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Summary
Scale prevention is important to ensure continuous production
from existing reserves that produce brine. Wells could be abandoned prematurely because of poor management of scale and
corrosion. The objective of this paper is to present an overview
of scale prediction and control and the current research at Rice
University to solve these problems. In this paper, the challenges
of scale prediction at high temperature, high pressure, and high
total dissolved solids (TDS) and an accurate model to predict pH,
scale indices, density, and inhibitor needs at these conditions are
discussed and reviewed: specifically discussed are (1) the various
scale types found in oil and gas production and the condition under
which they form; (2) the relationship of pH, alkalinity, organic
acids, carbonates, and CO2 distribution; (3) the temperature (T),
pressure (P), TDS dependence of the thermodynamic equilibrium
constants and activity coefficients; and (4) the accuracy of the
Pitzer ion-interaction model-based scale-prediction algorithms and
their application. On the basis of a simple propagation of error
estimation, the overall estimated error for calcite saturation index
(SI) is 0.1. This algorithm has been validated with literature
solubility data for six minerals in the T, P, and TDS range of 0
to 200C, 0 to 15,000 psia, and 0 to 350 000 mg/L TDS; for pH
data at 25 and 60C; and density of weighting fluids with density
between 8 and 12.7 lbm/gal.
Introduction
By all accounts, oil and natural gas will be the major components of global energy production for decades to come. Although
proved oil and gas reserves may be declining, oil and gas production can increase with the development of new technologies to
extract energy from unproved reserves and improved economics
of production from both known reservoirs and marginal fields.
For example, oil and gas have gone to deeper and tighter formations with the advance of new production technologies. These
new developments in oil and gas production also bring challenges
in scale prediction and inhibition [e.g., at high T (150 to 200C),
P (1,000 to 1,500 bar), and TDS (greater than 300 000 mg/L)
commonly experienced at these depths]. Brines from different
zones are often mixed in the production tubing, subsea tieback,
or a common facility. Often the oil, gas, and brine composition in
each zone is quite different and consequently will cause significant
scaling. Steam, supercritical carbon dioxide, seawater, or alkaline
surfactant flooding are employed to mobilize residual or heavy
oil. Many of these cost-saving measures can result in significant
scaling problems. Scale prediction, control, and treatment are vital
to the success of these processes.
A major component of scale and corrosion management is the
ability to accurately predict the brine chemistry, pH, and scaling
tendency of a production system. The typical variables in oil and
gas fluid components are shown in Table 1. Because of the complexity of the system, scale prediction is not as straightforward
as one might imagine. In this paper, we attempted to address the
following: (1) the theoretical background of scale prediction and
reliability; (2) the impact of brine salinities, composition, and Ts
on pH, scale, and corrosion; (3) the impact of organic acids; (4)
the reliability of scale prediction at high T and P, and in complex
brine; (5) the impact of hydrate inhibitors on scale formation and
Copyright 2012 Society of Petroleum Engineers
This paper (SPE 132237) was accepted for presentation at the CPS/SPE International Oil &
Gas and Exhibition, Beijing, China, 810 June 2010, and revised for publication. Original
manuscript received 19 March 2010. Revised manuscript received 26 March 2011. Paper
peer approved 10 May 2011.
362
prediction; and (6) the prediction of scale inhibitor needed. Experimental data to validate the model prediction of pH, SI, and density
calculations are also examined, and an estimate of error because of
analysis is determined for a scale-prediction algorithm on the basis
of Pitzer theory of ion interaction to illustrate the interrelationship
of these parameters.
Common Scale Types Found in Oil and
Gas Production
Common oilfield scales can be classified into pH-independent
and pH-sensitive scales. The scaling tendency of sulfates (calcium sulfates, barite, and celestite) and halite scales are not a
strong function of brine pH. Although sulfate scale formation is
not pH sensitive, often the inhibitor reaction is sensitive to pH, as
will be discussed. The carbonates (calcite, dolomite, and siderite)
and sulfide scales are acid soluble, and their scaling tendencies are
strongly influenced by the brine pH. For pH-sensitive scales, the
scale prediction is more complicated because issues that control the
brine pH also affect their scaling tendencies. It should be noted that
at constant T, the solubility of all mineral scales decreases when
P decreases, more so for divalent ions.
Barite. Barite is the mineral name for barium sulfate (BaSO4).
When barite is formed rapidly (relative to geologic times)
from produced water it often contains up to one strontium ion
(Sr2+) per approximately seven barium ions (i.e., approximately
Ba0.88Sr0.12SO4). Sometimes, radioactive radium ions (226Ra2+) also
substitute into the barite crystal lattice and are the major source of
naturally occurring radioactive materials (NORMs).
Barite scale formation can occur because of a pressure drop during production from a reservoir wherein the brine is saturated with
BaSO4, but barite scale formation is generally a consequence of mixing high-sulfate waters such as seawater with formation water during
waterflooding operations or of mixing brine from a high-barium
zone with brine from a high-sulfate zone. Essentially, all minerals
in a reservoir are at equilibrium with the undisturbed connate, or
natural, water. The US Geological Survey (USGS) performed a
survey of log (barium) vs. log (sulfate) for a large group of wells
(Kharaka et al. 1988). The results showed that these wells produce
brine that is saturated with respect to barite at downhole conditions,
within experimental error. Often, either Ba2+ or SO42 concentration
is very low (the limiting reagent effect). Low concentrations of
Ba2+ (<1.0 mg/L) or SO42 (<15 mg/L) are difficult to measure. This
probably accounts for some of the scatter in field data. Therefore,
it is suggested that when production takes place from a single zone
and the well is not flooded, the brine is probably at saturation with
barite in the reservoir. The SI of barite increases as both the T and
P decrease, but it can be demonstrated that the typical T and P drop
from a well producing from a single zone would rarely be sufficient
to cause barite scale to nucleate and grow in the tubing.
