Effects of temperature on the scaling of calcium sulphate in pipes

Tung A. Hoang
a,b,

, H. Ming Ang
a
, Andrew L. Rohl
b,c
a
Department of Chemical Engineering, Curtin University of Technology, PO Box U 1987, Perth 6845, WA, Australia
b
Nanochemistry Research Institute and A.J. Parker CRC for Hydrometallurgy, Curtin University of Technology, PO Box U 1987, Perth 6845, WA, Australia
c
Interactive Virtual Environments Centre (IVEC), Technology Park, Kensington WA 6151, Australia
Available online 25 November 2006
Abstract
Calcium sulphate scaling is a serious problem encountered in many industrial and domestic applications. Supersaturation has been proven to be
the major driving force of scale formation, but the solubility of calcium sulphate changes with temperature. The main purpose of this work is to
investigate the effects of temperature on the formation of calcium sulphate scales in pipes, using a pipe flow system. Various levels of
supersaturation of the calcium sulphate solution have been employed at different temperatures. Results indicated that higher temperature produced
a large increase of scale amounts and a significant decrease of induction periods. Many forms of hydrated calcium sulphate were created at high
temperature. The relationship between deposited scale mass and temperature was deduced from experimental data. From the relationship between
induction period and temperature activation energies of the surface nucleation were estimated to be in the range of 42 to 48 kJ mol
1
.
2006 Elsevier B.V. All rights reserved.
Keywords: Calcium sulphate; Scale deposit; Pipe flow system; Temperature effects
1. Introduction
Scaling or the accumulation of materials depositing on the
surface of equipment is a complicated phenomenon, which
significantly affects a wide range of industrial processes, with
serious technical and economic consequences [14]. Calcium
sulphate is frequently encountered both in nature and in industry
[59]. It is also the most unwelcome scalant in the production of
oil and gas, in water cooling systems and in hydrometallurgical
processes [10].
Early studies on gypsum scaling control mainly focussed on
the kinetics of scale formation [11,12] but later investigations
emphasized the influence of external factors [8,9,1322]. A
systematic study of the effects of various process parameters
and the efficacy of some inorganic and organic additives in
controlling the formation of calcium sulphate in pipes was first
undertaken by researchers of the Department of Chemical
Engineering and A.J. Parker CRC for Hydrometallurgy at
Curtin University of Technology, WA. [23,24]. Using a self
designed pipe flow system and systematically altering the
process parameters they found that the scaling of calcium
sulphate was affected significantly by the supersaturation of the
solution, run time and flow rate [24].
Calcium sulphate precipitates in many different solid phases:
dihydrate (or gypsum), hemihydrate and anhydrous although
gypsum is the most common one at ambient temperature
[25,26]. The solubility of all forms of calcium sulphate changes
with increasing temperature (Fig. 1). The driving force for
crystallisation depends on the supersaturation level of the
solution. However, activation energy is another important factor
that needs to be considered.
2. Experimental
2.1. Equipment setup
The pipe flow system consisted of two glass vessels, one
containing CaCl
2
solution and the other Na
2
SO
4
solution. The
vessels were placed in a water bath with a heating unit to control
temperature. The solutions were transported through the test
section at the same flow rate by using a double-line peristaltic
pump (Fig. 2). The two solutions were mixed at the inlet of the
test section, which consisted of two stainless steel tubular units.
Eight pairs of stainless steel semi-annular coupons were inserted
into the tubular units, serving as scaling surface. Each semi
