Академический Документы
Профессиональный Документы
Культура Документы
www.elsevier.com/locate/ces
Abstract
The e/ects of CaSO4 on CaCO3 precipitation were studied in the batch tests at 60, 70 and 80 C in mixtures having calcium carbonate as the dominant salt and at a given total initial calcium concentration of 0:03 M with sulfate concentration ranging from 0 to
0:01 M. Solubility products and rate constants were determined from thermodynamic and kinetic studies and the results indicated that
even minute amounts of calcium sulfate a/ect the thermodynamics, kinetics and the scale structure and no longer the solubility data
and rate constants for the pure salt were applicable. Presence of CaSO4 from 0.002 to 0:01 M increased the calcium carbonate solubility product more than an order of magnitude. The e/ect of salt mixture on the solubility constant of non-dominant salt (calcium sulfate) was reverse as calcium sulfate solubility increased to its pure value with increases in its molar ratio. In addition, the rate equation
suggested in the literature (Nancollas and Reddy, J. Colloid Interface Sci. 37 (1971) 824; Reddy and Nancollas, J. Colloid Interface
Sci. 36 (1971) 166) for pure salt was not applicable to the experimental data. The general observations indicated that the presence
of CaSO4 had weakened the CaCO3 scale which is usually very adherent. The experimental results did take into account the e/ect
of solution ionic strength, however, they suggest that data for pure salt precipitation seem not to be extendable to co-precipitation.
? 2001 Elsevier Science Ltd. All rights reserved.
Keywords: Fouling; Precipitation; Co-precipitation; Calcium sulfate; Calcium carbonate; Composite fouling; Thermodynamics; Kinetics
1. Introduction
Fouling is the accumulation of undesired solid materials at the phase interfaces. Build-up of fouling =lm leads
to an increase in resistance and deteriorates the performance of process equipment such as membranes and heat
exchangers and is costing industries billions of dollars
annually. One of the major fouling phenomena encountered in the aqueous systems is scale formation due to
precipitation of salts present in the water. Lots of metals and anions exist naturally in the water; among them,
CaCO3 and CaSO4 are major fouling contributors. Both
these salts have inverse solubility behaviour where the
solubility decreases with increasing temperature and salts
0009-2509/01/$ - see front matter ? 2001 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 0 9 - 2 5 0 9 ( 0 1 ) 0 0 2 3 7 - 8
5392
Table 1
Summary of batch tests conditions
5393
Run
T ( C)
CaCO3 (M)
CaSO4 (M)
BT1
BT2
BT3
BT4
BT5
BT6
BT7
BT8
BT9
BT10
BT11
BT12
BM1
BM2
70
60
60
70
70
60
70
60
80
80
80
80
60
70
0.030
0.030
0.020
0.020
0.022
0.022
0.028
0.028
0.030
0.020
0.022
0.028
0.000
0.000
0.000
0.000
0.010
0.010
0.008
0.008
0.002
0.002
0.000
0.010
0.008
0.002
0.030
0.030
5394
sulfate concentration increases, the solubility concentration of calcium increases as well and the e/ect of sulfate
gradually levels-o/ as its concentration increases.
Figs. 1(b) and (c), respectively show the e/ect of co
80 C, presence of sulfate increased the equilibrium concentration of calcium and reduced the amount of precipitation but the e/ect levelled-o/ as it approached 0.008
at
0:002
M
SO
4
4
4 )
at given temperatures.
[HCO2
3 ]=
[CO2 ] =
(1)
(2)
(3)
2
CT = [HCO
3 ] + [H2 CO3 ] + [CO3 ]:
(4)
Based on the electroneutrality condition through the proton balance equation, the Total Alkalinity (T.A.) of water
with a total carbon species CT is
2
+
[T:A:] = [HCO
3 ] + 2[CO3 ] + [OH ] [H ]:
(5)
Table 2
SO2
4
60 C
(M)
Final Ca++
(ppm)
Precipitate
% decrease
Final Ca++
(ppm)
Precipitate
% decrease
Final Ca++
(ppm)
Precipitate
% decrease
0.000
0.002
0.008
0.010
552
632
732
740
0
7
15
16
520
592
700
716
0
6
15
16
512
552
700
696
0
3
16
15
70 C
80 C
5395
at 60 C, at 70 C, and 4 at 80 C)
5396
SO2
4 into the solution at 70 C the Ksp value for CaCO3
8
increased to 1:943 10 , by about 500% from the Ksp
(3:00109 ) for pure salt. The Ksp of CaCO3 in mixed so
lutions with 0.008 and 0:01 M CaSO4 at 70 C increased,
respectively, by 1205% and 1329% from that of pure
CaCO3 . The Ksp for CaSO4 was also calculated for all the
Table 3
Solubility product for CaCO3 and CaSO4 (CaCO3 Dominant)
Ksp for CaCO3
Solution
60 C
70 C
80 C
CaCO3 (Bott)
0:030 M CaCO3 (measured)
0:028 M CaCO3 + 0:002 M CaSO4
0:022 M CaCO3 + 0:008 M CaSO4
0:020 M CaCO3 + 0:010 M CaSO4
0:030 M CaSO4 (measured)
CaSO4 (Marshall and Slusher)
1.821E-09
4.011E-09
1.962E-08
4.000E-08
4.408E-08
1.386E-09
3.000E-09
1.943E-08
3.915E-08
4.288E-08
1.056E-09
1.910E-09
1.715E-08
3.415E-08
3.557E-08
60 C
70 C
80 C
5.051E-06
1.907E-05
2.076E-05
1.930E-05
3.594E-05
4.308E-06
1.795E-05
1.921E-05
1.760E-05
3.244E-05
3.615E-06
1.692E-05
1.870E-05
2.889E-05
As seen in previous discussion, the equilibrium concentration of both Ca2+ and CO2
3 ions has increased in presence of sulfate. The e/ect on the non-dominant ion is
much less though cannot be neglected at some ratios of
non-dominant to dominant ions. This means the Ksp values for the pure salts are not suitable to be used when predicting the equilibrium established in a co-precipitating
system.