Generally, barite scale occurs when either brines from multiple
zones or brines from different wells are mixed, or when there is
flooding of high-sulfate water, as occurs with seawater flooding.
When multiple zones are produced and it turns out that one of the
brines is high in sulfate and the other is high in barium and they
mix at the well bottom, barite scale forms at the bottom of the well,
but is generally delayed for a few feet until mixing is complete.
In both of these cases, the SI value for barite can be exceptionally high and large amounts of scale can form quickly. This can
even produce a supersaturation level that is not controllable with
inhibitors, regardless of the concentration of inhibitor. These are
probably the most dangerous conditions, but unfortunately they
appear to occur rather commonly.
June 2012 SPE Journal
Pressure
Oil
Brine
25 to 500F
or
4 to 260C
14 to 30,000 psi
or
1 to 2,000 atm
Aromatics
Paraffins
Waxes
Asphaltenes
Naphthenic acids
Na , K , Ca ,
2+
2+
2+
Mg , Ba , Sr ,
2+
2+
2+
2Fe , Zn , Pb , Cl , SO4 ,
HCO3 , Br ,
HS , HAc (acids),
SiO2
MeOH,
MEGs,
0.00 to 400,000 mg/L TDS
Processes
+
the solution and on the tubing walls at the bottom on the well. This
condition can be difficult to inhibit with chemical intervention.
B. If barite SI in the perforation region at the bottom of the well
is greater than approximately 0.3 to 1.5, then, in the absence of
inhibitors, there will be nucleation and precipitation on the tubing
walls at the bottom of the well. The kinetics of this scale growth on
the tubing walls will be quite rapid, and scale is expected to form
and build up at the bottom of the tubing, as often occurs. Because
of low barite solubility, the mass of barite scale formed per unit
brine is typically small and may not be detected for a long time.
For this reason the pattern of mineral buildup is often such that
by the time the brine reaches the surface, it is calculated to be at
equilibrium, and one is tempted to suspect that there is no problem.
In these cases, the buildup of barite can sometimes be calculated
by taking the reservoir brine component values minus the surface
values and summing for the barrels of brine produced.
C. If barite SI in the perforation region at the bottom of the well
is less than approximately 0.3, then nucleation will be delayed up
the well. This also applies to wells wherein the brine is at equilibrium with barite in the formation, as can occur in the absence
of seawater flooding. As the brine flows up the tubing, both lower
pressure and lower temperature increase the SI value for barite. All
else being equal, the rate of nucleation and scale growth increase
as the SI value increases. However, as the temperature decreases,
barite precipitation rate decreases quite rapidly. This can cause
barite to nucleate and grow farther up the tubing toward the sur-
SI + 1.5 (120 C)
SI + 3.0 (25 C)
SI + 0.3 (120 C)
SI + 1.3 (25 C)
SI = 0.00
2+
Precipitation and
growth occur only on
seed crystals of barite.
Equilibrium
363
7.5
7
6.5
6
5.5
0
25
50
75
drop that accompanies production. At pressure below the bubblepoint, this pressure drop removes carbon dioxide (CO2) from solution and increases the solution pH and causes calcite to precipitate.
Also, there is a secondary consequence of the pressure drop; the
inherent solubility of calcite in saltwater decreases as the pressure
decreases. Both of these effects tend to cause calcite to precipitate during production. Calcite crystals are composed mostly of
calcium carbonate (CaCO3), but often contain up to 20% iron or
magnesium carbonate, so that the average formula for calcite might
be represented as Ca0.8 to 1.0(Fe,Mg)0.2 to 0.0CO3.
Although naturally occurring calcite such as Iceland spar is
often essentially pure CaCO3, the scale formed from flowing brine
generally contains several mol% of iron. This coprecipitated iron is
often from corrosion products deeper in the well, but can also be a
result of naturally occurring siderite, FeCO3, or other materials in
the reservoir. Most divalent metal ions, such as manganese (Mn2+),
lead (Pb2+), and strontium (Sr2+), can substitute into the calcite
crystal lattice (Deer et al. 1983). Alsaiari et al. (2010) studied the
coprecipitation of iron and calcium carbonate. Calcium ions have a
strong influence in increasing the solubility of iron carbonate. On
the other hand, ferrous iron does not significantly affect the solubility of calcium carbonate. Although calcium carbonate has higher
solubility and also the SI of calcium carbonate was lower than that
of ferrous iron carbonate, calcium carbonate is the preferred phase
to precipitate and the precipitate has a higher molar ratio of Ca/Fe
than that in solution. Additional discussion on scale formation and
inhibition can be found in Frenier and Ziauddin (2008).
pH Definition and the Interpretation of
pH Value of Brine
pH determines the scaling tendency of the pH-sensitive scales
and is of value in interpreting other brine chemistry, such as in
scale, corrosion, or emulsion formation. Yet, the procedures used
to calculate or to measure pH are often of questionable reliability
in oilfield applications. The pH is defined to be equal to the negative of the logarithm (base 10) of the hydrogen-ion activity on a
molality scale (moles of H+ per 1.000 kg of water) with the reference-state activity coefficient equal to 1.000 at infinite dilution in
water [i.e., pH log10 (aH + ) = log10 (mH + H + )].