Powder Technology 179 (2007) 3137
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Corresponding author.
E-mail address: hoanganhtung@hotmail.com (T.A. Hoang).
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doi:10.1016/j.powtec.2006.11.013
annular coupon had a length of 3 cm and an internal diameter of
1.3 cm. The mixed solution coming out from the test section
was collected into a waste container. The test section and
connection hoses were covered with insulating material to keep
the temperature constant.
The conductivity of the output solution was measured using
a Yokogawa Model SC82 conductivity meter, which has two
operational ranges from 0 to 20 S/cm and from 0 to 200 mS/
cm. The meter was equipped with an auto range function and an
automatic temperature compensation.
2.2. Chemicals
Calcium chloride dihydrate (CaCl
2
U2H
2
O), AR grade, and
sodium sulphate (Na
2
SO
4
), AR grade, were from Chem Supply
Pty Ltd., South Australia.
2.3. Procedure
Equimolar solutions of calcium chloride and sodium
sulphate in predetermined concentrations were placed in a
water bath until they reached the required temperature. These
solutions were pumped and mixed together before going into
the test section. After a predetermined time, the pump was
switched off and the test section disconnected. The semi-
annular coupons were withdrawn out of the units and placed in
an oven at 60 C overnight, then cooled down to room
temperature and weighed. The difference between the masses
before and after the experiment was the mass of scale deposit.
The concentration of the solutions, the run time and the
temperature were altered to investigate their effects. To estimate
the induction period, a 50 mL aliquot of the existing solution
was taken every 2 min during the run and its conductivity was
measured immediately. The induction period could be deter-
mined by drawing the best fit lines through the two sections of
the conductivity-time curve and reading the time corresponding
to their intersection.
3. Results and discussion
3.1. Effect of temperature on scale formation
The effect of temperature is shown in Fig. 3. Generally,
within the investigated temperature range from 20 C to 60 C,
the higher the temperature, the more scales formed. Tempera-
ture seemed to significantly promote the scaling of calcium
sulphate. For a 0.075 M solution of calcium sulphate, a small
rise of temperature from 20 C to 30 C tripled the scale
amounts formed after 3 h from 0.0212 kg/m
2
to 0.0603 kg/m
2
.
At 40 C, scale mass increased to 0.1599 kg/m
2
, almost 8 times
as much as that at 20 C. At 50 C and 60 C, the scales were
formed so abundantly that it started blocking the flow after 2 h.
In contrast, the solubility of gypsum does not change much
within this temperature range (Fig. 1). It slightly increases from
2.02 g/L at 20 C to 2.08 g/L at 30 C and 2.10 g/L at 40 C,
Fig. 1. Solubility of calciumsulphate in water as a function of temperature. (Data
from Linke, Marshall and Slusher, Silcock, [2729]).
Fig. 2. Diagram of a pipe flow system.
Fig. 3. Effect of temperature on the scale formation. Flow rate=30 mL/min., Ca
2+
concentration=0.075 M, run time=3 h.
32 T.A. Hoang et al. / Powder Technology 179 (2007) 3137
then reduces to 2.07 g/L at 50 C and 2.01 g/L at 60 C. These
results indicate that solubility change was not the only cause of
the increase in scaling rate. Higher temperatures provided
enough energy to the molecules to overcome the activation
energy of the precipitation reaction and sped up the transport of
scale components from the bulk solution to the surface.
To determine the correlation between scaling and temperature,
logarithm of scale mass is plotted against inverse temperature
(Fig. 4). The curve is linear, indicating an exponential rela-
tionship between the scaling mass and temperature. An equation
could be calculated from the graph using Microsoft Excel.
logscale mass 4047:1
1
T

