Inhibition of calcium carbonate precipitation in NaCl

brines from 25 to 908C

Shiliang He, Amy T. Kan, Mason B. Tomson
Department of Environmental Science and Engineering, MS 317, Rice University, 6100 Main Street, Houston, TX 77005-1892, U.S.A.
Received 18 November 1996; accepted 18 November 1997
Editorial handling by Y. Kharaka
Abstract
The nucleation induction period of CaCO
3
in NaCl brines in the absence and presence of scale inhibitors was
experimentally measured at temperatures from 25 to 908C. A semi-empirical mathematical inhibitor model is presented
for the CaCO
3
scale control in industrial processes based upon nucleation theory and experimental observations.
Results show that the minimum inhibitor dosage (C
inh
) may be obtained from: C
inh
=f(s)/b
inh
log [t
inh
/t
0
], where t
inh
is
the inhibition time, e.g., 20 min, t
0
is the nucleation induction period in the absence of inhibitors, b
inh
is the inhibitor
eciency, and f(s) is the safety factor, e.g., 2. Important factors for the kinetics of both nucleation and inhibition have
been incorporated in this model including the calcite saturation index (SI), temperature (T), and the molar ratio of Ca
to HCO
3
alkalinity (R). In this paper, model parameters are presented for commonly used inhibitors, including 1-
hydroxyethylidene-1,1-diphosphonic-acid (HEDP) and nitrilotri(methylene phosphonic) acid (NTMP). Results show
that HEDP and NTMP are the best inhibitors for calcite scaling in the systems examined. #1998 Elsevier Science Ltd.
All rights reserved.
1. Introduction
Calcium carbonate is the most common scale deposit
(e.g., Cowan and Weintritt, 1976) that occurs widely in
many processes where water is used, such as municipal
and household appliances, cooling towers, boilers, heat
exchangers, mining and mineral processing, and desali-
nation plants. It also occurs in geothermal systems as
well as oil and gas production facilities where natural
brines are produced. The formation of CaCO
3
scale in
these industrial processes where water is used is due to
increases in either temperature or the concentration of
salts including CaCO
3
and alkalinity, while precipitation
of CaCO
3
from produced water is often as the result of
CO
2
degassing and resultant pH increase when the
pressure drops during the production (Rogers et al.,
1990).
Although CaCO
3
scale is fairly easy to treat and
handle, it still presents a problem for the industry.
Among the many methods to control and treat CaCO
3
scale (e.g., addition of acids to lower the pH or addition
of chelating agents to complex Ca
2+
), threshold inhi-
bition by chemical additives (inhibitors) is the most
common and economic approach (Ralston, 1972).
Inhibitors commonly used in the industry include phos-
phates and polyphosphates, phosphate esters, organic
phosphonates, polyacrylates, and various other poly-
mers and copolymers of phosphonates, carboxylates,
and sulfonates (e.g., Ralston, 1972; Matty and Tomson,
1988). The choice of inhibitors depends on the particular
solution composition, compatibility, stability and tem-
perature. Although the inhibition method was invented
in 1936 by Rosenstein (1936), the mechanism of inhi-
bition is still not understood. In addition, there is no
appropriate theory or model available for the use of in-
hibitors in the control of scale deposits, including
CaCO
3
(Vetter, 1976). The appropriate inhibitor to use
and its eective concentration still remain empirical
Applied Geochemistry 14 (1999) 1725
0883-2927/99/$ - see front matter # 1998 Elsevier Science Ltd. All rights reserved.
PII: S0883- 2927( 98) 00033- X
PERGAMON
often requiring extensive testing for each individual
case.
Recently, we have developed a semi-empirical inhibi-
tor model for the control of BaSO
4
scale based on the
nucleation theory and experimental observations (He et
al., 1996). This model predicts which inhibitor to use
and its eective dosage and is found to be consistent
with laboratory dynamic inhibitor testing results and
preliminary eld observations. In this paper, we report
our experimental data of the nucleation induction
period of CaCO
3
over a wide range of saturation indices
and temperatures in the presence and absence of scale
inhibitors. A semi-empirical model for CaCO
3
scale con-
trol similar to that of BaSO
4
will be presented based on
the experimental data.
