Scale Formation in Reservoir and
Production Equipment During Oil
Recovery: An Equilibrium Model
Torsteln Haarberg, * Ingrid Selm, Dag B. Granbakken, * * and TerJe fatvold, Norwegian Inst. of
Technology, and Peter Read, SPE, and TerJe Schmidt, SPE, Statoil A/S
Summary. This paper presents a reliable model for the solubility products of scale-forming minerals. Our model solubilities are
in relatively good agreement (±5% to 10%) with the most reliable solubilities in aqueous solutions of up to twice the seawater concen-
tration at temperatures of 20 to 150°C and pressures up to 40 MPa. An equilibrium model for the reactions responsible for scale forma-
tion is developed. The CO 2 equilibria between the gas, oil, and water phases and in the water phase itself are considered. By combining
a hydrodynamic model for the transport of water through an oil reservoir during waterflooding with the proposed equilibrium model,
we can estimate the amount of precipitate formed in the reservoir.
Introduction
Many inorganic salts and amorphous materials may be found as
solid materials adhering to the inner walls of tubing, pumps, and
other production equipment during oil recovery. In the present work,
however, we consider only the most common and troublesome scales
found: CaC0 3 , CaS04, CaS04 '2H 20, SrS04, and BaS04'
To predict the conditions under which these minerals may form
scale, one must know the solubility products of these salts and how
these solubility products vary with composition, temperature, and
pressure.
We reviewed literature on models for activities of the most com-
mon scale-forming minerals. A quasitheoretical solubility model
is proposed here that can predict reasonable solubilities in temper-
ature, pressure, and composition regions where experimental data
are available. The solubility model then was used to calculate the
amount of precipitate formed at equilibrium when typical forma-
tion water and seawater are mixed under conditions that may com-
pare with conditions found during waterflooding operations.
Solubility Models for Some
Scale·Formlng Minerals
The solubility product of a salt MX 'nH 20, Ksp(MX), which dis-
solves in water according to
MX' nH 20(s) = MX(aq) +nH 20, ..................... (1)
is defined by
K sp (MX)=C M2+ C X 2-, ............................ (2)
where C M2+ and C X2- are the molal concentrations of the M2+
and X2- ions of the completely dissociated MX salt in the aqueous
phase in equilibrium with solid MX. The solubility product defined
in this way may vary with the composition of the aqueous phase.
The thermodynamic solubility product, however, which is in-
dependent of concentration, is defined as
Ks~(MX)=CM2+ C M2- I'M2+ I'X2- a~20' .............. (3)
where I'M2+ and I'M2- are the two ionic activity coefficients and
aH20 is the water activity.
A reasonable model for the activity coefficient of the precipitat-
ing salt, together with experimental data of the temperature and
pressure variations of the thermodynamic solubility product, is thus
sufficient to give a reasonable estimate of the solubility of any scale-
forming mineral under various conditions.
Pressure Dependence of Solubility. Very little is known about the
pressure variation of the solubility of scale-forming minerals. The
published data lack the necessary accuracy to show the expected
trends when solubility is measured as a function of pressure. This
'Now at Hydro Aluminum.
'"Now at the State Pollution Control Authority.
Copyright 1992 Society of Petroleum Engineers
SPE Production Engineering, February 1992
is a result of the experimental difficulties involved in obtaining ac-
curate solubilities of these very insoluble salts.
The reaction volume ofEq. 1, however, is connected to the ther-
modynamic solubility product of the MX salt through the relation
d In Ks~/dp= -AVVRT+Ac~pIRT, .... : ............. (4)
where p=pressure, R=gas constant, T=absolute temperature,
AV~ = standard molal volume change, and Ac~ = standard com-
pressibility change for Eq. 1. The two standard states are pure, solid
MX, and an ideal 1 M solution of MX. The pressure variations
of the activity coefficients (infinite dilution reference state) may
be obtained from
RT(d In I'r/dp)=~i-Vr-(Ci-Cr)p, .................. (5)
where ~i and ci are the partial molal volume and compressibility
ci
of Component i, respectively, and Vr and are the same quanti-
ties for i in the ideal 1 M solution.
By combining Eqs. 4 and 5, we can calculate the pressure de-
pendence of the solubility product:
din Kspldp=-AVlIRT+AclPIRT, ................... (6)
where AVl and ACl are the real volume and compressibility
changes for Eq. 1. Table 1 gives the ACl values for CaC0 3 ,
CaS04, CaS04 '2H 20, SrS04, and BaS04 in pure water and
seawater.
In our calculations, linear extrapolations with ionic strength are
used to calculate ACl values outside the experimental ranges. The
temperature variations observed in Ac 1 values 1 are neglected in
the present calculations because data for salt solutions are avail-
able only up to 25°C. The justification for this approximation is
found in Eqs. 4 and 6, where the AClplRTterm is about 10% of
the total pressure variation of In Ksp at 20.3 MPa.
The volume changes ofEq. 1 are known as functions of temper-
ature at infinite dilution in pure water and in seawater. l,2 These
data, together with data obtained in our laboratory on the direct
volume changes of Eq. 1, are used to obtain an equation that can
describe how AVl varies with temperature and ionic strength, I,
of the saturated solution. For all the systems investigated,
AVl =A +BT+CT2 +Dl+EI2 ........................ (7)
could be Qsed in the temperature range of 0 to 200°C. Table 2 gives
the different coefficients in Eq. 7, and Table 3 gives the volume
data of the solid minerals.
Millero l predicted solubilities of SrS04 and CaC0 3 in aqueous
solutions at pressures up to 100 MPa using partial molar volume,
compressibility data, and Eq. 6. His results agreed well with ex-
perimental solubilities at high pressures for both minerals.
Blount 3,4 measured the solubility of BaS04 up to 300°C and 140
MPa in pure water and NaCI solution and ofCaS04 in pure water.
Fig. 1 compares Blount's and our calculated values of K{P/Ks~'
A reasonable agreement is observed between experimental and
75
 TABLE 1-ISOTHERMAL COMPRESSIBILITY CHANGES (EQ. 1), ~C1' OF MINERALS
DISSOLVING IN AQUEOUS SOLUTIONS1 AT 1 atm AND 25°C