There are at least three fundamental problems with the concept
of pH and they can only be approximately addressed thermodynamically (Bates 1973): (1) It is impossible to separate the required
activity coefficient product ( H + Cl ) ; (2) there will always be a
junction potential Ej(V) between the solution and the reference
electrode; and (3) the infinite-dilution transfer potential from one
solution to another (e.g., pure water to methanol/water) cannot be
determined. With that realization, a practical approach is adapted to
standardize the pH measurement by comparing the electromotive
force (emf) of a sample to the emf of a standard reference buffer
measured with a glass electrode under well-defined conditions. We
use the operational definition of the pH as is used by the National
Institute of Standards and Technology, which is pH PH(S) +
(EX ES)/(2.303RT/F), where pH is the value read on a pH-meter,
pH(S) is the value assigned to as standard reference buffer [e.g.,
pH(S) = 4.008 for 0.05 m potassium hydrogen phthalate buffer at
June 2012 SPE Journal
pH of pure water vs. T with no added salt, which is the predominant part of the T dependence of the pH. The salt effect on
pH can be derived from solving the equilibrium (K w = aH + aOH )
and the charge-balance ([H+] = [OH] equations simultaneously,
pH = log10 (aH + ) = log10 ( K w1/ 2 ( H + OH )1 2 ). That is, the pH
differs from the pure-water value, just given, only by the square
root of the ratio of the activity coefficients of the hydrogen and the
hydroxide ions. The activity coefficient of the hydroxide ion is almost
always less than that of the hydrogen ion. At 1.0 M NaCl, or 23 000
mg/L Na+ and 35 450 mg/L Cl, and 25C: H+ = 0.876 and OH =
0.610, and pH = log10[10140.876/0.610) = 6.92. Because of the
salt effect on pH electrode junction potential, the pH reading will
be that corrected [i.e., pHmeter reading = 6.92 0.13(1.0 M)1/2 = 6.92
0.13 = 6.79]. In the presence of CO2, the pH will decrease and the
effects of T and P can become large and cause the steel to corrode
(i.e., the classical CO2 corrosion). In the presence of 1% CO2 in the
gas and at room temperature and 1-atm pressure, the pHmeter reading =
4.68. Increasing the temperature to 200F but remaining at 1 atm
pressure raises the pH from 4.68 to 4.96. This is because of the fact
that at the same PCO2 = 0.01 atm, the amount of CO2 that is pushed
into solution is less than that at 77F (25C). There is a secondary
impact of the change in the ionization constants of carbonic acid and
of water, but the primary effect is because of the decreased solubility of CO2 in water at the higher temperature. Next, raising the P
to 10,000 psi at the same T of 200F would lower the pH to 3.76.
This is because the increased pressure greatly increases the PCO2 and
the amount of CO2 that is pushed into the salt water. Overall, these
calculations illustrate the effect of temperature, pressure, TDS, and
CO2 on pH. Water at neutral pH can become corrosive downhole
or scale can form at the surface from nonscaling calcite-saturated
brine. A number of operators developed downhole pH sensors to
measure reservoir pH directly (Breng et al. 2003; Raghuraman
et al. 2007). However, the accuracy of such methods has not been
well documented and is difficult to validate, and international
accepted standards have not been adopted.
Relationship of Alkalinity, Bicarbonate,
Sulfide, and Organic Acids
Bicarbonate is a crucial variable in carbonate-scale prediction,
and it buffers the brine pH. Because bicarbonate concentration
can change with pressure down a well, it is not a conservative
parameter to be used in scale prediction. The change with pressure
is strongly dependent on the specific PCO2, the relative volume of
water, gas, and oil produced; and the total carboxylic acids present.
A useful way to address this problem is by using the concept of
alkalinity (Alk). The advantage of this concept derives from the
fact that although the actual concentration of the weak-acid anions
and pH change with pressure and PCO2, the Alk is constant, as long
as no net acids or bases are added such as CaCO3 precipitates or
dissolves. Note that neither adding nor losing electronically neutral
CO2, H2S, or SiO2 causes any change in Alk. Once the total Alk
and organic acids concentrations are determined by the procedure
discussed, the theoretically corrected bicarbonate concentration
and/or pH at any given operating temperature and pressure can
be calculated.
The origin of Alk is reactions of weak acids from diagenesis
and metabolism with minerals in the formation, such as CaCO3,
Fe(OH)2, MgSiO3, and Na2SiO3, to form weak-acid buffer solutions,
as shown by the following reaction scheme:
minerals
(H 2 CO3 + HAc + H 2S + HCl)aq metal
(HCO3 + CO32 + Ac + HS + S2 )
This is essentially a statement of the charge balance for a solution (Alk =Na+ + K+ + 2Ca2+ + 2Mg2+ Cl 2SO42 ) (i.e.,
the net alkalinity is the sum of strong-base cations minus the sum
of strong-acid anions). Alk is often defined as the total capacity
of the solution to neutralize strong acids. For a system containing
only carbonate, sulfide, and carboxylic acid species, Alk is defined
by the following expression:
366
TAc (M)
0.01
0.011
P-CO2, psia
0
10
0
10
0
20
0.
