among DH, α-HH and anhydrite gypsum (AH) in some electrolytes
medium (e.g. phosphoric acid, sulfuric acid, calcium chloride, potassium chloride, sodium chloride,
etc) or methanol-water solution4.
α-HH is now mainly prepared by the dehydration of DH, the raw material mostly comes from
natural gypsum. However, in recent years there is massive industrial byproduct gypsums such as,
phosphogypsum, flue gas desulfurization gypsum, etc. were produced every year with rapid
development of industry . In 2010, with the growing demand of phosphoric fertilizer the production
of PG was up to 70 million tons in China, and only 20.0% is used at present, More and more PG are
continuing to accumulate in large sludge ponds and retaining stockpiles, which not only occupies
plenty of lands but also causes many problems in ecological environment. The best option for dealing
with this problem appears to be the commercial use of PG. Researches have been widely performed
on the utilization of PG as building/road materials, agricultural fertilizers and as an amendment to the
physical and chemical properties of soil5,6.The forms of calcium sulfate such as β-HH or anhydrite
(AH) from PG have been ignored due to their relatively high cost of manufacture.It is essectial to
utilize PG in a high-valued and low-cost way.
Guan7 conducted a pilot scale preparation of –HH from flue gas desulfurization gypsum in mixed
salt solutions under atmospheric pressure, the product obtained in pilot scale has a purity of 95%
with 2 h bending strength of 5.6–6.2 MPa and 3 d compressive strength of 15.7~25.3 MPa, Which

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 Advanced Materials Research Vols. 554-556 571

proved that a-HH can be prepared from industrial byproduct gypsums in a energy-saving way under
atmospheric pressure. In view of this, this paper performed an exploratory research on preparation
of α-HH from PG in CaCl2 solution under atmospheric pressure.

Experimental section
(1)Raw materials
PG used in this study was obtained from Hubei Yihua Fertilizer Co., Ltd of China. PH value of the
material was 3.14.The chemical composition and X-ray diffraction(XRD) tests of PG are given in
Table 1 and Fig.1 respectively. These tests of PG indicating the phase composition are DH phases. Its
scanning electronic microscopy (SEM) microgram(Fig.2) displays a rhombus or parallelogram shape
with cracked ends and surfaces. CaCl2 used in the experiments was calcium chloride dihydrate of
analytical grade. α-HH obtained by steam pressure method was purchased from Junsheng Gypsum
Co., Ltd of China.

Table1.Chemical composition of PG and Reaction Product

Constituent(%) SiO2 AL2O3 Fe2O3 CaO MgO TiO2 SO3 P2O5 BaO SrO H2O
phosphogypsum 4.2 0.54 0.23 36.27 0.91 0.081 47.24 1.72 0.043 0.074 19.37

(2)Methods
The experiments were carried out in a 1.0 L three-necked flask reactor with a reflux condenser, a
teflon stirrer and a thermometer. The reactor was thermostatically regulated by an electric jacket at
85-100 ºC with a deviation of 0.3 ºC. In each run, 300 g CaCl 2 solution of certain concentration was
added to the reactor and preheated to the expected temperature at a constant stirring rate of 150 rpm.
100g PG previously dried at 45 ºC was added into the hot solution to form the reaction slurry. During
each batch operation, hot slurry samples were withdrawn at certain time intervals after the slurry was
stirred for at least 60 minutes and then dripped onto glass slides. Immediately, the samples were
completely dispersed by ethanol and examined under a digital microscope (KP-7700, Hirox Co. Ltd.)
to investigate whether the DH had any morphological change. At the same time, 10ml sample was
withdrawn and immediately filtered by a syringe filter with 0.45 um cellulose membrane. 5 ml of the
leachate was taken and diluted in a 50 ml flask for ions test. Sulfate ion was determined by the baryta
yellow spectrophotometric method. The filter residue was quickly washed three times with boiling
deionized water , then separated by vacuum filtration, rinsed with acetone once, and dried at 60 ºC in
an oven for 4 h. Then the solid phases were examined by scanning electronic microscopy (SEM,
JSM-5610LV, Japan) to investigate the crystal morphology. X-ray diffraction (XRD, D/MAX-RB,
RIGAKU Corporation, Japan) analysis was conducted using Cu Ka radiation at a scanning rate of
10°/min in the 2θ range from 5ºC to 70 ºC. Thermal analysis was performed on a simultaneous
thermogravimetry and differential scanning calorimeter (TG-DSC, STA449c/3/GNETZSCH,
Germany).
572 Advances in Chemistry Research II