Pure water Seawater

Salt ( -1 0 3 ~C 1/cm 3/mol· bar) ( -1 0 3 ~C 1/cm 3/mol· bar)
CaC0 3 14.95 10.59
CaS04 14.35 10.25
CaS04 '2H 2 0 12.72 8.62
SrS04 15.96 11.63
BaS04 15.79 11.33

TABLE 2-COEFFICIENTS IN EQ. 7 FOR THE

DIFFERENT MINERALS

A B 10 3 C D E
Salt (cm 3/mol) (cm 3 /mol'K) (cm 3 /mol'K2) (cm 3/mol) (cm 3/mol)
CaC0 3 -328.7 1.738 -2.794 o o
CaS04 -282.2 1.438 -2.222 21.7 -9.8
CaS04' 2H 2 0 -263.8 1.358 -2.077 21.7 -9.8
SrS04 -306.9 1.574 -2.394 20.0 -8.2
BaS04 -343.6 1.746 -2.567 11.9 .... 4.0

model data in the pressure region of 0 to 40 MPa, which is of spe-

TABLE 3-MOLAR VOLUMES 5 OF SOME SOLID
MINERALS, V ~ cial interest for the present study.
For the carbonate system, the pressure dependence of the solu-
VOs bility may be calculated by introducing the volume changes for all
Mineral (cm 3/mol) the carbonate equilibria:
CaC0 3 36.93 CO 2 (g) = CO 2 (aq) , ................................ (8)
CaS04 45.94
CaS04' 2H 2 0 74.69 H 2 0 +C0 2 (aq) = HC03" +H+, ...................... (9)
SrS04 46.25 HC03" =CO~- +H+, ............................. (10)
BaS04 52.10
and Ca2+ +CO~- =CaC0 3 (s) ........................ (11)

2.4 25 'c 2.4

2.0 2.0
-----c.
-;;- 1.6 ..,,;:
-.. 1.6
~ 0...:;:-
~ 1.2 "" 1.2
-= O.B -= O.B
0.4 0.4
0
0 200 400 600 BOO 1000 200 400 600 BOO 1000
P/BARS P/BARS

O.B 24
130'C
2.0
0.6
-~ 1.6
-~
c..~ 0.4 0...}1.2
""c::
-= O.B
0.2
0.4
0
200 400 600 0 200 400 600 BOO 1000
P/BARS p/BARS

Fig. 1-Solublllty of BaS04 and caso 4 as a function of pressure: (a,b) BaS0 4 In pure water
at 25°C and 200°C; (c) BaS0 4 In two NaCI solutions at 100°C; (d) CaS0 4 in pure water at
130°C. (+, x: Blount 3,4; - - : model curves Eq. 6, - - : model curves (upper) Eq. 6 with
.:1Co =0.)

76 SPE Production Engineering, February 1992

 -20

-30 "h,
..::.:
0015
o
E
~ -40 ~ 0010
,.,E
E .0
:::>
.:: -50 (5
>- <.r> 0005
<l

-60
O~~~~UW~~~~
-70 o 20 40 60 80 100 120 140 160 180 200
20 40 60 80 100 120 140 160 180 200 Tt'C
Tn Fig. 3-Solubllity of gypsum, CaS0 4 '2H 20, and anhydrite,
CaSO 4' as function of temperature. (_: PosnJak,16 0:
Bock,17 . : Partridge and Whlte,18 A: Hall et al., 19
Fig. 2-Reactlon volume changes for reactions (Eqs. 10 and x: Booth and Bldwell,20 D: Denman,21 +: Hulett and AI-
9) as a function of temperature. 10,ll (0: Eq. 10, D: Eq. 9, len,22 0: Posnjak,16 I!.: Marshall and Slusher,23 D:
-: model 12 .) Bock,17 v: Zdanovlskll and Siridonov, 24 and -: model.)

