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Kinetics of gypsum formation and growth during


the dissolution of colemanite in sulfuric acid

ARTICLE in JOURNAL OF CRYSTAL GROWTH · OCTOBER 2001


Impact Factor: 1.69 · DOI: 10.1016/S0022-0248(01)01525-1

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Journal of Crystal Growth 231 (2001) 559–567

Kinetics of gypsum formation and growth during the


dissolution of colemanite in sulfuric acid
E. Çetina, I. .
’ Erog& lua, S. Ozkarb,
*
a
Department of Chemical Engineering, Middle East Technical University, 06531 Ankara, Turkey
b
Department of Chemistry, Middle East Technical University, 06531 Ankara, Turkey

Received 18 May 2001; accepted 24 May 2001


Communicated by M. Schieber

Abstract

One of the most important boron minerals, colemanite, is dissolved in aqueous sulfuric acid to produce boric acid
whereby gypsum is formed as byproduct. Filtration of gypsum has an important role in boric acid production because
gypsum affects the efficiency, purity and crystallization of boric acid. The formation and growth kinetics of gypsum
during the dissolution of colemanite in aqueous sulfuric acid were studied in a batch reactor by varying the temperature
(60–901C), stirring rate (150–400 rpm), and initial concentrations of the reactants. The initial CaO/H2SO4 molar ratio
was varied between 0.21–0.85 by keeping the initial concentration of sulfate ion at [SO24 ]o=0.623 mol/l, and 0.85–3.41
by keeping the initial concentration of colemanite at [B2O3]o=0.777 mol/l. The crystallization of gypsum from the
solution was followed by monitoring the calcium ion concentration in the solution as it is decreased by the formation of
calcium sulfate precipitate. The calcium ion concentration in the liquid phase first undergoes a rapid exponential decay
and then slowly approaches an asymptotic value of the saturation concentration at the respective temperature.
The saturation concentration decreases with the increasing temperature from 5.2 mmol/l at 601C to 3.1 mmol/l
at 801C, however, further increase in the temperature up to 901C causes an increase in the saturation concentration to
5.1 mmol/l. The stirring rate was found to have no significant effect on dissolution in the range of 150–400 rpm. The
minimum saturation concentration of the calcium ion was obtained at 801C when the initial CaO/H2SO4 molar ratio is
0.85. The boric acid concentration in the solution decreases with the decreasing initial concentration of sulfuric acid.
After the fast dissolution reaction of colemanite in aqueous sulfuric acid, the nucleation of the gypsum crystals first
occurs from the supersaturated solution and then the crystals grow on these nuclei. The needle like crystals become
wider and taller on prolong crystallization. The rate of gypsum crystallization reaction was second order with respect to
saturation level. The evaluation of the kinetic data in an Arhenius plot gives an activation energy of 3472 kJ/mol for
the crystal growth of gypsum from the supersaturated solution obtained by dissolution of colemanite in aqueous
sulfuric acid. r 2001 Elsevier Science B.V. All rights reserved.

Keywords: A1. Optical microscopy; A1. Solubility; A1. Supersaturated solutions; A2. Growth from solutions; B1. Calcium
compounds; B1. Inorganic compounds

*Corresponding author. Tel.: +90-312-210-3212; fax: +90-312-210-1280.


.
E-mail address: sozkar@metu.edu.tr (S. Ozkar).

0022-0248/01/$ - see front matter r 2001 Elsevier Science B.V. All rights reserved.
PII: S 0 0 2 2 - 0 2 4 8 ( 0 1 ) 0 1 5 2 5 - 1
560 E. Çetin et al. / Journal of Crystal Growth 231 (2001) 559–567