2. Methodology
The experimental method used in this study of the
nucleation kinetics of CaCO
3
was the same as that for
other sparingly soluble minerals, e.g., BaSO
4
(He et al.,
1995). The occurrence of detectable turbidity in a super-
saturated solution was used as an indication of nuclea-
tion and precipitation. Basically, the supersaturated
solution was prepared by mixing two solutions contain-
ing Ca
2+
and HCO

3
ions, respectively, in a tempera-
ture-controlled reactor in a closed system allowing no
head space for a gas phase. The starting solutions were
ltered through 0.45 mm membranes twice and main-
tained at the desired temperature before mixing. The in-
hibitor was added to the solution with HCO
3
solution in
the inhibition experiments. The induction period is the
time lapse between the creation of the supersaturation
(at the start of mixing) and the rst noticeable turbidity
occurring in the supersaturated solution measured by a
turbidimeter and visual inspection.
Chemicals used in this study, such as NaCl,
CaCl
2
2H
2
O, and NaHCO
3
, were all analytical reagent
grade. All inhibitors were technical grades except
sodium tripolyphosphate which was analytical reagent
grade and no purication was made. These inhibitors
and their molecular weight are listed in Table 1.
The saturation index (SI) of the solution with respect
to calcite is dened as the logarithm of the ion activity
product divided by the thermodynamic solubility con-
stant of calcite {SI = log [(Ca
2+
)(CO
2
3
)/Ksp]}. The SI
was calculated based on a computer program
(EQPITZER) (He and Morse, 1993a) which employed
Pitzer equations for the calculation of activity and
osmotic coecients. This program can be applied to the
carbonate system in NaKCaMgClSO
4
solutions
to 908C (He and Morse, 1993b). The eect of inhibitors
present in the solution on the activity coecient of
Ca
2+
and thus on the SI of calcite was ignored, because
their concentrations were negligible compared to Ca
2+
concentration.
3. Results and the inhibitor treatment model
The induction period of calcium CaCO
3
nucleation in
1 molal NaCl solution was determined at temperatures
of 25, 50, 70 and 908C in the absence of inhibitor addi-
tives and is summarized in Appendix A. Based on the
classic nucleation theory (e.g., Nielsen, 1964), the logar-
ithm of induction period is inversely proportional to SI
2
and T
3
. With a limited range of supersaturation and
temperature as in this study, the logarithm of nucleation
induction period of CaCO
3
in the absence of scale in-
hibitors (t
0
), similar to that of other sparingly soluble
crystals (e.g., BaSO
4
), is found to be proportional to 1/
SI at a given temperature (Fig. 1A) and proportional to
1/T (8K) at a given SI (Fig. 1B) (Nielsen, 1964; He et al.,
1995). Therefore, t
0
can be modeled as a simple function
of SI and T as in Eq. (1):
log t
0
= a
1

a
2
SI

a
3
T

a
4
SI
+
T
(1)
where a
1
to a
4
can be obtained from nonlinear re-
gression analysis from the experimental data of t
0
(Appendix A) over a wide range of saturation indices
and temperatures (SI from 1.0 to 2.6 and T from 258C
to 908C). The results are:
a
1
= 4X22; a
2
= 13X8; a
3
= 1876X4; a
4
= 6259X6
Table 1
List of inhibitors and their molecular weights (in acid forms) used in this study
Inhibitor name Abbreviation Molecular weight
Tripolyphosphoric acid H
5
P
3
O
10
258
1-Hydroxyethylidene-1,1-diphosphonic acid HEDP 206
Nitrilotri(methylenephosphonic) acid NTMP 299
Polyacrylic acid PAA 3500
2-Phosphono 1,2,4-butanetricarboxylic acid PBTC 270
Phosphinopolycarboxylic acid PPPC 1900