2
0.
05
0.
01
4.00
0.007
0.008
0.002
20
5.00
0.005
0.006
0.004
0.004
0.005
0.006
0.007
0.008
0.009
6.00
0.003
0.004
0.006
7.00
0.008
0.
2
pH
8.00
0.001
0.002
0.
05
9.00
0.01
0.
01
0
0.001
0.002
0.003
HCO3 conc., M
10.00
TAc (M)
0.012
P-CO2, psia
0.009
0.01
0.011
Fig. 3Plots of the variation of pH and HCO3 concentration vs. PCO2, gas and TAc concentrations, all at a final Alk = 0.01 eq/L 610
mg/L as HCO3. The equilibrium constants used are at 212F and 15 psia and 1 M I. Note that with any specific well, the change
in pressure will typically be by a factor of 100, or less.
Alk0 HCl( M ) =
HCO
10 pH
TAc
10 pH Ac
+ 1
K
HAc HAc,aq
= a 10
pH
TAc
b 10 pH + 1
. . . . . . . . . . . . . . . . . . . . . . . . (2)
where Alk0 is the initial brine alkalinity (equiv.-liter1) and each
mole of added HCl exactly neutralizes one equivalent per liter of
alkalinity. Note that the activity coefficients and equilibrium constants in Eq. 2 are constant for a specific brine and, therefore, the
product of these constants in the first and second terms of Eq. 2 can
be regarded as two adjustable constants, a and b. The titration data
(HCl added vs. pH) can be fitted to Eq. 2 using a nonlinear leastsquares procedure by minimizing the sum of the squares of the
difference between the calculated and the experimental pH, subject
to the constraints of the function S min = in=1 ( pHcaic, i pH exp, i )2
being fitted to to determine the values (Alk0, TAc, a, and b). These
calculations can be performed using Microsoft Excel Solver utility. This method has been tested on three oilfield brines by four
independent laboratories of oil and service companies. Excellent
agreement was observed from the blind round-robin test results
(Table 2).
Typical reactions that may alter the initial brine Alk during
sample storage include oxidation and precipitation, as illustrated
in the following reactions:
June 2012 SPE Journal
9
7
6
pH
6
Gas
Saturation
Bottle
Titration
apparatus
(a)
4
5
6
7
8
9/20/2000
C
Temp (F)
TDS (mg/L)
77.0
9,972
BJ
CO2 (%)
1.00
Std. Err.
Well Name
Total Alk
(mg/L)
986
Location
Carboxylic
acid (mg/L)
411
Field
r2
A
Sample ID
Date
Operator
0.9997
8.0
7.0
pH
6.0
5.0
4.0
3.0
0.00
0.01
(b)
0.01
0.02
0.02
"Exp"
"Calc"
Fig. 4(a) Schematic of the titration apparatus. The parts are (1) CO2/N2 gas cylinder, (2) gas regulator, (3) regulating valve, (4)
1/8-in.-outer-diameter Teflon tubing, (5) glass bottle with a GL-45 2 valve cap, (5) sparging filter, (6) 8-oz. jar with a 1.5-in. stirring
bar, (7) magnetic stirrer, (8) pH electrode, and (9) pH meter. (b) typical titration-results curve fitted by the BCC Total Alkalinity
and Carboxylic Acid Simultaneous Titration at Constant PCO2 program.
2. If both mg/L HCO3 and mg/L CO32 are given, then total Alk
(mg/L HCO3) =2.303(mg/L CO32) + (mg/L HCO3).
3. If you are given a value for phenolphthalein Alk as mg/L
CaCO3 in addition to bicarbonate alkalinity as mg/L CaCO3, then
total Alk (mg/L HCO3) = 1.22(phenolphthalein Alk + bicarbonate
Alk, mg/L CaCO3).
Relationship of pH, PCO2, Alk, and SI
The total moles of each gas component present in the gas, oil,
and brine can be used at all subsequent temperature and pressure
combinations to calculate pH as well as all other solution species at
the new temperatures and pressures. Only two out of the three key
parameters (i.e., PCO2, Alk, and pH) are needed to calculate the total
mass of CO2. Once the pH and PCO2 are measured or calculated,
the total moles of CO2 at specific volumes of gas, oil, and water
368
1
K H 2 CO 3 K1H 2 CO 3 K 2HCO 3 ,
+ 1
+
aH 2 CO 3
CO 2,aq aH HCO 3
. . . . . . . . . . . (4)
TABLE 2ROUND-ROBIN TEST RESULTS OF THE RICE UNIVERSITY TOTAL ALKALINITY, CARBOXYLIC ACID SIMULTANEOUS
Organic
Acid
(mg/L)
Organic
Acid
(mg/L)
Std
Dev
1082
1234
14
401
557
47
514
10
15
12
1123
1254
13
386
418
50
484
32
49
33
1024
1138
10
377
15
229
64
529
91
60
73
1126
1175
10
386
494
60
532
107
41
89
1119
1172
12
377
483
31
525
35
1122
1041
46
329
486
134
543
1111
1220
24
337
381
34
516
1120
1270
34
353
432
39
516
1125
1248
354
431
60
1106
1235
GC analysis
Mean
1186
1133
297
222
0
0
1106
1199
18
359
435
58
520
32
25
27
Standard
error
10
22
31
10
15
13
Standard
deviation
32
69
13
24
93
31
17
43
24
35
pH and PCO2, PH2S can be calculated from nTCO2 and nTH2S at other
temperatures and pressures.