12:141 1
with the Pearson product moment correlation coefficient
R
2
=0.9995.
From Eq. (1) it can be seen that the higher the temperature
or the lower 1/ T, the larger log (scale mass), and accordingly
scale mass increased by an exponential factor when temper-
ature rose.
scale mass C
T
:10
4047:1
1
T
2
where C
T
is a constant.
Since secondary nucleation is not significantly affected by
temperature, it could be concluded that the primary nucleation
dominated the scaling mechanism. This is consistent with
results from other researchers, who reported that in the precipi-
tation of sparingly soluble substances, secondary nucleation
either did not occur [30] or did occur only to a small extent
[31,32]. The number of crystals formed by secondary nucleation
during precipitation was substantially lower than those resulting
from primary nucleation [33].
3.2. Relationship between scaling rate and temperature
Plotting the amounts of calcium sulphate formed after the
induction period at different temperatures against time shows
that the curves are parabolic indicating scale amount is a
quadratic function of run time (Fig. 5).
To obtain the value of average scaling rate, the scale
amount deposited after every hour was divided by time.
Plotting average scaling rate against run time produces a
Fig. 4. Correlation between log (scale mass) and temperature. Ca
2+
concentration=0.075 M, flow rate=30 mL/min., run time=3 h.
Fig. 5. Plots of scale amounts against time at various temperatures. Flow
rate=30 mL/min. Ca
2+
concentration=0.05 M. Temperature: a. 20 C, b. 25 C,
c. 30 C, d. 40 C.
Fig. 6. Comparison of scaling rates at different temperatures. Ca
2+
concentration=0.05 M. Flow rate=30 mL/min: a. 20 C, b. 25 C, c. 30 C,
d. 40 C.
Table 1
Rate constant at different temperatures Ca
2+
concentration=0.05 M, flow
rate=30 mL/min
Temperature k(kg/m
2
.min
2
) R
2
40 C 1.421510
6
0.9986
30 C 1.197310
6
0.9993
25 C 1.003710
6
0.9910
20 C 0.785010
6
0.9940
33 T.A. Hoang et al. / Powder Technology 179 (2007) 3137
straight line (Fig. 6) with the slope k as indicated in Eq. (3)
below:
1
A
r
dm
dt
kt C 3
where,
dm/ dt the scaling rate (kg/min)
A
r
the scaling area (m
2
)
t run time (min)
C constant
k constant, referring to the change rate of the scaling rate
(kg/m
2
.min
2
)
The k constants derived from the curves in Fig. 6 are listed in
Table 1.
It is indicated that the rate constant also increases when
temperature rises.
3.3. Effect of temperature on induction period
Induction period is the period of time that elapses between
the achievement of supersaturation and the first detection of
crystal deposit onto the pipe walls.
t
ind
t
n
t
g
4
where t
n
is the time necessary for the critical nucleus to be formed
and t
g
represents the time for this nucleus to grow to visible size.
From the statistical concept of nucleation, the mean time of
critical nucleus formation is proportional to J
1
[34]
t
n
~
1
J
5
where J is the steady-state rate of homogeneous or heteroge-
neous primary nucleation. If the time period necessary for the
critical nucleus to be formed is much longer than the time for it
to grow to a measurable size, the induction period is determined
primarily by the former.
Thus,
t
ind
t
n
6
The rate of solid phase nucleation from a supersaturated
solution is [35]
J X exp
DG