1. Introduction tion of calcium sulfate in aqueous solutions,


depending on the conditions of temperature and
Boron is the most important element in the the concentration of the dissolved ions, may yield
world from both strategic and industrial point of only three forms: Calcium sulfate dihydrate
view. Although the element is not used directly, its (Gypsum, CaSO4  2H2O), calcium sulfate hemi-
compounds have a wide range of applications hydrate (CaSO4  1/2H2O), and calcium sulfate
almost in all the manufacturing areas, except food. anhydrite (CaSO4) [7]. Calcium sulfate dihydrate
More than one half of the boron compounds is is either found in nature as a mineral [8] or
consumed in the production of glass and fibers of precipitated from aqueous solutions [9], as well as
various kinds, e.g. in borosilicate glasses. Boron from the hydration of calcium sulfate hemihydrate
compounds are also widely used in detergents, fire [10,11]. Calcium sulfate dihydrate forms small
retardants, nuclear reactors, agriculture, and needle-like crystals having a monoclinic, prismatic
material processing [1]. Boric acid is the most structure with water molecules between the cal-
commonly used boron compound which has a cium and sulfate ions in the unit cell. The crystal
surprising variety of applications in both industrial structures of calcium sulfate dihydrate and calcium
and consumer products [2] and serves as a source sulfate hemihydrate differ from each other because
of B2O3 in many fused products including textile of the amount of lattice water [12]. The formation
fiber glass, optical and sealing glasses, heat- of calcium sulfate dihydrate from aqueous solu-
resistant borosilicate glass, ceramic glazes, and tion has been investigated by using different
porcelain enamels [3]. Boric acid is also used as structural techniques such as microscopy, IR
starting material in the preparation of many boron spectroscopy, differential scanning calorimetry,
chemicals including synthetic organic borate salts, and X-ray diffraction [13–16]. The solubility of
boron phosphate, fluoroborates, boron trihalides, calcium sulfate forms including gypsum decreases
borate esters, boron carbide, and metal alloys such with increasing temperature [17–19], a fact that is
as ferroboron. responsible for the formation of calcium sulfate
Boron is oxophilic and, therefore, occurs scale on heat exchanger surfaces [20]. Thus the
primarily as oxide (borates) in nature. Boron temperature is an important parameter affecting
minerals occur in a few locations in the world. the precipitation of calcium sulfate in the super-
The largest reserves of boron minerals in the world saturated solutions [21]. The solubility of calcium
are in the western part of Turkey [4]. Colemanite sulfate also depends on the concentration of the
(2CaO  3B2O3  5H2O), which is a kind of hydrated ions present in the solution as expected. However,
calcium borate, is one of the most important a study on the solubility of calcium sulfate
boron minerals. Boric acid is produced in Turkey dihydrate in a temperature range of 52–901C in
and Europe mainly from the reaction of colema- solutions containing 0–21% boric acid (H3BO3) has
nite with sulfuric acid [5]. The overall reaction is as shown that the solubility of gypsum is independent
follows: of H3BO3 concentration, but is strongly affected by
2CaO  3B2 O3  5H2 O þ 2H2 SO4 þ6H2 O the H2SO4 concentration in H3BO3 solutions [22].
The crystal growth kinetics of calcium sulfate
-2CaSO4  2H2 O þ 6H3 BO3 ð1Þ
dihydrate in aqueous solutions has been studied
Calcium sulfate dihydrate (Gypsum, Ca- under various conditions; in supersaturated solu-
SO4  2H2O) crystallizes in the reactor. Filtration tions over the temperature range of 25–801C [21], at
of gypsum crystals after the reaction is a crucial heated metal surfaces [23], on the added seed
process in the production of boric acid in high crystals [24], in the presence of polyelectrolytes [25],
purity and with high efficiency, as the subsequent phosphates [26], organophosphorus compounds
crystallization of boric acid from the supernatant [12], polymers [27,28], sodium chloride [29], and
solution is affected by contaminations. in low supersaturation [30].
Although six different calcium sulfate crystal Dissolution of the colemanite mineral in sulfuric
phases have been claimed to exist [6], the forma- acid solutions, yielding a slurry of gypsum crystals
E. Çetin et al. / Journal of Crystal Growth 231 (2001) 559–567 561