The following illustration is to show how changes in volume
of water or gas will affect the calculated downhole pH by changing the relative fraction of gas-phase CO2 with pressure. At STP
conditions with 0.01-atm PCO2 and a gas/oil/water ratio of 2,000
scf/1 STB/10 STB, the solution pH is 7.25 and dissolved CO2
concentration ([CO2,aq]) is 2.8104 m. When the system is pressurized to 400 atm and is at 25C, PCO2 becomes 0.44 atm, more
CO2 dissolves into the aqueous phase ([CO2,aq]=0.0120 m), and the
solution becomes more acidic (pH 5.76). At the bubblepoint (513
atm) and 25C, the gas phase disappears and all CO2 is dissolved
in the oil and brine phases, the aqueous-phase CO2 concentration
increases to 0.0123 m, and the pH drops to 5.62.
K 2HCO 3
3
3
= log10
SI = log10
H 2 CO 3
aCO2 ,aq K sp K1
aCO2 ,aq
K 2HCO 3
+ log10
(T , P ) .
H 2 CO 3
K sp K1
2
2
aCa 2 + aHCO
mCa 2 + mHCO
Ca 2+ ( HCO )2
3
3
3
=
log
where log10
10
a
m
CO2 ,aq
CO 2, aq
CO2 ,aq
. . . . . . . . . . . . . . . . . . . . . . . . (6)
Scale Prediction
Scale formation tendency can be represented by the thermodynamics-based SI and is defined in the following for calcite:
The SI values for all scale types (e.g., BaSO4 or FeCO3) are calculated by an equation analogous to Eq 5. When SI values at both the
bottomhole and the surface conditions are calculated, SI (= SIsurface
SIbottom hole) can be determined. This SI approach represents the
change in SI vs. (T, P) up the well. If the mineral(s) are at equilibrium in the formation, SIbottomhole = 0. Any calculated deviation from
SIbottomhole = 0.00 is a result of uncertainties in the various measured
parameters, the equilibrium constants, or the calculation procedure
itself. Thereby, most analytical and theoretical uncertainties might
be minimized by using the SI approach. This is often a reliable
way to interpret scale phenomena. Note that the carbonic acid
activity in Eq. 6 can be related to CO2 partial pressure by Henrys
CaCO3,solid Ca 2+ + CO32
aCa 2+ aCO32
Ion Activity Product
SI (Calcite ) Log10
= log10 Calcite
.
K
T
P
)
(
,
K sp (T , P )
sp
. . . . . . . . . . . . . . . . . . . . . . . . (5)
Alkalinity by Titration
Corrected Alkalinity
HDPE
PVS
550
Alkalinity (mg/L)
Alkalinity (mg/L)
PVC
500
450
400
350
300
0
(a)
4
6
Time (Days)
HDPE
550
500
450
400
350
300
0
10
(b)
4
6
Time (Days)
10
Fig. 5Measured Alk of an Fe2+(154 mg/L) containing HCO3 solution (471 mg/L) in 1 M NaCl vs. brine storage time in PVC vs.
HDPE bottles (a) and corrected Alk of the data in Fig. 5a by the procedure (b).
June 2012 SPE Journal
369
SUPCRT92
Eq. 8
9
0
50
100
150
200
250
9.5
10
Activity Coefficients
The Pitzer model is the most accepted ion-interaction model for high
ionic strengths. It has been shown to accurately model the behavior
of electrolyte solution up to 6 mol/kg H2O (Pitzer 1995). At high
TDS, the high ion density of solution can lead to binary interaction
of species of equal and opposite charge and ternary interactions
between three or more ions. The Pitzer model takes into account both
the short-range interactions in concentrated solution and the longrange electrostatic effects of a Dehye-Hkel-type model (Harvie
et al. 1984; Pitzer 1995). The excess free energy is assumed to be
a virial (power series) expansion of binary and ternary interactions
with a leading term of a Debye-Hckel type. Essentially,
10.5
11
11.5
12
Temperature (C)
aCO2,aq
K sp K1HCO 3
= Log10
CO2
HCO 3 CO2
P
K sp K1 K H
CO2 gas
Excess
GPitzer
= RT [ ww f + ww1 ij ( I )ni n j + ww2 ijk ni n j nk ]
i, j
ijk
2
I 1/ 2
f = A
+
ln(1 + 1.2 I 1/ 2 )
1/ 2
1.2
1 + 1.2 I
. . . . . . . . (7)
where K1HCO 3 and K 2HCO 3 represent the first and second ionization
CO 2
constants of carbonic acid, gas
represents the fugacity coefficient
CO 2
of CO2 in the gas, and K H represents the Henrys law constant
for the partitioning of CO2 between gas and water. This is the
recommended procedure, when possible, because generally the
partial pressure of CO2 is better known and more easily measured
than the surface brine pH.