However, the· concentration and temperature dependence of these
reaction volumes are not well known. Standard volume changes
are known for Eqs. 10 and 11 up to 60 to 70°C, 1,2,5-7 and for Eqs.
8 and 9 up to 2000C. 8-11
Experimental data indicate that ~Vo from Eq. 9 does not equal
~Vo from Eq. 10. This can be observed in Fig. 2. If we further
assume, as a first approximation, that all the ~ V for the carbonate
system are concentration-independent, we can calculate the pres-
sure dependence of the solubility of CaC0 3 . The pressure depend-
ence of the reaction volumes ofEqs. 8 through 10 is not considered
because of the above-mentioned approximations. Haarberg 12 gave
a detailed description of the model used for calculation of the pres-
sure dependence of CaC0 3 precipitation.
Temperature Dependence of the Solubility Product. By fitting
the values obtained for Ks~ and KD for the equilibria (Eqs. 8
through 10) to
In K=A+B(TIK)-1 +C In (TIK)+D(TIK)+E(TIK)-2,
................................... (12)
one may observe in Table 4 how well this equation fits experimental
data. The thermodynamic equilibrium constant, KD, is concentra-
tion-independent. This fact may be used to model this quantity. By
a combination of experimental solubility data in the binary systems
H 20/MX and model activity coefficients, K£' for the mineral MX
may be calculated as a function of temperature. Because the actual
MX salts have low solubilities in pure water, the model activity
coefficients will have high degrees of accuracy in these solutions.
By fitting a reasonable temperature function to these values of K£' ,
we have easy access to Ks~ data for this mineral in any aqueous
solution for varying temperatures as long as the activity coefficients
can be calculated. The values of K~(C02)' KY(H 2 C0 3), and
K~(H2C03) for the carbonate system given in Table 4 are from
Plummer and Busenberg, 13 who developed reliable expressions for
these constants that are valid in the temperature range of 0 to 250°C.
Calculation of Activity Coefficients. In the binary H 20/MX so-
lutions, the extended Debye-Hiickel equation is useful in predict-
ing activity coefficients. The ionic concentrations found in waters
connected with oil production, however, are outside the range of
application for this equation.
A convenient way to extend the treatment of electrolyte solutions
to concentrations above the Debye-Hiickel region is to use a model
for the excess Gibbs energy, G, of the solution taking into account
ionic interactions beyond those considered in the Debye-Hiickel
model. In the present work we have used the following model:
G=GD_H +GB-G + G UN1 ' .......................... (13)
where Go-H is a Debye-Hiickel term; GB-G is the so-called
Gr(msted-Guggenheim 14 term, which takes into consideration cat-
ion/anion Interactions; and GuN! is a local composition term based
on the UNIQUAC model. 15
By fitting the theoretical equation for the activity coefficient ob-
tained from Eqs. 5 and 13 to experimental data, we can determine
the unknown constants in this equation for each mineral.

TABLE 4-COEFFICIENTS IN EQ. 12, In KO =f(T) AND STANDARD DEVIATIONS IN

THE FIT OF EQ. 12 TO EXPERIMENTAL SOLUBILITIES

In KO =A + B(TIK) -1 + C In(TlK) + D(TIK) + E(TIK) - 2

Relative Standard
Deviation
A B C 10 3 D E (%)
K~(CaC03) -395.448 6461.5 71.558 -180.280 24847.0 0.6
K~(BaS04) 207.807 -12238 -33.293 0 0 0.4
K~(SrS04) 83.792 -3828.9 -15.117 0 0 1.9
K~(CaS04) 1316.776 -44 840.3 -218.224 224.99 0 2.7
K~(CaS04 'H 2O) 815.729 -26 182.0 -138.469 171.02 0 0.4
K~ (CO 2)" 249.5691 -15932.8 -40.451 54 45.70806 1 541 270.0
KV(H 2C0 3)* -820.4327 50275.5 126.8339 -140.2727 -3879660.2
K~(H2C03)* -248.4192 11 862.4 38.92561 -74.89962 -1 297999.0
'From Ref. 16.

SPE Production Engineering, February 1992 77

 0.05 0.06

0.05
..0> 0.04
~
..""
~
0.04
Cl Cl
E
-;.,003 --
E
>.
003

:Ei Ll
0.02
:::J :::J
C5 0.02 C5
V'> V> 001

0
0.01 0 0.2 0.4 0.6 0.8 12 1.4
0 0.2 0.4 0.6 0.8 IONIC STRENGTH/(mol/kg water)
IONIC STREGTH/mollkg water)
Fig. 5-Solublllty of gypsum as a function of NaCI, MgCl z,
FIg. 4-Solubliity of gypsum as a function of temperature and and NazSO. additions st 25 DC. (NaCI-O: Madgln and
Ionic strength (NaCI additions). (At 40DC- 11 : Bock,17 v: Swales, Z5 11: Bock, 17 +: Marshall and Slusher, 23 ¢:
Denman, 21 +: Marshall and Slusher. 23 At BODC. .: Marshall Frledel,2' x: Tanll,z7 and v: Denman. 21 MgCI 2-O: Tan-
& Slusher.23 -: model.) 11,27 and *: Friedel. 2. NazSO.-O: Block and Waters, 28 v:
Denman, 21 x: Tanll,27 11: Hili and WlIIs,28 and Friedel. 28
-: model.)
Comparison With Experimental Data. A comparison between cal-
culated and experimental results may now be presented with model
activity coefficients and K1J, values obtained from binary H2 0IMX SrS04. In Figs. 7 and 8, the solubility of SrS04 is shown as
solutions. a function of temperature and composition. The data are well rep-
caS04 and CaS04 ·2Hz O. In Figs. 3 through 6, the solubili- resented by the model as a function of both temperature in the
ties of caS0 4 and CaS04 ·2H20 are shown as functions oftem- SrS04/H20 system and ionic strength in NaCI, MgCI 2 , and
perature and ionic strength in different salt solutions. The model Na2S04 solutions. Some experimental data show a large scatter,
describes well the temperature variation of the solubility (Fig. 3) however, and a large deviation from what seems to be the "best"
and the solubility variation with ionic strength and temperature (Fig. values.
4). The solubility enhancement observed when MgCl2 is substitut- BaS04. In Figs. 9 and 10, the solubility of BaS04 is compared
ed for NaCI and the solubility decrease observed when Na2S04 with model calculations as a function of both temperature and ion-
ic strength. The effects of MgCI 2 , CaCI 2, and KCI additions are
is substituted for NaCI are shown in Fig. 5. Solubility data are also
well represented by the model. The temperature variations of the
described reasonably well by the model in multicomponent salt so-
solubility are also well described in both the BaS04/H20 and the
lutions (Fig. 6).
BaS04/H20/NaCI systems.
CaC03 • In Figs. 11 through 15, the solubility and the ther-
modynamic solubility product of CaC0 3 are compared with model
calculations as a function of temperature, CO 2 pressure, and ion-
3.6 ic strength in NaCl solutions. As can be observed, the model data
compare well with experimental observations. In Fig. 15, the ther-
modynamic solubility product, Ks~' is compared with model cal-
culations by use of experimental solubilities and calculated activity
, 12 coefficients. When Ks~ is calculated as a function of seawater
~"" salinity in percent (Fig. 15a) or as a function of the Mg2+ ICa2+
Cl
ratio at constant ionic strength (Fig. 15b), maximum variations of
"0 --
E
2.8