Sulfonated polyacrylic acid SPA 3000
S. He et al. / Applied Geochemistry 14 (1999) 1725 18
It is generally observed that the nucleation induction
period of CaCO
3
in the presence of inhibitors (t
inh
) will
be delayed compared to t
0
and the length of t
inh
will
increase the inhibitor concentration increases (Williams
and Ruehrwein, 1957; Nielsen, 1964; Packter and
Sanders, 1970; Dalas and Koutsoukos, 1990; Xyla et al.,
1991). One exception found is when the cation, e.g.,
Ca
2+
, forms an insoluble precipitate with the anion of
inhibitor additives. A dimensionless parameter, called
the ``nucleation inhibition index'' (NII), is dened as the
logarithm of the induction period in the presence of in-
hibitor (t
inh
) divided by the induction period in the
absence of inhibitor (t
0
). The NIIs are experimentally
measured for a number of inhibitors, such as tripho-
sphate (H
5
P
3
O
10
), organic phosphonates (HEDP and
NTMP), polyacrylates (PAA), phosphinopolycarboxy-
lates (PBTC and PPPC), and sulfonated polyacrylates
(SPA). The results are summarized in Appendix B. The
NIIs have been found to be directly proportional to the
concentration of the inhibitor used as in Eq. (2):
NII = log(t
inh
at
0
) = b
inh
C
inh
(2)
where C
inh
is the eective inhibitor concentration in mg/
l or mmol/l and b
inh
is the slope called the inhibitor e-
ciency in l/mg or l/mmol which is a constant for a given
set of chemical and physical parameters, such as super-
saturation (SI), molar ratio of [Ca
2+
]/[HCO

3
], and tem-
perature (T) (Tables 2 and 3). An example of the linear
relationship between NIIs and inhibitor concentration is
illustrated in Fig. 2 for NTMP at 3 dierent degrees of
supersaturation (SI = 1.22, 1.44 and 1.62) at 708C.
Table 2
The eciencies (b
inh
) of various inhibitors for CaCO
3
at 708C
Inhibitor inhibitor eciency (b
inh
, l/mg)
Inhibitor Conditions
SI 1.22 1.44 1.62 1.80 2.20
log R 1.52 1.30 1.10 0.90 0.60
HEDP 41.09 14.91 6.60 2.71 0.60
NTMP 22.13 9.15 4.25 1.52 0.43
PBTC 17.24 8.10 4.09 1.51 0.73
PAA 13.96 5.20 1.69 0.70 0.26
H
5
P
3
O
10
14.54 5.64 2.59 0.83 0.21
PPPC 8.29 3.02 1.27 0.33 0.20
SPA 3.48 1.24 0.57 0.35 0.06
Fig. 2. Nucleation inhibition index (NII) of NTMP for
CaCO
3
at 708C. Line A and crosses are SI of 1.22. Line B
and diamonds are SI of 1.44. Line C and circles are SI of
1.62.
Fig. 1. Saturation index (SI) and temperature (T) dependence
of the nucleation induction period of (t
0
) calcium carbonate
in 1 m NaCl brines without inhibitor. (A) SI dependence at
708C. (B) T Dependence at SI of 1.75.
S. He et al. / Applied Geochemistry 14 (1999) 1725 19
Generally the greater the value of b
inh
, the greater the in-
hibitor eciency.
The minimum inhibitor concentration can be then
predicted from the following equation:
C
inh
=
f (s)
b
inh
|log(t
inh
) log(t
0
)] (3)
where C
inh
will be set equal to the time period in which
the system should be protected from scaling. Therefore,
it is the residence or detention time of the supersaturated
solution in a system which determines the amount of in-
hibitor needed. In the oil and gas production systems, the
inhibition time ranges from minutes to hours depending
on the well parameters and operation conditions (He et
al., 1996), typically about 20 min. A safety factor [ f(s)] is
added in the model to account for the fact ignored in the
laboratory experiments, such as heterogeneous nuclea-
tion on equipment surfaces and micro-particles sus-
pended in the uid and turbulence which play a role in
precipitation in natural and industrial processes.