Temperature and Pressure Dependence
of Equilibrium Constants
In SI calculations, the temperature and pressure dependence of the
thermodynamic equilibrium constants and the activity coefficients
is needed. Temperature and pressure dependence of equilibrium
constants has been reported extensively by Helgesons group (Helgeson 1967; Tanger and Helgeson 1988; Johnson et al. 1992). The
Helgeson theory is derived from the temperature and pressure
dependence of the partial molar volume and appropriate integration
and differentiation with Maxwells equations to yield the free energy
of formation and the equilibrium constants at any temperature and
pressure. These equations contain 10 to 88 adjustable parameters.
However, at typical oil- and gas-production temperatures and pressures, the Helgeson equations can be greatly simplified because oiland gas-production temperature and pressure are much below the
critical temperature and pressure of water (373.946C and 22 060
kPa, respectively). Most equilibrium constants can be represented
by approximately five adjustable parameters, as has been done by
USGS (Kharaka et al. 1988). For example, Eq. 8 for barite can be
used to replace the Helgeson equations:
Log10Ksp (for Barite) = 136.035 7680.41 / T(K) - 48.595
Log10[T(K)]+[0.394 0.0001119 T(C)] P(atm) / 500.
. . . . . . . . . . . . . . . . . . . . . . . . (8)
370
Then,
G Excess / RT
ln( i ) = Pitzer
ni
T , P ,n j
= Pitzzer activity coefficients after considerablle rearrangement.
. . . . . . . . . . . . . . . . . . . . . . . (10)
For example for a metal (M) and cations ions (c), anions (a),
and neutral molecules (n):
G Excess / RT
ln( M ) = Pitzer
= z m2 F ( I ) + ma (2 BMa + ZC Ma )
nM
a
T , P ,n j
+ mc (2 Mc + ma Mca )
c
+ z M mc ma Cca + 2 mn nM
c
. . . . . . . . . . . . . . . . . . . . . . . . 11
The Pitzer coefficients BMa, CMa, Mc, Mca, Mca, Cca, and
nM are functions of temperature, pressure, ionic strength, and
composition. For NaCl, a total of 36 constants were included in
Pitzers original derivation, but, for other ions, many parameters
have not been determined. According to Pitzer (1995), the ionpair formation of 2-2 electrolytes (e.g., CaCO30 and CaCO 04 )
has been included in the BMa implicitly.
Pitzer coefficients were derived mostly in binary and ternary systems, such as NaCl-H20 and NaCl-Na2S04-H2O. Several
researchers proposed that an additional explicit ion pair term should
be added if the association constant is greater than 500 for 2-2 type
ion pairs or greater than 20 for 2-l type ion-pairs (Harvie et al. 1984;
He and Morse 1993a, 1993b). Mller (1988) studied the chemical
June 2012 SPE Journal
Parameter
Parameter
Initial
Value
Parameter
Final
Value
SI With
Final
Value
(SI / param.)
( SI)/
SI
(Final-Initial)
SI
parameter
Estimated Error
of Parameters
parameter (parameter)
Estimated
2
2 . Error From
SI
T (F)
340
350
0.73139
0.06718
-6.72E-03
4.51E-05
2.50E+01
1.13E-03
P (psia)
7000
7700
0.56316
-0.10105
1.44E-04
2.08E-08
100
1.00E+04
2.08E-04
1.44E-02
19872
20872
0.63995
-0.02426
2.43E-05
5.89E-10
1000
1.00E+06
5.89E-04
2.43E-02
Na (mg/L)
+
K (mg/L)
500
1500
0.64977
-0.01444
1.44E-05
2.09E-10
25
6.25E+02
1.30E-07
3.61E-04
2+
(mg/L)
54
154
0.65621
-0.008
8.00E-05
6.40E-09
2.50E+01
1.60E-07
4.00E-04
2+
(mg/L)
6500
6600
0.67016
0.00595
-5.95E-05
3.54E-09
325
1.06E+05
3.75E-04
1.94E-02
Mg
Ca
Sr
3.36E-02
2+
(mg/L)
700
800
0.66265
-0.00156
1.56E-05
2.43E-10
35
1.23E+03
2.99E-07
5.47E-04
2+
(mg/L)
550
650
0.66308
-0.00113
1.13E-05
1.28E-10
27.5
7.56E+02
9.65E-08
3.11E-04
Fe
2+
(mg/L)
12
20
0.66487
0.00066
-8.25E-05
6.81E-09
4.00E+00
2.72E-08
1.65E-04
Zn
2+
(mg/L)
10
20
0.66403
-0.00018