kT

7
where,
X the pre-exponential factor depending on diffusion
coefficient in solution and interplanar distance in the
crystal lattice (s
1
m
3
)
G

the energy barrier to nucleation, which corresponds to

the change of Gibbs energy accompanying formation
of the critical nucleus (J)
k Boltzmann constant
T absolute temperature (K).
Combining these three equations and performing a few mathe-
matical transformations gives a relationship between the induction
period and temperature, which is similar to the Arrhenius equation
for the dependence of rate constant on temperature
logt
1
ind
A
E
2:303RT
8
where,
E the molar activation energy for nucleation (J mol
1
)
R universal gas constant =8.31451 J K
1
mol
1
A constant
Fig. 7. Dependence of induction period on inverse temperature. Flow rate=30 mL
min
1
. Coupon diameter =1.3 cm. CaSO
4
concentration: a, 0.05 M; b, 0.075 M.
Table 2
Activation energy for different supersaturation ratios estimated from the slopes
of the curves
CaSO
4
conc. (mol L
1
) Slope=E/ 2.303R E (kJ mol
1
)
0.050 2517.4 (R
2
=0.9986) 48.2
0.075 2215.1 (R
2
=0.9993) 42.4
Table 3
Activation energy for calcium sulphate dihydrate crystallisation from literature
Mode C
CaSO4
(mol L
1
) E
a
(kJ mol
1
) References
Unseeded batch 0.04 160 [36]
Unseeded batch 0.030.1 5361 [6]
Unseeded batch 0.030.1 5171.5 [37]
Seeded batch 0.0414 632 [38]
Seeded batch 0.0148 598 [39]
Seeded batch 0.04 75 [40]
Seeded batch 0.010.02 60 [41]
Seeded batch 0.0155 60 [42]
Seeded batch 0.05 60 [43]
Table 4
Water content of the calcium sulphate scales deposited at different temperature
Temperature (C) 20 30 40 50 60
Water % 20.21 20.07 19.40 13.52 6.31
34 T.A. Hoang et al. / Powder Technology 179 (2007) 3137
Eq. (8) indicates that the induction period of the scaling
depends strongly on temperature. The molar activation ener-
gy corresponding to any supersaturation ratio can be esti-
mated from the slope of the curve plotting log (t
ind
1
) against
1/ T. (Fig. 7). Results of these estimations are given in
Table 2.
The activation energy values estimated here corresponding
to CaSO
4
concentrations of 0.050 and 0.075 mol L
1
are 48.2
and 42.4 kJ mol
1
, respectively, a little lower than those found
by other researchers (Table 3). These values suggest that the
mechanism of scaling in pipes might be different from scale
precipitation in stirred crystallizers. The wall of a pipe can act as
a nucleating site similar to foreign substances causing
heterogeneous nucleation, which requires less energy because
the foreign substances reduce the surface energy of the nucleus
[44].
Also, the mechanism could be partly contact nucleation,
since the change of free energy for contact nucleation is lower
Fig. 8. SEM images of calcium sulphate scale deposited on the pipe walls at
20 C. From top: a, ML=75; b, ML=300; c, ML=1000.
Fig. 9. SEM images of calcium sulphate scale deposited on the pipe walls at
50 C. From top: a, ML=75; b, ML=300; c, ML=1200.
35 T.A. Hoang et al. / Powder Technology 179 (2007) 3137
than that of homogeneous or heterogeneous nucleation [45].
Contact nucleation occurs when a growing particle contacts the
pipe wall. However, the deposition of calcium sulphate is
generally a surface controlled process, since the activation
energy for surface controlled precipitation is typically greater
than 40 kJ mol
-1
, while for a diffusion controlled process it is
expected to be 10 20 kJ mol
-1
[34].
3.4. Forms of scale deposit
The solubility of calcium sulphate as a function of tempera-
ture is illustrated in Fig. 1. Within the range from 0 to 40 C,
calcium sulphate dihydrate has the lowest solubility. Therefore,
it is expected that the scale will contain mainly the calcium
sulphate dihydrate form. At temperatures higher than 40 C the
solubility of other forms decreases significantly, resulting in the
deposition of many forms at the same time. Table 4 presents the
water content in the scales determined by TGA (Thermal
gravimetric analysis).
The water content in pure calcium sulphate dihydrate is
20.9%. Therefore, more than 90% of the scales depositing at a
temperature lower than 40 C would be in the dihydrate form.
At 50 C and 60 C, the water content decreased significantly.
Results from X-Ray Diffraction analysis indicated that the
scales formed at 30 C or 40 C contain only calcium sulphate
dihydrate while there are other hydrate and anhydrous forms
exist in the scales formed at higher temperatures. This led to the
extremely fast deposition of scales at 50 C and 60 C, causing
the blockage of the flow in the test units.
SEM images of the scales reveal different crystalline shapes
formed in low and high temperatures. At 20 C there are scales in
the floral structures created by numerous plate-like and needle-
like crystals. The needles are orthorhombic or hexagonal
prismatic, which are typical forms of gypsum crystals (Fig. 8,
ML = magnification level). On the other hand the floral structures
disappear at 50 C, the number of plate-like crystals reduces and
needles with thinner and longer shape dominate (Fig. 9). The
trend continues as temperature rises to 60 C (Fig. 10).
4. Conclusion
Solution temperature proved to have important effects on
the formation of calcium sulphate scales. High temperature
speeds up the scaling process by significantly reducing the
induction time and enormously increases the scaling rate.
Results indicate the scaling rate is a linear function of time and
the scale mass is an exponential function of inverse absolute
temperature. The activation energies for scaling process
estimated from logarithmical relationship between induction
period and inverse temperature are in the range from 42 to
48 kJ mol
1
, indicates that the deposition of calcium sulphate
is generally a surface controlled process, but contact nucle-
ation partly affects the scaling mechanism. High temperature
also changes the hydrate forms of the scale deposit. At tem-
peratures lower than 40 C, only calcium sulphate dihydrate
is formed, but beyond 40 C, many hydrated and anhydrous
forms precipitate simultaneously.
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