The parameter b
inh
, as the inhibitor eciency, is
found experimentally to be a function of saturation
index (SI), temperature (T8K), and the molar ratio of
Ca concentration to HCO
3
concentration (R) as in
Eq. (4) (see Fig. 3).
log b
inh
= a
5
a
6
SI a
7
aT a
8
log R (4)
Eq. (4) and our experimental data are consistent with ob-
servations that higher inhibitor concentrations are
needed for higher degrees of supersaturation or higher
temperatures because of faster nucleation rates. The R
dependence of b
inh
comes from the fact that at a given SI,
T and inhibitor concentration, the inhibition eciency
increases as the ratio of lattice cations in the nucleating
crystals (Ca
2+
in CaCO
3
) to the lattice anion (CO
2
3
)
increases. The improved inhibition eciency when R>1
might be due to the fact that the positively-charged
nucleii surface in lattice cation dominated solutions tends
to attract more eciently the negatively-charged inhibi-
tor anions and results in increased interactions and sur-
face coverage (He et al., 1994). Similar phenomena have
been observed in other systems, such as barite and gyp-
sum (He et al., 1994, 1996). In this study, the concen-
tration of HCO

3
is used instead of CO
2
3
in the equation
for the purpose of convenience, because in most cases the
concentration of CO
2
3
has to be calculated while the con-
centration of HCO

3
is the dominant species and can be
approximated as the carbonate alkalinity in oileld
brines. These coecients (a
5
to a
8
) for inhibitors HEDP
and NTMP are tted from our experimental data
(Table 3) and are listed in Table 4.
Table 3
Summary of the inhibitor eciencies (b
inh
) of HEDP and
NTMP under various conditions for CaCO
3
inhibition
log b
inh
(l/mg)
T (8C) log R SI
(HEDP) (NTMP)
70 1.52 1.22 1.614 1.345
70 1.30 1.44 1.174 0.961
70 1.10 1.62 0.820 0.628
70 0.90 1.80 0.433 0.183
70 0.60 2.20 0.219 0.371
70 2.00 1.62 0.957 0.760
70 1.70 1.62 0.910 0.714
70 1.10 1.62 0.820 0.628
70 0.70 1.62 0.742 0.578
70 0.00 1.62 0.670 0.505
70 0.30 1.62 0.628 0.467
70 0.60 1.62 0.576 0.394
70 1.00 1.62 0.535 0.352
25 1.00 1.62 1.425 1.166
50 1.10 1.62 0.977 0.846
90 1.16 1.62 0.666 0.427
Fig. 3. Dependence of the inhibition eciency parameter (b)
of NTMP on saturation index (SI), temperature (T), and
molar Ca
2+
/HCO

3
ratio (R). A: 708C and R of 12.6. B: SI of
1.62. C: 708C and SI of 1.62.
S. He et al. / Applied Geochemistry 14 (1999) 1725 20
Seven inhibitors were tested in this study as CaCO
3
inhibitors, such as polyphosphate (H
5
P
3
O
10
), organic
phosphonates (HEDP and NTMP), and various poly-
mers and their derivatives (PAA, PBTC, PPPC, and
SPA). Phosphonates HEDP and NTMP are the best
performers in the NaCl solutions. In addition, PBTC
and PAA are also very ecient in inhibiting CaCO
3
nucleation. The mechanism of scale inhibition is still
poorly known and remains to be studied.
4. Applications to CaCO
3
scale control in oil and gas
production systems
The inhibitor model presented in this paper, similar
to the one for BaSO
4
(He et al., 1996), is based on the
nucleation theory and experimental observations. It
can be applied to a variety of industrial processes
where CaCO
3
deposits occur. The model can be used
to predict which inhibitor to use and its eective con-
centration under a given condition. Examples are given
in Fig. 4 for typical oil or gas wells, e.g., at 908C and
20 min inhibition (Fig. 4A) or at 708C and 4 h inhi-
bition (Fig. 4B).
A eld example is given here for the CaCO
3
scale
control in a typical oil well, N. R. Smith #4 well, in
Texas which had a history of CaCO
3
scaling problem.
The well produced 80 mcf of natural gas, 39 bbl of oil
and 2300 bbl of brine per day. The produced brine is
NaCl dominated with an ionic strength of 0.89 m. The
chemical composition of the produced brine and other
information of the well are given in Table 5.
The saturation index of the brine is calculated to be
0.37 at the static reservoir condition (71.18C and 129
bars) indicating undersaturation with respect to calcite.