1.80E-05
3.24E-10
4.00E+00
1.30E-09
3.60E-05
2+
(mg/L)
0.66421
0.00E+00
0.00E+00
4.00E+00
0.00E+00
0.00E+00
Cl (mg/L)
43000
44000
0.67331
0.0091
-9.10E-06
8.28E-11
2150
4.62E+06
3.83E-04
1.96E-02
2-
15
0.66431
1E-04
-1.00E-05
1.00E-10
2.50E+01
2.50E-09
5.00E-05
F (mg/L)
11
0.66407
-0.00014
1.40E-05
1.96E-10
1.00E+00
1.96E-10
1.40E-05
Br (mg/L)
10
20
0.66425
4E-05
-4.00E-06
1.60E-11
2.00E+00
3.20E-11
5.66E-06
SiO2 (mg/L)
10
20
0.66421
0.00E+00
0.00E+00
3.00E+00
0.00E+00
0.00E+00
Alk (mg/L)
281
291
0.7019
0.03769
-3.77E-03
1.42E-05
14.05
1.97E+02
2.80E-03
5.29E-02
10
0.62817
-0.03604
3.60E-03
1.30E-05
10
1.00E+02
1.30E-03
3.60E-02
1.04
1.14
0.63055
-0.03366
3.37E-01
1.13E-01
0.01
1.82E-04
2.06E-05
4.54E-03
1.09E+01
1.19E+02
0.0005
2.50E-07
2.97E-05
5.45E-03
0.66386
-0.00035
3.50E-06
1.22E-11
425
1.81E+05
2.22E-06
50
2.50E+03
8.82E-06
2.97E-03
2.50E+01
7.92E-08
2.82E-04
Ba
Pb
-
SO4 (mg/L)
-
Organic acids
(mg/L)
CO2 (%)
pH=7.1627 pH=7.1240
H2S (%)
0.0283
-0.66421
0.97266
pH=7.1627 pH=7.1722
3
0.30845
-0.66421
8500
Oil (BPD)
1000
1100
0.67015
0.00594
-5.94E-05
3.53E-09
100
200
0.66984
0.00563
-5.63E-05
3.17E-09
Brine (BPD)
SI-initial =
8600
0.66421
SUM Sqrs =
Estimated error in Calcite SI value, (SUM Sqrs)
1/2
6.84E-03
=
0.08270
Calcite, 140 F
Barite, 203 F
Halite, 32-536 F
Bypsum, 122 F
Barite
1.0
Anhydrite, 122 F
Celestite, 169 F
0.5
Barite SI
Calculated SI
1.5
1
0.5
0.0
0.5
1 m NaCl
0
1.0
0.5
200
400
Temperature (F)
1.5
2
(b)
0
Ionic Strength
(a)
Barite
372 F
478 F
1
0.8
0.6
0.4
0.2
0
0.2
0.4
0.6
0.8
1
1.0
0.5
Calcite SI
Barite SI
205 F
0.0
0.5
1.0
10000
200
20000
Pressure (psia)
(c)
400
600
Temperature (F)
(d)
Fig. 7Plot of Pitzer-theory-based SI of selected literature-reported mineral-salt-solubility data: (a) the calculated SI of selected
solubility data for calcite, barite, halite, gypsum, anhydrite, and celestite at different temperature and ionic strength where the
pressure is typically close to the vapor pressure of water (Ellis 1959; Templeton 1960; Bock 1961; Ellis 1963; Marshall et al.
1964; Blount 1977; Pitzer et al. 1984; Wolf et al. 1989; Howell et al. 1992); (b) barite SI of solubility data at 77 to 400F (Kan et al.
2005); (c) barite SI of solubility data at 200 to 400F and 0- to 15,000-psia pressure (Blount 1977); and (d) calcite SI of solubility
data from 77 to 500F and vapor pressure of water (Ellis 1959, 1963; Wolf et al. 1989).
pH
K
10
H+
CO 2
H
PCO2 g ,CO2 K
H 2 CO 3
1
HCO
or
10 pH
CO
(10 pH )2
TAc
Kw
= 0.
10 pH Ac
10 pH OH
+
1
K
HAc HAc,aaq
. . . . . . . . . . . . . . (12)
I (m)
T (C)
P (psia)
SI S.D.
Calcite
0 6.24
0 200
14.7 174
0.047 0.121
30
Barite
0 5.0
22 250
14.7 14,417
-0.013 0.147
36
Halite
6.097 10.4
0 300
14.7 1,244
-0.003 0.041
13
Gypsum
0 6.08
0 70
14.7 50
0.036 0.144
18
Anhydrite
0 6.30
150
14.7
-0.087 0.081
Celestite
04
20 150
14.7 7,409
-0.137 0.156
19
0 10
0 200
0% MeOH
Gypsum
1.E-02
1.E-03
Barite SI
1.E-01
Celestite
1.E-04
1.E-05
Barite
1.E-06
0 .0
0.1
0.2
-0.013 0.14
14.7 15,000
0.3
25% MeOH
2
1.5
1
0.5
0
0.5 0
1
1.5
2
100
0.4
(a)
123
75% MeOH
49% MeOH
200
300
400
Temperature (F)
(b)
Methanol Conc. (Mole Fraction)
25% MeOH
49% MeOH
75% MeOH
Literature
1.0
7
6
25 C
5
Halite SI
0% MeOH
Obs.
4
3
2
0
20
40
60
80
0.0
0
100
200
300
400
100
MeOH (wt%)
(c)
1.0
Temperature (F)
(d)
Fig. 8(a) Sulfate salts solubility in methanol/NaCl/water solutions; (b) calculated barite SI using barite solubility data in 075%
methanol/NaCl/water solution at 77 to 400F; (c) literature-reported and observed halite solubility in methanol/NaCl/water solution
at 25C; and (d) calculated halite SI using halite solubility data in 0 to 75% methanol/NaCl/water solution at 77 to 400F.