.c
.
•
:::J 2.4
Cl
";-
0.000.6
V>
-><""
(5

2.0 --
E
>. 0..0.0.0.4 "= +

:E
=>
0 0.0.0.02
V>
o o
o U2 U4 U6 0.8 1.0
CMgCl z o
0. 40 80. 120. 160. 20.0. 240. 280.
TI"C
FIg. 6-Solublllty of CaSO. In MgClz-NaCI-CaSO.-HzO s0-
lutions (System 1) and In MgSO.-MgClz-NaCI-CaSO.-HzO Fig. 7-Solublllty of srSO. as a function of temperature. (0:
solutions (System 2) at 25 DC. Z5 ( 11, . : total molality of 0.1 Booth and Bldwell,2O +: StrObel,30 ¢: Kohlrausch,31 11:
and 0.15 M, respectively. 0, .: total molality of 0.1 and 0.15 Booth and Pollard,32 x: Vetter et a/., 33 v: Jacques et a/., 34
M, respectively. -: model.) -: model.)

78 SPE Production Engineering, February 1992

 .,0>
0.004
-'II::

0
E
--
>-
-I
en
-""
0.004
<5
0.002 E
:.c
::>
C5
<f')
--
>-
0.002
:.c
:;:)

<5
V')

0.2 0.4 0.6 0.8 1. 0 1.2 1.4

0
IONIC STRENGTH/(mol/kg water) 20 40 60 80 100
Fig. &-Solubility of srSO 4 88 a function of NaCI, MgCI 2, and
Na2S04 additions at 25°C. (NaCI-O: Brower and TIt
Renault,3I1 +: VeHer et a/., 33 ¢: Davis and Collins," t:.:
Jacques et a/., 34 x: Lucchesi and Whitney, 37 and v:
MOiler." MgCI 2- . : Brower and Renault,35 0: VeHer at Fig. 11-S01ubillty of Ceco 3 as a function of temperature at
a/.,33 . : Davis and Colllns. 3S Na 2SO 4: 0: Lucchesi and PC02 =0.25 atm. (0: Plummer and Bu..nberg'3 and -:
Whltney.37 -: model.) model.)

10.8
-
-""
I
0>
1.8

1.6
• 11 10.4
C5
--
..,
I
0
E
1.4
.'"
::.::
CL
10.0

9.6
- >.
.t::J
:;:)
1.2
CL

9.2

C5 1.0 8.8
V>

0.8 S.4

o 20 40 60 80 100 120 140 160 180 0 20 40 60 SO

Tt"C
100 120 140 160
TIt
Fig. 12-The thermodynamic solubility product of CaC0 3
Fig. 9-Solublllty of BaSO 4 as a function of Ionic strength [pK:' (CaC0 3)] as a function of temrzerature. ( 0 : Plummer
and temperature. (0: Kohlrausch,31 +: Melcher, 31 ¢: Tem- and Bu..nberg,'3 ¢: Segnlt et a/. 2 (average values), -:
pleton,40 t:.: Blount. 3 -: model.) model.)

2.4
I
c::n 2.0 0.Q10
-'II::

"0
E 1.6 ~ OD08 o
.; "0 o
E
b 1.2 :; 0006
:t::- :J5
08 ~ 0.004
:c
::>
V>

0
V')
0.4 0.002

0
0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 20 60
IONIC STRENGTH/(mollkg water)
Fig. 10-Solublllty of BaS0 4 as a function of Ionic strength
and temperature. (NaCl-+: Templeton,40 0: Davis and Col- Fig. 13-50lublllty of cac0 3 88 a function of pcoz. and tem-
IIns." MgCI 2- ¢ : Davis and Colllns,3S t:.: Neuman. 41 -: perature. (0: Segnlt et a/.,42 0: Mlller,43 ¢: Ellls.44 -:
model.) model.)

SPE Production Engineering. February 1992 79

 001 I
8.54
., en
0.008 8.52
-"" ~ 8.50 I-
(5 ;,.,
E 0006 Cl. 8.48
>.
8.46
.c
~
0.004 8.44 f
0
0 20 40
V>
0002 a Salinity (%.)