As the brine ows to the surface, the pressure drops
greatly and thus the brine becomes supersaturated with
the calcite. For example, SI is about 1.7 at the surface
if the pressure drops to one atmosphere while the tem-
perature remains the same as the reservoir temperature
(71.18C). This supersaturation was mainly the result of
CO
2
degassing and pH increase as pressure is lowered.
The SI increase with decrease in pressure is plotted in
Fig. 5, assuming constant temperature (71.18C). The
inhibitor dosage of NTMP needed under these con-
ditions is calculated and also plotted in Fig. 5 based
on the inhibitor model presented above. The inhibition
time here is set to 20 min.
It is concluded from these calculations that serious
CaCO
3
scale deposition can occur in the Smith well,
because the SI of calcite can be as high as 1.7. The
NTMP concentration needed increases rapidly as SI
increases to above 1.2. The Smith well was reported to
Table 4
Inhibitor coecients of HEDP and NTMP for inhibition of
CaCO
3
nucleation
Inhibitor a
5
a
6
a
7
a
8
HEDP 0.233 1.6912 1082 0.141
NTMP 0.529 1.6106 1226 0.133
Fig. 4. Model prediction of the minimum inhibitor dosage of
NTMP for CaCO
3
scale control for typical oil or gas wells
under dierent conditions: A: Temperature = 908C and
t
inh
=20 min, and B: Temperature = 708C and t
inh
=4 h.
Table 5
Chemical composition and other information of N.R. Smith
well from Odem Field, San Patricio, Texas
Concentration
Species
mg/l mM
Na 19100 829
Mg 146 6.1
Ca 480 12.0
Ba 19.0 0.14
Cl 30000 857
SO
4
14.0 0.15
HCO
3
1170 19.2
Ionic strength 890
CO
2
(gas) 2.7%
Temperature (reservoir) 71.18C
Pressure (reservoir) 129.3 bar
Depth 1615 m
S. He et al. / Applied Geochemistry 14 (1999) 1725 21
Fig. 5. The scaling tendency (SI) of the N.R. Smith well as
the reservoir pressure drops during the oil production (curve
A). Also shown is the inhibitor (NTMP) dosage (mg/l) pre-
dicted by the inhibitor model under these conditions, using
f(s) = 1 (curve B).
have CaCO
3
scale formation both downhole in the
tubing and in the surface equipment. The well was
treated with downhole ``squeeze'' (pressurised injec-
tion) of the inhibitor NTMP. Once the inhibitor con-
centration in the produced waters dropped below 2 to
3 mg/l, a new treatment was conducted to prevent
CaCO
3
scaling. These eld observations seem to be
consistent with our model prediction. More eld test-
ing is needed to verify the applicability of this inhibitor
model to eld situations.
5. Conclusions
A wide range of scale inhibitors have been found to
inhibit eectively the nucleation and crystal growth of
CaCO
3
in the range of threshold concentrations (0.1 to
10 mg/l). Among them, phosphonates HEDP and
NTMP ranked the best on the weight basis. The in-
hibitor eciency and dosage were modeled based upon
the nucleation theory and experimental observations.
The semi-empirical inhibitor model can be applied for
CaCO
3
scale control which needs commonly measured
or calculated parameters, such as saturation index (SI),
temperature (T), and the molar ratio of Ca concen-
tration to HCO
3
concentration (R). Preliminary eld
observations seem to be consistent with the model pre-
diction.
Acknowledgements
This work was supported by the Brine Chemistry
Consortium including Amoco, Aramco, Baker-
Petrolite, Champion Technologies, Chevron, Conoco,
Shell, Texaco and Unichem, but in no way does this
constitute an endorsement by these companies of any
products or views contained herein.
Appendix A
Summary of the experimental data of the nucleation induction period of CaCO
3
in 1.0 m NaCl and 0.1 m CaCl
2
brines.
