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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
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
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
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
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)
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