and boric acid, has been investigated in the given in Table 1. All the other chemicals used in
temperature range of 20–901C [31]. Although the the analysis were purchased in reagent grade from
filtration of gypsum slurry has been carried out in Merck (Darmstadt, Germany).
the production of boric acid on large scale, there Experimental setup and procedures The experi-
exist no study on the crystal growth kinetics of mental setup consists of a reactor, a mechanical
calcium sulfate dihydrate in the dissolution of stirrer, a heating jacket, a thermocouple and a
colemanite with sulfuric acid in the literature. The temperature control unit. The reactor having an
lack of kinetic data in this industrially important inside diameter of 12 cm and a height of 30 cm (the
field prompted us to start a study dealing with the bottom section) is made up of borosilicate glass
formation and growth of gypsum crystals in ’
(Ildam Kimya, Ankara, Turkey). The top section
dissolution of colemanite with the ultimate goal of the reactor has three entrances; the one at the
of obtaining kinetic parameters which will be used center is for mixing by using a glass propeller.
in designing the filtration of gypsum slurry leaving Thermocouple is placed inside the reactor through
the pure boric acid in the solution from which it one of the other entrances. The last entrance is
can be crystallized. Here we report the first results used for taking samples out of the reactor by
of the investigation on the formation and growth means of a syringe.
kinetics of gypsum during the dissolution of A given amount of sulfuric acid was added into
colemanite with sulfuric acid in a batch reactor one liter of distilled water in the reactor, yielding a
by varying the temperature, stirring rate, and solution with the initial concentration of SO2 4 ion
initial concentrations of the reactants. in the range of 0.156–0.623 M. The reactor was
heated to the reaction temperature. Certain
amount of colemanite was fed into the reactor at
one lot, providing an initial concentration of B2O3
2. Experimental procedure
in the range of 0.194–0.777 M. This time was
considered as the starting point of the reaction.
Materials Colemanite mineral (an average par-
The samples were taken in time intervals and
.
ticle size of 2.5 cm, Hisarcık-Kutahya, Turkey) and
filtered through a blue band filter paper. The
sulfuric acid (93% b.w.) were supplied by Eti
percentage of solid phase in the solution was
Holding A.S. , (Ankara, Turkey). The colemanite
determined as follows: The samples taken during
was crushed in a jaw crusher, grinded in a hammer
the experiment were first weighed and then filtered
mill, and then sieved. The particles smaller than
immediately. The filtrates were first dried and then
250 mm were used in the experiments. The chemical
weighed. The boric acid concentration of the liquid
composition of the colemanite mineral used is
phase was determined as follows: 2 ml sample
solution was transferred into a test tube by using a
2 ml glass-pipette. Two or three drops of concen-
Table 1
Composition of the colemanite used in the experiments,
trated hydrochloric acid and then 10 ml concen-
determined by chemical analysis of the dried sample trated sulfuric acid were added into the solution.
After having mixed the solution for 30 min, 10 ml
Component (wt %)
of carmine solution was added into the solution
B2O3 37.71 which was stirred for 1 h. The absorbance of the
CaO 20.79 solution was measured at 650 nm on a UV-vis
Na2O 0.65
spectrophotometer (Jenway 6105). The absor-
MgO 2.16
Al2O3 1.79 bance values were converted to the concentrations
SiO2 4.08 of boric acid by using the calibration curve
Fe2O3 0.82 prepared by using standard solutions containing
SrO 0.69 known amount of H3BO3. The calcium ion
TiO2 0.17
concentration was determined by Atomic Absorp-
K2O 1.59
tion Spectrophotometer (Philips PU 9200X).
562 E. Çetin et al. / Journal of Crystal Growth 231 (2001) 559–567

Micrographs of gypsum crystals were obtained


by a light microscope (Prior Laboratory Micro-
scope Model B 3000) that was connected online to
a computer by a Pro Series, high performance
CCD Camera. Images were analyzed by using the
analytical imaging software called Image Pro Plus
3.0 for Windows.
Experiments were performed at different tem-
peratures (60–901C), stirring rates (150–400 rpm),
and B2O3 to SO24 molar ratios (0.3–5).
Fig. 1. Variations in the calcium ion concentration during the
dissolution process of colemanite in aqueous sulfuric acid at
3. Results and discussion different temperatures (stirring rate 200 rpm; initial concentra-
tions are [B2O3]o=0.777 and [SO2 4 ]o=0.623 mol/l).