T (8C) NaHCO
3
(mm) pH SI (Calcite) log t
ind
(s)
25 3.00 7.38 1.089 4.236
25 4.00 7.38 1.215 3.697
25 5.00 7.38 1.312 3.359
25 6.00 7.38 1.392 3.087
25 7.00 7.38 1.459 2.866
25 8.50 7.38 1.545 2.611
25 10.0 7.38 1.616 2.417
25 11.4 7.38 1.674 2.340
25 12.7 7.38 1.721 2.265
25 14.0 7.38 1.764 2.167
25 15.9 7.38 1.821 2.057
25 17.6 7.38 1.865 1.892
25 19.4 7.38 1.909 1.806
25 21.1 7.38 1.946 1.724
25 25.0 7.38 2.019 1.477
25 30.0 7.38 2.104 1.322
T (8C) NaHCO
3
(mm) pH SI (Calcite) log t
ind
(s)
25 35.0 7.38 2.173 1.231
25 40.0 7.38 2.234 1.146
25 45.0 7.38 2.288 1.041
25 50.0 7.38 2.336 0.954
25 60.0 7.38 2.420 0.845
25 80.0 7.38 2.556 0.778
25 90.0 7.38 2.612 0.699
25 100 7.38 2.663 0.602
50 2.00 7.33 1.059 4.066
50 2.50 7.33 1.156 3.538
50 3.00 7.33 1.235 2.971
50 4.00 7.33 1.359 2.625
50 5.00 7.33 1.456 2.158
50 7.50 7.33 1.631 1.863
50 10.0 7.33 1.755 1.623
50 20.0 7.33 2.053 1.146
S. He et al. / Applied Geochemistry 14 (1999) 1725 22
T (8C) NaHCO
3
(mm) pH SI (Calcite) log t
ind
(s)
50 25.0 7.33 2.148 0.954
50 30.0 7.33 2.226 0.869
50 35.0 7.33 2.292 0.790
50 40.0 7.33 2.348 0.707
50 45.0 7.33 2.398 0.602
50 50.0 7.33 2.441 0.518
50 60.0 7.33 2.520 0.415
50 70.0 7.33 2.590 0.255
70 0.75 7.30 0.770 3.860
70 1.00 7.30 0.890 3.441
70 1.25 7.30 0.990 3.117
70 1.50 7.30 1.070 3.010
70 2.00 7.30 1.190 2.713
70 2.50 7.30 1.290 2.301
70 3.00 7.30 1.370 2.029
70 4.00 7.30 1.490 1.857
70 5.00 7.30 1.590 1.634
70 6.00 7.30 1.670 1.505
70 8.00 7.30 1.790 1.335
70 10.0 7.30 1.890 1.104
70 12.5 7.30 1.991 0.963
70 15.0 7.30 2.060 0.875
T (8C) NaHCO
3
(mm) pH SI (Calcite) log t
ind
(s)
70 17.5 7.30 2.130 0.748
70 20.0 7.30 2.190 0.544
70 30.0 7.30 2.360 0.322
70 40.0 7.30 2.480 0.114
70 50.0 7.30 2.570 0.045
90 0.60 7.16 0.663 3.812
90 0.75 7.16 0.760 3.571
90 1.00 7.16 0.884 3.054
90 1.50 7.16 1.060 2.625
90 2.00 7.16 1.185 2.390
90 3.00 7.16 1.360 1.892
90 4.00 7.16 1.484 1.690
90 5.00 7.16 1.581 1.362
90 6.00 7.16 1.658 1.230
90 7.00 7.16 1.725 1.146
90 8.00 7.16 1.783 1.079
90 9.00 7.16 1.832 0.954
90 10.0 7.16 1.878 0.863
90 20.0 7.16 2.051 0.623
90 30.0 7.16 2.341 0.041
90 40.0 7.16 2.460 0.194
90 50.0 7.16 2.550 0.508
Appendix B
The nucleation inhibition index (NII) of various scale inhibitors for CaCO
3
in 1 m NaCl brines.