Mineral
Cosolvent
I (mol/Kg H2O)
T (C)
Barite
MeOH
0 75
03
0 200
Barite
MEG
0 75
13
0 200
Barite
TEG
0 90
13
0 25
Halite
MeOH
0 90
2.8 6.2
0 200
Halite
MEG
0 80
6.2 8.6
0 200
Celestite
MeOH
0 50
03
0 25
Gypsum
MeOH
0 50
03
25
Calcite
MeOH
0 75
03
0 100
Calcite
MEG
0 75
03
0 100
373
Calc pH (I)
Obs pH (I)
Calc pH (II)
Obs pH (II)
6.5
I. HAC=8.53 mM
6.0
y = 0.998x
II. HAC=35.18 mM
R = 0.98
6.10
5.5
pH
Calc. pH
5.90
5.0
5.70
5.50
4.5
5.30
4.0
5.3
0
100
200
(a)
300
400
500
5.8
600
(b)
PCO2 (psi)
6.3
Measured pH
Fig. 9pH calculated from Eq. 12 vs. measured pHs. (a) the pH of two solutions at equilibrium with different CO2 partial pressure in the gas phase. The experimental data were from Kaasa (1998). The solutions contained 16.53 mM sodium bicarbonate
and either 8.53 or 35.18 mM acetic acid. The pHs were measured at 60C, and the solution is at equilibrium with 0- to 500-psi
CO2 partial pressure (0 to 40 bar). (b) The pH of calcite-saturated solutions containing various weight% of methanol or MEG at
0 to 1 atm of CO2 partial pressure.
Density Calculation
The excess molar volume can be estimated from the pressure derivative
of Pitzer activity coefficients [i.e., Vi ex = log( i P ) RT ]. Therefore,
the density of the salt solution can be estimated from Pitzer theory by
1000 + mi MWi
. . . . . . . . . . . . . . . . . . (13)
Salt Solution
374
Conc. (M)
Reported in CRC
Handbook of
Chemistry and Physics
Density (g/mL)
Calculated by Eq. 13
Deviation
(g/mL)
Acetic acid
6.255
1.043
1.049
0.006
Na Acetate
4.243
1.160
1.170
0.010
KCl
3.742
1.168
1.162
0.006
NaCl
5.326
1.197
1.185
-0.012
MgCl2 6H2O
4.021
1.276
1.287
0.011
BaCl2
1.597
1.279
1.282
0.003
MgSO4 7H2O
2.799
1.296
1.262
-0.034
CaCl2 2H2O
5.03
1.395
1.420
0.026
HCl
6.022
1.098
1.097
-0.001
NaBr
5.495
1.414
1.421
0.007
SrCl2
2.293
1.298
1.303
0.005
H2SO4
5.313
1.303
1.288
-0.015
0.012
KHCO3
2.801
1.169
1.181
K2CO3
4.093
1.414
1.473
0.059
NaHCO3
0.743
1.043
1.042
-0.001
Na2CO3
1.638
1.157
1.170
0.013
Average deviation
0.0060.019
13.0
y = 0.9981x
12.5
R2 = 0.998
12.0
11.5
11.0
10.5
10.0
9.5
9.0
8.5
8.0
8.0
8.5
9.0
9.5
10.0
10.5
11.0
11.5
12.0
12.5
13.0
Fig. 10Density of commercial weighting fluids calculated by Eq. 13 vs. that measured at 25C.
Calcite SI
NTMP
70
60
2.5
50
40
1.5
30
NTMP (mg/L)
Calcite SI
1
20
0.5
10
0
0
50
100
0
150
Temperature (C)
Fig. 11Calculated calcite SI and inhibitor need vs. time. The
brine composition of a gas well in Texas is used for illustration.
June 2012 SPE Journal
(
+
/SI +
binh ( L /mg ) = 10
Cinh ( mg /L ) =
/T ( K ) +
3 /(SI T ( K ))
) . . . . . . . . . . . . . . . . . . (14)
+ 1SI + 2 /T ( K ) + 3 pH +4 logRinh
) . . . . . . . . . . . (15)
t (sec)
1
log inh
binh (L /mg)
t0 (sec) , . . . . . . . . . . . . (16)
No Inh
1 mg/L DTPMP
5 mg/L DTPMP
10 mg/L DTPMP
20 mg/L DTPMP
Exp Obs
10000
1000
100
10
0.1
0
500
1000
1500
2000
2500
3000
Fig. 12Plot of barium vs. sulfate concentrations that can be tolerated for 120 minutes without precipitation in the presence 0
to 20 mg/L of a scale inhibitor [diethylenetriaminepentaphosphonic acid, (DTPMP)]. The results calculated with Eqs. 14 through
16 were compared to the laboratory-observed results where 10 or 20 mg/L DTPMP was used, and the concentrations are labeled
in parentheses in the plot.
nwCO 2
nwHCO3
2
nwCO3
Ni
PCO2
R
Rinh
SI
t0
tinh
T
TAc
Vg
Z
I
I
CO2, g
CO,o
i
pHj
ij
ijk
=
=
=
=
=
=
=
=
=
=
=
=
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Amy Kan is the codirector of the Brine Chemistry Consortium at
Rice University. She holds a PhD degree from Cornell University.
She serves as the associate editor for SPEJ, and as member
of the executive committee on SPE International Oilfield
Scale Conference and SPE International Nanotechnology
Conference.
Mason B. Tomson has been a professor of civil and environmental engineering at Rice University since 1987. He holds a PhD
degree in physical chemistry from Oklahoma State University.