3.1. Dissolution of colemanite in aqueous sulfuric


acid

The colemanite mineral with a particle size


smaller than 250 mm were dissolved in sulfuric acid
at different temperatures 601C, 701C, 801C, and
901C under vigorous stirring. In course of each
dissolution process, concentrations of the boric
acid and the calcium ion as well as the amount of
the solid material in the reactor were determined at
certain time interval to follow the reaction between
the colemanite and the sulfuric acid. It was found
Fig. 2. Variations in the solid content of the reactor during the
that the formation of boric acid is almost dissolution process of colemanite in aqueous sulfuric acid at
completed within the first minute and then the different temperatures (stirring rate 200 rpm; initial concentra-
concentration of boric acid in the liquid phase tions are [B2O3]o=0.777 and [SO2 4 ]o=0.623 mol/l).
remains practically unaltered throughout the
experiment. As a result, the dissolution process undergoes a rapid exponential decay and then
of colemanite in aqueous sulfuric acid is a very fast slowly approaches an asymptotic value, which is
reaction. However, it does not mean that the the saturation concentration at the respective
formation and precipitation of calcium sulfate temperature. In agreement with the previous data,
crystals is as fast as the boric acid formation. The the saturation concentration decreases with the
latter reaction involves the nucleation and growth increasing temperature from 5.2 mmol/l at 601C to
of calcium sulfate, which might require longer time 3.1 mmol/l at 801C, however, further increase in
than that needed for the formation of boric acid. the temperature up to 901C causes an increase in
The crystallization of gypsum from the solution the saturation concentration to 5.1 mmol/l.
can be followed by monitoring the calcium ion Fig. 2 illustrates the changes in the solid content
concentration in the solution as it is decreased by of the reactor during the dissolution process of
the formation of calcium sulfate precipitate. Fig. 1 colemanite in aqueous sulfuric acid at different
illustrates the changes in calcium ion concentra- temperatures (stirring rate 200 rpm; initial con-
tion during the dissolution process of colemanite centrations are [B2O3]o=0.777 and [SO2 4 ] o=
in aqueous sulfuric acid at different temperatures 0.623 mol/l). In all of the experiments, the initial
(stirring rate 200 rpm; initial concentrations are amount of solid in the reactor is 12%. One
[B2O3]o=0.777 and [SO2 4 ]o=0.623 mol/l). The observes a fluctuation in the experimental results
calcium ion concentration in the liquid phase first due to the large uncertainty in the determination
E. Çetin et al. / Journal of Crystal Growth 231 (2001) 559–567 563

of solid content especially at high temperature.


However, a general trend is recognizable; a rapid
increase in the solid content of the reactor to 14%
is observed within the first minute and then it
remains between 14–16% for all the experiments
except the one carried out at 801C in which the
solid content of the solution increases up to 18%.
This is in accordance with the fact that the
maximum amount of gypsum precipitate is ob-
tained at 801C. The small decrease in the solid
content with time may be attributed to the
precipitation of larger particles because of insuffi-
cient stirring. Fig. 3. Variations in the calcium ion concentration depending
on the initial CaO/H2SO4 molar ratio during the dissolution of
In order to investigate the effect of stirring rate colemanite in aqueous sulfuric acid at 801C and a stirring rate
on the dissolution of colemanite in aqueous of 200 rpm. The initial CaO/H2SO4 molar ratio is varied
sulfuric acid, the experiments were performed between 0.21–0.85 by keeping the initial concentration of
at 150, 200 and 400 rpm at 801C starting with sulfate ion at [SO2
4 ]o=0.623 mol/l, and 0.85–3.41 by keeping