0 8.54
100 120 140 160 180 2
852
TI"C
Fig. 14-Solublllty of CaC0 3 as a function of NaCI concen- ~
;,.,
8.50 1
tration and temperature at PC02 = 12 atm. (0: EIIIs 45 and -: Cl. 8 48 1
mOdel.)
8.46 t- 0

"'" 0.5 % between a constant "theoretical" value and the model value
are observed.
Equilibrium Model
When all the Ca 2+ , Sr2+ , Ba2+ , CO~- , and SO~- ions, together
with CO 2 and an organic acid, HA, are present in a seawater-type
solution that is in equilibrium with an oil and a gas phase contain-
ing CO 2 , establishing a set of equations describing the precipita-
tion equilibria is necessary for calculation of the amounts of the
different minerals that actually precipitate. Solid solution of BaS0 4
and SrS04 is not considered in the present calculation.
Possible Equilibria. K sp (CaC0 3 ) is
CaC0 3 (s)=Ca2+ +CO~- .......................... (14)
K sp (CaS04) is
caS0 4(s)=Ca 2 + +SO~- .......................... (15)
K sp (CaS04 '2H 20) is
CaS04 . 2H 20(s)=Ca 2+ +SO~- +2H 20 .............. (16)
K sp (SrS04) is
SrS04(s)=Sr 2+ +SO~- ........................... (17)
Ksp(BaS04) is
BaS04(s)=Ba 2+ +SO~- .......................... (18)
K H (C0 2 ) is
844 -.l -.l -.l
o 2 4 6 8 10 12 14 16 18 20
b Mol ratio Mg/Ca
Fig. 15-The thermodynamic solubility product (pK ~) of
CaC0 3 at 25°C as a function of water salinity (1) and Mg/Ca
ratio at constant Ionic strength, 1=0.695 m (2). (0: Mucci et
a/. 48-48 and -: pure-water value. The experimental data are
treated by the model to obtain K~ values.)
cgr2+ =CSrSo/s)+ CSr 2+ ......................... (26)
C~a2+ = CBaS04 (s) + CBa 2+. . ....................... (27)
cgoz - =CcaS0 (s)+CCaS04 '2HzO(S)+CSrS04 (s)+ CBaS04 (s)
4 4
+CS0 2- . ................................. (28)
4
C~A =CA+CHA · . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . (29)
C~02 = CC0 2(g)+CCO/O)+ CCO/aq)+ CCOi- +CHC0 3"
+CCaC0 3 (s) ................................ (30)
In Eqs. 25 through 3D, Cj is the molal concentration of Compo-
nent i.
By relating the total number of moles of CO2 to the mass of pure
water, we can write the CO 2 mass balance on a molal basis as
C~o 2 =pco 2V/(zRTmH 20)+CCo 2(O)mo/mH 2o+CCOz(aq)

CO 2(g)=C0 2(aq) ................................ (19) +CCoz- (aq)+ CHCO - (aq)+ CCaCO (s), ......... (31)
3 3 3

K O(C0 2 ) is where mH2o=mass of pure water, kg; mo=mass of pure oil, kg,
without CO 2; V=total gas volume; and z=compressibility factor.
CO 2(aq)=C0 2(oil). . ............................. (20) p C02 is a yariable and not a fixed parameter. The possible change
K t (H 2 C0 3 ) is in total gas volume, V, caused by changes in Pco when CaC0 3
precipitates is neglected. 2
CO 2(aq)+H 20=HC03" +H+ ...................... (21)
K 2(H 2 C0 3 ) is Electroneutrality. In the electroneutrality equation, we consider
only those ions that may precipitate or change composition as a
HC03" =CO~- +H+ .............................. (22)
result of the precipitation reactions. Thus, the sum of the positive
KHA is minus the negative charges will be a constant:
HA=A - +H+ ................................... (23) k=2CCa2+ +2CSr 2+ +2CBa 2+ +CH+ -2Cso2 - -2CCo 2-
4 3
K HzO is -CHC0 3" -CA- -COH - .......................... (32)
H 20=H+ +OH- ................................ (24)
Model Calculation. The strategy we developed to solve the chem-
Mass Balances. ical equilibrium problem is first to calculate the equilibrium state
before precipitation/dissolution. After the local minimum in Gibbs
C~a2+ = CCaC0 3 (s) + CCaSO/s) +CCaS04' 2H zO(S) +CCa z+ . energy of the system is obtained, it has to be determined whether
................................... (25) precipitation or dissolution is required to decrease the Gibbs energy
80 SPE Production Engineering, February 1m