Results and Discussion

2.1 Phase-transition of PG in CaCl2 Solutions
The phase- transition times of solid phases in different concentrations of CaCl2 solutions at
85-100 ºC were listed in Table 2. At 85 ºC and in 16 wt.% CaCl2 solutions when reaction time was no
more than360 minutes, all the solid samples showed rhombus or parallelogram shapes of raw
material PG with no reaction signs of other phase, and the solid phases of samples appeared needle
or rod-like shapes with a mixture temperature rising from 90 ºC to 100 ºC when the percentages of
CaCl2 were greater than or equal to 20 wt.%. Therefore, the reaction time of raw PG to the new phase
was significantly shortened by higher reaction temperature and CaCl2 content of the mixtures. More
incomplete finely needle shape crystals were displayed at 100 ºC,meanwhile more CaCl2 addition
suggests a higher product cost. So the suitable temperature and CaCl2 addition of the mixture was 95
º
C and 24 wt.% respectively, morphology of the corresponding dehydration product phase with
reactio n time of 270 minutes (Fig.3) revealed the rod-like shape of new phase and no rhombus or
parallelogram shapes of raw material.

TG-DSC curves of the phase-transition

product of PG in 24 wt.% CaCl2 solution with Table 2. Reaction Time of Phosphogypsum (PG) in
reaction time of 270 minutes (Fig.4) indicated the mixtures
o
of different CaCl2 percentages at
that the new phase was α –HH, which was 85-100 C
characterized by an endothermic peak at 142.7 CaCl2 percentage Reaction time (minute)
º
º
C and the subsequent exothermic peak at (wt.%) 85 C 90 ºC 95 ºC 100 ºC
170.6 ºC. The endothermic peak was 16 >360 >360 >360 >360
accompanied by 5.52% mass loss that 20 >360 >360 360 330
implicated the dehydration process from α 24 >360 >360 270 240
–HH to AH,the exothermic peak corresponds 30 >360 360 240 180
to the transformation of soluble anhydrite
gypsum to thermodynamically stable insoluble anhydrite.So α –HH can be prepared from PG in hot
CaCl2 solution under mild reaction condition .
2.2Thermodynamic analysis
According to the phase transformation theory of crystallization8, only one polymorph is thermody-
namically stable under specific temperature and pressure except at a transition point; all other
polymorphs are unstable and potentially capable of transforming to the stable polymorph. In the
present study, PG was transformed from DH into α-HH in hot CaCl2 solution at atmospheric pressure
was based on dissolution-crystallization mechanism,which suggests that the solubility of α-HH must
be lower than that of DH in this researched system.The solubilities of α-HH, DH from PG have been
measured in experiments under the same conversion conditions (Fig.5). This result is in accordance
 Advanced Materials Research Vols. 554-556 573

with the report by Mullin8 that the more stable phase will always have a lower solubility in any given
solvent. The increasing addition of CaCl2 in solution makes the solubility of all CaSO4 decrease
sharply due to the common ion effect. During the conversion, PG was added to the CaCl2 solution and
dissolved before the first occurrence of conversion.When the concentration of calcium sulfate in
solution was in equilibrium with solid PG (DH), it was supersaturated for solid α-HH. Because DH is
the thermodynamically unstable crystal phase in the researched system, α-HH crystals begin to
nucleate and grow until complete dissolution of PG conversion to α-HH occurs. The presence of
CaCl2 can suppress the transformation of hemihydrate to anhydrite9.

Summary
Preparation of α-HH from PG in CaCl2 solutions under atmospheric pressure was systematically
investigated. The following conclusions have been drawn.
The phase transition of PG from DH to α-HH can perform in CaCl2 solutions under atmospheric
pressure, the reaction time of phase transition was significantly shortened by higher reaction
temperature and CaCl2 content of the mixtures. The suitable tempture and CaCl2 addition of the
mixture were 95 ºC and 24 wt.% respectively, morphology of the corresponding dehydration product
phase is rod-like shape.
Preparation of α-HH from PG in hot CaCl2 solution at atmospheric pressure was based on
dissolution-crystallization mechanism,the increasing addition of CaCl2 in solution makes the
solubility of CaSO4 decrease sharply due to the common ion effect.
These conclusions can provide a reference for the preparation of a-HH from PG in a low-cost and
enery-saving method.

Acknowledgements
This work was financially supported by the fund of Chinese National Technology Support
Project (Project No. 2011BAJ03B03) and Science and Technology Plan of Hubei Province,China
(Project No. DZS0005).
574 Advances in Chemistry Research II

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[8] Mullin, J.W., Crystallization, 3rd revised edition, Butterworth Heinemann, London (1997).
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Advances in Chemistry Research II
10.4028/www.scientific.net/AMR.554-556

Preparation of α-Calcium Sulfate Hemihydrate from Phosphogypsum in CaCl2 Solution under

Atmospheric Pressure
10.4028/www.scientific.net/AMR.554-556.570