the initial concentrations of [B2O3]o=0.777 and the initial concentration of colemanite at [B2O3]o=0.777 mol/l.
[SO24 ]o=0.623 mol/l). The results obtained shows
that the stirring rate does not have any significant the saturation concentrations of the calcium ion.
effect on dissolution in the range of 150–400 rpm. The minimum saturation concentration of the
Indeed, the calcium ion concentration shows calcium ion is obtained when the initial CaO/
similar variations at all stirring rates and one H2SO4 molar ratio is 0.85. Deviation from this
obtains the same solid content of the reactor at the ratio causes a rapid increase in the saturation
stirring rates of 200 and 400 rpm while the non- concentration of calcium ion. These results in-
uniform mixing at 150 rpm does not allow to take dicate the significance of the initial CaO/H2SO4
a representative sample for the determination of molar ratio for obtaining the maximum amount of
the solid content of the reactor. From the gypsum precipitate after the dissolution of cole-
observation that the dissolution of colemanite in manite in aqueous sulfuric acid.
aqueous sulfuric acid is fast and independent of The calcium ion concentrations obtained at the
the stirring rate in the range of 150–400 rpm, one beginning of reaction are much higher than the
can conclude that the reaction is mass transfer saturation values and, therefore, can be considered
limited [32]. This is not unlikely for such a as the supersaturation concentration. Depending
heterogeneous reaction between a solid and a on the initial CaO/H2SO4 molar ratio, the super-
liquid. The rate of the fast dissolution reaction is saturation concentration of calcium ion varies
limited by the rate of diffusion of the sulfuric acid between 0.020–0.065 M. These values are in
through the surface of the solid colemanite accordance with the supersaturation concentration
particles, which is continuously refreshed as the of Ca2+ reported previously for the dissolution of
fast reaction proceeds. colemanite in aqueous sulfuric acid [31]. The
Fig. 3 shows the variations in the concentration supersaturation concentration is between 0.02–
of calcium ion depending on the initial CaO/ 0.035 M, if the initial CaO/H2SO4 molar ratio is
H2SO4 molar ratio during the dissolution of 0.85, for the dissolution of colemanite in aqueous
colemanite in the sulfuric acid at 801C. The initial sulfuric acid at different temperature as shown in
CaO/H2SO4 molar ratio is varied between 0.21– Fig. 1. It is interesting to note that the saturation
0.85 by keeping the initial concentration of sulfate concentration decreases to 0.0031–0.0052 M at the
ion at [SO2 4 ]o=0.623 mol/l, and 0.85–3.41 by end of these experiments.
keeping the initial concentration of colemanite at Another key observation is that the boric acid
[B2O3]o=0.777 mol/l. It is meaningful to consider concentration in the solution decreases with the
564 E. Çetin et al. / Journal of Crystal Growth 231 (2001) 559–567

decreasing initial concentration of sulfuric acid.


This indicates that some colemanite remains
unreacted if the amount of sulfuric acid used is
less than that required to dissolve all the colema-
nite added (if the initial CaO/H2SO4 molar ratio is
greater than 0.85).

3.2. Crystal growth of calcium sulfate dihydrate

Calcium sulfate formed during the dissolution


reaction of colemanite with sulfuric acid crystal-
lizes as calcium sulfate dihydrate (Gypsum,
CaSO4  2H2O) in the reactor at the reaction
temperature. The gypsum crystals were separated
from the supernatant solution by suction filtration,
dried and examined under microscope. Fig. 4
shows the micrographs of the calcium sulfate
dihydrate crystals obtained from the dissolution of
colemanite in sulfuric acid at 801C and 200 rpm
with initial concentrations of [B2O3]o=0.777 and
[SO2
4 ]o=0.623 M at various stage of the process.
After the fast dissolution reaction of colemanite in
aqueous sulfuric acid, the nucleation of the
gypsum crystals first occurs from the supersatu-
rated solution and then the crystals grow on these
nuclei. The induction period, the time passed after
the formation of supersaturated solution until the
appearance of the nuclei, is quite short for the
formation of calcium sulfate dihydrate crystals
(less than a few minutes). Therefore, measurement
of the induction period could not be achieved.
Nevertheless, we could follow the growth of the
gypsum crystals under microscope by taking
samples at certain time after the dissolution of
colemanite in aqueous sulfuric acid. The first
sample taken in 3 min after the dissolution of
colemanite in aqueous sulfuric acid shows needle-
like crystals having average dimensions of 1 mm
width and 10–20 mm length (Fig. 4a). The crystals
become wider and taller on prolong crystallization Fig. 4. Light microscope images of the gypsum samples taken
as it can be seen from the images of the samples from the dissolution of colemanite in aqueous sulfuric acid at
taken at 30th, 60th and 90th minutes of crystal- 801C and a stirring rate of 200 rpm after (a) 3 min, (b) 30 min,
lization in Figs. 4b–4d, respectively. The gypsum (c) 60 min, (d) 90 min.
crystals grow up to 10 mm wide and 80 mm tall
within 90 min. Temperature and stirring rate do dissolution of colemanite in aqueous sulfuric acid
not have a significant effect on the size of gypsum at various temperatures and stirring rate but
crystals when comparing the micrographs of starting with the same initial concentrations of
gypsum samples taken at 270th minute after [SO2
4 ]o=0.623 and [B2O3]o=0.777 mol/l.
E. Çetin et al. / Journal of Crystal Growth 231 (2001) 559–567 565