80.----.----.----.----,----,
.., 60
E Ion
en
"-
:§ 40
0.
O~--~~--~----~~~L---~
o 20 40 60 80 100
% seawater
Fig. 16-Preclpltatlon of Ba80 4 , Sr80 4 , and CaC0 3 when
seawater and formation waters given In Table 5 are mixed un-
der reservoir conditions. (P, =300 bar, T=70°C.)
of the system further. This can be achieved by use of the satura-
tion ratio, Fs, for a mineral MX·nH 20. Fs is defined by
FS=CM 2+ CX 2- -Yla~20/Ks~'
MX 'nH 20 is any of the minerals considered in the model.
As expressed by the above equation, F s is proportional to the
driving force for precipitation. If Fs> 1, the water is supersatu-
rated and precipitation is likely to occur. If Fs< 1, dissolution will
occur if the MX mineral is present in the solid state. It is necessary
to perform the above-mentioned local minimum calculation only
in cases where CaC0 3 may precipitate to obtain the initial con-
centrations of the species describing the carbonate system.
The set of equations describing this initial equilibrium state is
the total set of equations minus those including the solid species.
Thus, the system, without chemical reactions for solid species, is
described by nine unknowns: PC02' Cco 2 (aq), CC0 2 (0), CHC0 2- ,
CH +, COH -, CA-, and CHA(aq). 3
In our calculation to obtain the global minimum of the Gibbs ener-
gy of the multicomponent system, we consider only precipitation
of either anhydrite, CaS04, or gypsum, CaS04 ·2H20. We there-
fore have 17 unknowns and 17 equations. These equations can be
combined into two equations with two unknowns.
In the mathematical model described above, the stoichiometric
equilibrium constants are treated as constants. However, the ac-
tivity coefficient of any aqueous species is, in principle, dependent
on the concentrations of all components in the aqueous solution.
This implies that when a mineral starts to precipitate, its Ksp value
will change, as will all other stoichiometric equilibrium constants
in the system. This has been taken into consideration in the present
model, where Johnson and Riess'49 iterative procedure was used
to obtain new equilibrium constants when precipitation/dissolution
occurred.
Vetter et al. 's50 solution to the sulfate precipitation problem is
only partly correct because their model does not properly take si-
multaneous precipitation into consideration. They failed to solve
the mathematical problem of simultaneous precipitation correctly,
although that solution is, in fact, very simple.
In the mathematical formulation of the chemical equilibrium prob-
lem, we have implicitly assumed that all initially supersaturated min-
erals will precipitate. This means that the solubility products of all
initially supersaturated minerals must equal the ionic products when
equilibrium is reached. In some cases, precipitation of one miner-
al alone is sufficient to reach global equilibrium, even if other min-
erals were initially supersaturated. If this occurs during a calculation,
negative precipitation of these minerals will be computed. If nega-
tive precipitation of one mineral is detected, the procedure is sim-
ply to perform a new calculation with this mineral omitted from
the set of equations. If more than one mineral has negative precipi-
SPE Production Engineering, February 1992
TABLE 5-SEAWATER AND FORMATION-WATER
COMPOSITIONS AS GIVEN BY CHEMICAL
ANALYSIS AT 1 atm AND 20°C
Seawater C Formation Water C
(mg/L) (mg/L)
Na+ 124E?5 14859
K+
Mg2+ 1130 335
Ca 2+ 450 1275
Sr2+ 9 335
Ba 2 + 50
CI- 20950 26200
SO~- 3077
HCO"3 170 415
pH 8.13 6.20
tation, the situation is more complicated. A new calculation is then
performed with the mineral having the largest negative precipita-
tion removed. The procedure is repeated until no negative precipi-
tation of any mineral is detected.
In the first version of Qur model, 51 an assumption of known CO 2
pressure at any point in the production system was used. This sim-
plification restricted the use of our model to areas in the produc-
tion system where a gas phase was present and where data for the
partial pressure of CO 2 were available. Partial pressures of CO 2
are not easily obtained experimentally in a well under production,
and a model that can estimate these pressures along the production
tubing is much more useful when CaC0 3 precipitation is to be es-
timated along this tubing.
PreCipitation of Minerals In Formatlon-Waterl
Seawater Mixtures Under Formation Conditions
Estimating formation-water concentrations is not easy. Water sam-
ples of produced water are normally taken at the wellhead and thus
may be low in the concentration of the precipitating minerals.
Moreover, care must be taken in the handling of these waters, which
are sampled at high pressure and temperature. Either the ions must
be kept in solution when the water is brought to ambient pressure
and temperature, or an analysis of the solids that precipitate dur-
ing this treatment must be performed.
It is also important to control the HC03" concentration in solu-
tion if the CaC0 3 scaling tendency is to be estimated.
Using the equilibrium model and the solubility models described
previously, we can predict whether precipitation of the different
minerals will occur when seawater and formation water are mixed.
Fig. 16 presents results of a calculation at reservoir conditions using
the seawater and formation water given in Table S. Fig. 16 may
be compared with the data obtained when waters are mixed in a
model reservoir under seawater injection.
Mineral Precipitation in a Model Reservoir. To enhance oil recov-
ery, water injection may be preferable. Mixing of seawater and for-
mation water, however, may result in mineral precipitation, which
in tum may create a loss in production. With model calculations,
it should be possible to estimate reasonably the formation damage
resulting from such mineral deposition.
ECLIPSE 100 52 is a fully implicit, three-phase, 3D, general-
purpose, black-oil simulator. We used ECLIPSE 100 to calculate the
flow of water and oil in a defined cross section of a reservoir dur-
ing water injection. Fig. 17 presents the cross section of the model
reservoir used in the present calculation. The positions of the in-
jection well, I, and the production well, P, are indicated. The cross
section is divided in different cells, and the flow between the differ-
ent cells is reported for each timestep.
No simple model can accurately describe the mixing of different
waters entering a cell in the reservoir. The two extremes are rep-
resented by a complete mixing model and by a model in which no
mixing takes place. In our calculation, a complete mixing of waters
is used. This is in accordance with the water-mixing model used
in ECLIPSE 100.
81
 Production TABLE 6-PERMEABILITIES, k, AND POROSITIES, q"
well IN THE MODEL RESERVOIR USED IN THE
PRESENT CALCULATION
rnA Layer Height k
(m -1)
100
Layer (md) -1
-.!L
1 25 2600 0.33
75 2 15 2800 0.33
60 3 30 450 0.31
4 20 200 0.30
30 5 10 30 0.25
15~~
o -------zoo- 400
The most interesting results from the presented reservoir simu-
o lation are not the quantitative amounts of minerals precipitated in
Fig. 17-Schematic cross section of the model reservoir used. the different cells of the reservoir cross section, but the general
conclusions that can be drawn from our results.
1. CaC0 3 precipitation caused by a temperature increase in the
The pressure in each cell, but not the temperature, is calculated injected seawater may cause problems in the injection well area.
by ECLIPSE 100. We calculated the temperature in each cell using 2. If the conditions for mixing incompatible waters are favora-
enthalpy balances. The temperature of the injection water as it entersble in the reservoir, BaS04 may precipitate in the reservoir itself
the reservoir is also calculated. and thus cause less harm in the production well area.
Table 6 gives the data for the model reservoir. The composi- 3. Precipitated SrS04 in the reservoir may redissolve at high
tions of the formation water and the seawater used in the present seawater content and eventually cause problems in the production
calculation are given in Table 5. The results from the simulation well area.
are shown in Figs. 18 through 21. In Fig. 18, the fraction of in-
jection water in the mixed water is shown at different locations in Conclusions.
the reservoir. Fig. 19 shows the temperature in different parts of With the present equilibrium model, we can simulate scale forma-
the reservoir. In the present simulation, CaC0 3 , BaS04, and tion in an oil reservoir during waterflooding. Because of the rela-
SrS04 were precipitated. CaC0 3 pI'ecipitatednear the injection , tively slow water and oil movements in the reservoir itself, the
well, as shown in Fig. 20. The injected seawater becomes super- assumption of chemical equilibrium for all the reactions responsi-
saturated with CaC0 3 when it enters the reservoir because of in- ble for precipitation and dissolution of the scale-forming minerals
creasing temperature. When the fraction of seawater near the is reasonable. The main weakness in our prediction, however, is
injection well becomes high enough, CaC0 3 will precipitate (see probably the ability of the ECLIPSE 100 model to estimate water con-
also Fig. 16). Using our original equilibrium model,51 which need- centrations in the reservoir and the degree of mixing of injection
ed a given CO 2 partial pressure,51 we could not predict this ef- and formation waters in the pore system of the reservoir.
fect. BaS04 precipitation is shown in Figs. 20 and 21, and SrS04 In areas of the production system-e.g., the near-well areas and
precipitation is shown in Fig. 21. the production tubing-the rapid liquid movements do not comply
The variations observed in these precipitations with time can be with chemical equilibrium for precipitation and dissolution of scale-
understood in view of the fraction of injection water observed as
a function of time in the 1.3 and 1.5 cells of the model reservoir
and the precipitation occurring when formation water and seawater 70
are mixed (Fig. 16).
BaS0 4 and SrS04 precipitate because the two waters are incom- 60
patible. Precipitated SrS04 in the reservoir redissolves when the
seawater content becomes high enough. BaS04 is practically in-
soluble because of its very low solubility product, and the precipi- ..... 50
tated BaS04 in a reservoir cell will not redissolve noticeably.
40