Cinh
(mg/l)
T
(8C)
SI
(calcite) log R NTMP HEDP
(NII)
PBTC H
5
P
3
O
10
PPPC PAA SPA
0.01 70 1.22 1.52 0.245 0.45
0.025 70 1.22 1.52 0.643 0.88 0.56 0.441 0.274 0.37
0.037 70 1.22 1.52 0.907 1.61
0.05 70 1.22 1.52 1.097 0.93 0.793 0.508 0.79 0.322
0.075 70 1.22 1.52 1.345 1.26 1.019 1.03
0.1 70 1.22 1.52 0.838 0.556
0.25 70 1.22 1.52 0.9
0.025 70 1.44 1.3 0.169 0.39 0.15
0.05 70 1.44 1.3 0.495 0.74 0.36 0.301 0.2
0.075 70 1.44 1.3 0.754 0.94 0.78 0.512
0.1 70 1.44 1.3 0.959 1.63 0.91 0.744 0.204 0.46 0.113
0.175 70 1.44 1.3 1.525 2.58 1.5 1.081 0.502 0.94
0.25 70 1.44 1.3 2.319 1.96 1.406 0.839 0.327
0.3 70 1.44 1.3 1.47
0.375 70 1.44 1.3 1.025 2.05
0.5 70 1.44 1.3 1.51 0.621
0.75 70 1.44 1.3 1.021
1 70 1.44 1.3 1.118
S. He et al. / Applied Geochemistry 14 (1999) 1725 23
Cinh
(mg/l)
T
(8C)
SI
(calcite) log R NTMP HEDP
(NII)
PBTC H
5
P
3
O
10
PPPC PAA SPA
0.1 70 1.62 1.1 0.19 0.41 0.11
0.175 70 1.62 1.1 0.9 0.56
0.25 70 1.62 1.1 1.017 1.52 0.96 0.613 0.097 0.041
0.3 70 1.62 1.1 0.38
0.375 70 1.62 1.1 1.518 2.41 1.34
0.5 70 1.62 1.1 2.042 2.91 1.97 1.423 0.505 0.218
0.6 70 1.62 1.1 0.81
0.75 70 1.62 1.1 2.692 1.89 0.924
1 70 1.62 1.1 2.665 1.404 1.71 0.352
0.25 70 1.8 0.9 0.222 0.49 0.28
0.5 70 1.8 0.9 0.509 1.29 0.86 0.368 0.16
0.75 70 1.8 0.9 1.398 1.72 1.08 0.637
1 70 1.8 0.9 1.61 2.88 1.75 0.872 0.325 0.43 0.347
2.5 70 1.8 0.9 3.055 2.08
0.5 70 2.2 0.6 0.125 0.43 0.37
1 70 2.2 0.6 0.368 0.6 0.56 0.336 0.301 0.3 0.125
1.75 70 2.2 0.6 0.727
2.5 70 2.2 0.6 0.865 1.03 1.16 0.564 0.564 0.6 0.368
3 70 2.2 0.6 2.07
3.75 70 2.2 0.6 2.95
5 70 2.2 0.6 0.97 0.87 0.426
7.5 70 2.2 0.6 1.609 2.18
10 70 2.2 0.6 2.024 2.46 0.523
0.602
0.025 25 1.62 1 0.25 0.57
0.05 25 1.62 1 0.732 1.33
0.05 50 1.62 1.1 0.47
0.1 50 1.62 1.1 0.677 0.95
0.25 50 1.62 1.1 1.75
0.1 90 1.62 1.16 0.41
0.25 90 1.62 1.16 0.625 1.29
0.5 90 1.62 1.16 1.157 2.31
0.75 90 1.62 1.16 2.054
0.25 70 1.62 2 1.44 2.27
0.5 70 1.62 2 2.87
0.25 70 1.62 1.69 1.309 2.04
0.5 70 1.62 1.69 2.585
0.25 70 1.62 0.69 0.947 1.38
0.5 70 1.62 0.69 1.924
0.25 70 1.62 0 0.76 1.17
0.5 70 1.62 0 1.599 2.34
0.25 70 1.62 0.3 0.732 1.06
0.5 70 1.62 0.3 1.353 2.2
0.25 70 1.62 0.6 0.614 0.95
0.5 70 1.62 0.6 1.287 1.94
0.25 70 1.62 1 0.586 0.86
0.5 70 1.62 1 1.124 1.8
S. He et al. / Applied Geochemistry 14 (1999) 1725 24
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