3.3. Crystallization kinetics

Recent studies have shown that the crystal


growth of calcium sulfate dihydrate on seed
crystals follows a second order kinetics from the
solution supersaturated in calcium and sulfate ions
[15,23,24,29]. The crystallization of gypsum from
the supersaturated solution obtained by dissolu-
tion of colemanite in aqueous sulfuric acid also
obeys a second order rate law which is expressed as
follows by assuming that the initial concentrations
of calcium and sulfate ions are equal:
d½Ca2þ 
rate ¼  ¼ kð½Ca2þ   ½Ca2þ sat Þ2 ; ð2Þ
dt
where the crystal growth rate is given in
mol l1 s1, k is the rate constant in l mol1 s1 Fig. 5. Reciprocal concentration versus time plot for the
which is assumed to be constant during the growth crystallization of gypsum from the supersaturated solution
process and [Ca2+]sat is the saturation concentra- obtained by dissolution of colemanite in aqueous sulfuric acid
tion of the calcium ion in solution. at different temperatures (stirring rate is 200 rpm; initial
concentrations are [B2O3]o=0.777 and [SO24 ]o=0.623 mol/l).
Colemanite is almost completely dissolved in
aqueous sulfuric acid within the first few minutes
(t1 ) and about 90% of calcium sulfate gets
precipitated out in the form of calcium sulfate
dihydrate. If [Ca2+]sup is the supersaturation aqueous sulfuric acid at different temperatures
concentration of calcium ion at time t1 ; Eq. (2) (stirring rate is 200 rpm; initial concentrations are
can be integrated between t1 and t; as follows [B2O3]o=0.777 mol/l and [SO2 4 ]o=0.623 mol/l) as
1 shown in Fig. 5. This indicates that the crystal-
¼ kðt  t1 Þ
½Ca   ½Ca2þ sat
2þ lization of gypsum is a second order process. The
1 slope of the straight line gives the rate constant for
þ : ð3Þ the second order crystallization of gypsum at
½Ca sup  ½Ca2þ sat

respective temperature. Table 2 gives the list of the
The reciprocal concentration of calcium ion kinetic data including the supersaturation concen-
versus time plot gives a straight line for the tration ([Ca2+]sup) obtained at time t1 after the
crystallization of gypsum from the supersaturated dissolution, saturation concentration ([Ca2+]sat),
solution obtained by dissolution of colemanite in the second order rate constant (k) for the crystal

Table 2
Kinetic data for the crystal growth of gypsum crystals from the supersaturated solution obtained by dissolution of colemanite in
aqueous sulfuric acid at various temperatures and at a stirring rate of 200 rpm starting with initial concentrations of [SO2
4 ]o=0.623
and [B2O3]o=0.777 mol/l. [Ca2+]sup: supersaturation concentration obtained within the first few minutes of dissolution, [Ca2+]sat:
saturation concentration, k: the rate constant for the second order crystal growth

Temperature (1C) [Ca2+]sat (mol l1) [Ca2+]sup (mol l1) k (L mol1 s1)

60 0.0052 0.0279 0.07870.003


70 0.0033 0.0240 0.10870.004
80 0.0031 0.0193 0.14670.006
90 0.0051 0.0351 0.21870.008
566 E. Çetin et al. / Journal of Crystal Growth 231 (2001) 559–567

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