1.0
- 0.8
L..
<1> 200 400 600 800
0
~
a days
c:
0

u
<1> 0.6
2
c: 60
0 0.4
U
0
L..
..... 50
....... 0.2
40
0 30 L -__~__~____L-__-L__~
0 200 400 600 800 1000
1 3 4 5 6
days block nr.
b
Fig. 18-Fractlon of Injection water found In three cells In the
Injection and production area of the model reservoir as a func- Fig. 19-Temperature In some cells of the model reservoir
tion of time. as a function of time after start of seawater Injection.

82 SPE Production Engineering, February 1992

 .. Layer 3
"i" 0.18
E
C'J
~ 0.15
PWell 1: 0.05
C'J

..
~ "'"
:§ 0.12 ' ~
a.
0.04
PWeH
'0
~ 0.09 ~ 0.03
L-
c.
o 0.06
u
a.
5. 0.02
'
L-
a. o
c
'E 0.03 ~ 0.01
'E
200 400 600 800 1000 1200 1400 1600 o
o 200 400 600 800 1000 1200 1400 1600
days days
Fig. 20-Preclpltated CaCO 3 and BaSO 4 In Cell 1.3 as a Fig. 21-Preclpltated BaSO 4 and srSo 4 In Cell 1.5 as a func-
=
function of time (P, 300 bar). =
tion of time (p I 300 bar).

forming minerals, and the chemical kinetics of all reactions involved
has to be considered. By including hydrodynamic models for the
transport of gas, oil, and water close to the production well and
in the well itself and introducing the kinetics of the precipitation
and dissolution reactions of the scale-forming minerals in our model,
we also can take into consideration the most important parameters
in a proper model 53 for scale estimation in these areas of the pro-
duction system.
Nomenclature
aj = activity of Component i
Cj = compressibility of Component i
C j = concentration of Species i in mol/kg H 2 0
Fs = saturation ratio
G = Gibbs energy
I = ionic strength
K = equilibrium constant
Ksp = solubility product
M = mol/kg H 2 0
p = pressure
R = gas constant
T = temperature, K
V = volume ,
'Y j = activity coefficient of Species i
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SPE Production Engineering, February 1992 83