The e/ect of presence of foreign coprecipitating ionic
species upon the thermodynamic solubility constant of
pure salt could be explained from the thermodynamic
aspect. The formation of pure CaCO3 from Ca2+ and
CO2
3 proceeds according to the reaction below
Ca2+ + CO2
3 CaCO3 (s):
5397
Fig. 5. Comparison of Ksp for both salts in pure and mixed solutions.
(6)
(8)
(9)
5398
Table 4
Equations of Ksp for CaCO3 and CaSO4 (CaCO3 Dominant)
Solution composition
CaSO4
CaCO3
0:000 M
0:002 M
0:008 M
0:010 M
0:030 M
0:028 M
0:022 M
0:020 M
Ksp (CaCO3 )
Ksp (CaSO4 )
r
Ca2+ + CO2
3 CaCO3 (s);
d[Ca2+ ]
= kr {[Ca2+ ][CO2
3 ] Ksp }:
dt
(11)
(12)
in Eq. (12) is the concentration product of Ca2+ and
Ksp
2
CO3 at equilibrium. The experimental data shown in
Fig. 7 (a) indicated that there was a region, known as
initial surge growth, where the crystallisation rate could
not be predicted by Eq. (12). This initial surge was also
noted by Nancollas and Reddy (1971) who thus suggested applying Eq. (12) to the rate of crystallization but
at 60 C, at 70 C, and 4 at 80 C).
excluding the initial surge period and through this obtained linear relationship with slope of unity. Therefore,
the same approach of excluding the initial surge period
was used (as shown in Fig. 7(b)); however, the slopes
of the plots were greatly di/erent from unity. This would
mean that the crystallisation rate of calcium carbonate in
presence of calcium sulfate could not simply be modelled
as a second order reaction. This suggests that using the
rate equations suggested for a single salt crystallization
to crystallization of mixed salts might as well be questionable. Controlled experiments and possibly continuous monitoring of calcium concentration (e.g. by calcium
electrode) is necessary to provide more precise measurements for kinetic analysis during the very early stages
and hence determining the rate and order of reaction.
5. Concluding remarks
The e/ect of water quality is of great importance on
induction times and precipitation of calcium carbonate.
Also the presence of other cations or anions that may form
5399
sulfate. This suggests that there are two di/erent constants for dissociation and association of salt.
Solubility products for both salts were correlated with
temperature using vant Ho/ relationship (Atkins, 1995).
Heat of reaction was similar for solutions with 0.008 and
0:01 M of CaSO4 that exhibited similar solubility constants. This again may suggest and reinforce the hypothesis that presence of non-dominant ion a/ects the heat of
precipitation.
Kinetic data for calcium carbonate did not correspond
to a second-order reaction as suggested in the literature
(Nancollas & Reddy, 1971). But from the concentration
pro=le of the species, it was shown that there was an
initial surge followed by an exponential decrease before
reaching equilibrium. It is possible that the extent of supersaturation had caused this. It is highly recommended
to study the change in [Ca2+ ] and [CO2
3 ] at the initial
stage of crystallisation to examine what is the extent of
the surging process. Also the applicability of 2nd order
reaction rate should be examined with either less supersaturated solutions or with Ca2+ monitoring with electrochemical method that would permit more accurate measurements during initial periods.
References
Atkins, P. W. (1995). Physical Chemistry. Oxford: Oxford University
Press.
Augustin, W., & Bohnet, M. (1995). InJuence of the ratio of free
hydrogen ions on crystallisation fouling. Chemical Engineering
and Processing, 34, 7985.
Bansal, B., Muller-Steinhagen, H., & Chen, X. D. (1997). E/ect
of suspended particles on crystallisation fouling in plate heat
exchangers. ASME Journal of Heat Transfer, 119, 568574.
Blount, C. W., & Dickson, F. W. (1973). Gypsum anhydrite equilibria
in systems CaSO4 -H2 O and CaCO3 -NaCl-H2 O. The American
Minerologist, 58, 323331.
Bott, T. R. (1995). Fouling of heat exchangers. Amsterdam: Elsevier.
Bramson, D., Hasson, D., & Semiat, R. (1996). The roles of gas
bubbling, wall crystallization, and particulate deposition in CaSO4
scale formation. Desalination, 100, 105113.
EPRI, 1982. (Ed.) Design and operating guidelines manual for
cooling water treatment: treatment of recirculating water.
Electric Power Research Institute, Palo Alto, California.
Hardie, L. A. (1967). The gypsum-anhydrite equilibrium at one
atmosphere pressure. The American Mineralogist, Vol. 52, p.
171200.
Hasson, D. (1981). Precipitation foulingA review. In E. F. C.
Somerscales, J. G. Knudsen (Eds.), Fouling of heat transfer
equipment, (p. 527568). New York: Hemisphere Publishing
Corporation.
Hasson, D. (1999). Progress in precipitation fouling research, A
review. In R. Bott (Ed.), Proceedings of engineering foundation
conference, understanding heat exchanger fouling and its
mitigation (p. 6789). New York: Begell House.
Hasson, D., & Karmon, M. (1984). Novel process for lining water
mains by controlled calcite deposition. Corrosion Prevention and
Control, 31, 917.
Hasson, D., & Zahavi, J. (1970). Mechanism of calcium sulfate scale
deposition on heat-transfer surfaces. Industrial and Engineering
Chemistry Fundamentals, 9(1), 110.
5400