Authors
Selm Haarberg Granbakken
~tvold Schmidt Read
Tor.teln Haarberg has worked at Hydro Aluminum since
Jan. 1990. He holds MSc and PhD degraes In engineering from
the Inst. of Inorganic Chemistry, the Norwegian Inst. of Tech-
nology.lngrld him, a research associate at the Inst. of In-
organic Chemistry, holds an MSc degree In chemical
engineering from the Norwegian Inst. of Technology. Dag
B'.nar Granbakken, previously a research associate at the
Inst. of Inorganic Chemistry, Is senior executive officer at the
State Pollution Control Authority In Norway. He holds an MSc
degree In engineering from the Norwegian Inst. of Technol-
ogy. Ter,e "tvold, now a professor of Inorganic chemistry
at the Norwegian Inst. of Technology, was a reaearch fellow
at the U. of Chicago. He holds MSc and PhD degrees In engi-
neering from the Norwegian Inst. of Technology. A graduate
chemist from England, Peter Read worked 10 years at the
BP Research Centre, specializing In porous media, EOR, and
fluid Interactions. He Joined Statoilin 1980 and currently au-
pervlses the application of chemistry to well and production
problems. T_rt- Schmidt has been a aenlor engineer In
Statoll'a Well Technology Dept. alnce 1984, when he gradu-
ated from the U. of Bergen with an MSc degree In engineer-
Ing. He works In R&D of chemical treatments In the well and
wellbore area, with special Intereat In scale prediction and
control.
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bonate," Ind. & Eng. Chem. (1948) 40, No. 10, 1986-88.
33. Vetter, O.I.G. et al.: "SrS04 Scale: Basic Solubility Data," paper
SPE 11803 presented at the 1983 SPE Inti. Symposium on Oilfield and
Geothermal Chemistry, Denver, Iune 1-3.
34. Iacques, D.F., Goldberg, B.I., and Whiteside, W.C.: "Strontium Sul-
fate Solubility and the Effect of Scale Inhibitors," Exxon Chemical Co.,
Houston.
84
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Strontium Sulphate Solid Solution Series," circular 116, New Mexico
Bureau of Mines & Mineral Resources, Socorro, NM (1971).
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Sulphates in Strong Electrolyte Solutions," Environmental Sci. & Tech.
(1971) 5, No. 10, 1039-43.
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Aqueous Solutions of HC1, NaCl, H 20 4 and Na2S04 by the Radi-
otracer Method," J. Appl. Chem. (1962) 12, 277-79.
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NaCl- und KC1-Uisungen," N. Jahrbuchf MineraJogie (1960) 237-39.
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Calcium Sulfate at High Temperature," J. Am. Chem. Soc. (1910) 32,
50-62.
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Solutions From 25 to 95·C," J. Chem. Eng. Data (1960) 5, 514-16.
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Solutions of Strong Electrolytes," J. Am. Chem. Soc. (1933) 55, 879-84.
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Calcite in Aqueous Solutions-I The Solubility of Calcite in Water Be-
tween 75 and 200· at CO 2 Pressures up to 60 atm," Geochim. Cos-
mochim. Acta (1962) 26, 1301-31.
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Dioxide-Water, With Geological Applications," Am. J. Sci. (1952) 250,
161-203.
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Am. J. Sci. (1959) 257, 354-71.
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at High Temperatures," Am. J. Sci. (1963) 261, 259-67.
46. Morse, I.W., Mucci, A., and Millero, F.I.: "The Solubility of Cal-
cite and Aragonite in Seawater of35% Salinity at 25·C and Atmospheric
Pressure," Geochim. Cosmochim. Acta (1980) 44, 85-94.
47. Mucci, A.: "The Solubility of Calcite and Aragonite in Seawater at
Various Salinities, Temperatures, and One Atmosphere Total Pressure,"
Am. J. Sci. (1983) 283, 780-99.
48. Mucci, A. and Morse, I.W.: "The Solubility of Calcite in Seawater
Solutions of Various Magnesium Concentrations, 1=0.679 m at 25·C
and One Atmosphere Total Pressure," Geochim. Cosmochim. Acta
(1984) 48, 815-22.
49. Iohnson, L.W. and Riess, R.D.: NumericalAnalysis, Addison-Wesley
Publishing Co., Reading, MA (1982) 169-71.
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Problems Due to Injection of Incompatible Waters," JPT (Feb. 1982)
273-84.
51. Haarberg, T. et al.: "Scale Formation in Reservoir and Production
Equipment During Oil Recovery-I. An Equilibrium Model," Proc.,
Third Inti. Symposium on Chemicals in the Oillndustry, P .H. Oge (ed.),
Manchester (April 19-20, 1988) 121-34.
52. ECLIPSE Reference Manual, Exploration Consultants Ltd., Oxford-
shire, England (1987).
53. Haarberg, T. et al.: "Scale Formation in Reservoir and Production
Equipment During Oil Recovery-ill. A Kinetic Model for the Precipi-
tationlDissolution Reactions," Acta Chern. Scand. (1991) 45, 892-901.
81 Metric Conversion Factors
atm x 1.013 250* E+02 kPa
bar x 1.0* E+02 kPa
ft x 3.048* E-Ol m
OF (OF-32)/1.8 °C
'Conversion factor Is exact. SPEPE
Original SPE manuscript received for review Jan. 3, 1989. Revised manuscript received
Nov. 13, 1990. Paper (SPE 19449) accepted for publication Dec. II, 1990.
SPE Production Engineering, February 1992