SPE 8991
SPE
PREDICTION OF CaC03 SCALE UNDER DOWNHOLE CONDITIONS
by O.J. Vetter and.V. Kandarpa.
Vetter Research
©Copyright 1980, American institute of Mining, Metallurgical, and Petroleum Engineers, Inc.
This paper was presented at the SPE Fifth International Symposium on Oilfield and Geothermal Chemistry, held in Stanford, California, May 28-30, 1980. The material is subject to
correction by the author. Permission to copy is restricted to an abstract of not more than 300 words. Write: 6200 N. Central Expwy., Dallas, Texas 75206.
ABSTRACT
CaC0 3 is one of the most common scales in oilfield
and geothermal operations. Various thermodynamic
models have been reported in the literature to predict
the precipitation of CaC03. Each of these existing
models has its limitation when applied to the real
situations of the field operations. Some models (e.g.,
Stiff-Davis method) ignore many conditions leading to
CaC03 precipitation.
In the present paper, we describe a model to pre-
dict the CaC03 scale formation at any location within
the fie"ld as a function of water composition, tempera-
ture and pressure. This model is based on equilibrium
thermodynamics, but uses only the experimentally
measured parameters. The input data for the ,model are
(1) one water analysis, (2) one pH measurement at any
location in the field, (3) the temperature at which
the only field pH measurement is made, (4) the C02 con-
centration of the gases (if a gas phase exists up-
stream or at the point where the liquid sample is
taken and the pH is measured), and (5) the amount of
flash (if a gas phase exists upstream or at the point
of sample collection). The model then takes these
measured data and calculates the equilibrium brine
composition (including pH) in the reservoir.
The calculated brine composition data can then
be used either to predict the CaC03 preCipitation
for any set of prescribed conditions or to predict
the CaC03 precipitation at various locations within
an oilfield or geothermal operation. For a set of
temperature and pressure, the model goes through a
decision to determine whether a single phase or two
phase condition exists for the brine.
For the case of the existence of the single phase
brine, the model calculates the amount of CaC03 pre-
cipitate taking into account the pertinent chemical
reactions involving the various carbonate species.
For the case of the existence of two phase brine,
the model first computes the C02 emission and its
effect on the pertinent reactions involving the various
carbonate species and, hence, calculates the amount of
CaC03 precipitate.
References and illustrations at end of paper.
155
Society of PetroIe\m EngIneers of "'ME
.
INTRODUCTION
Calcium carbonate scale (CaC03) is one of the most
common and most annoying scales in oilfield and geo-
thermal operations. As opposed to most other types
of common scales (e.g., BaS04, SrS04. CaS04), CaC03
scale formation requires not only the consideration of
pressures, temperatures and water compositions, but
also the consideration of the ehemica1 reactions within
the brine.
As shown in a number of publications,1-3 pressure
and temperature have an effect on the solubility of
sparingly soluble salts leading to the formation of
scale. In the case of sulfate scales, a simple change
of pressure and/or temperature in a given brine may
lead to the precipitation of sulfates which, in turn,
can lead to the formation of scale at any given 10ca-
tion within field operations. Thus, the normal pres-
sure drop encountered across the sandface in a flowing
well (see Figure 1) can lead to the formation of scale
and, w.ith that, to a critical decrease of the well
productivity.
Within 1imitations,2-5 we can calculate the
amount of sulfate scale formed by pressure and temper-
ature changes based on fairly simple thermodynamic
correlations. A similar situation is encountered in
the case of CaC03 as long as no carbon dioxide (C02)
escapes from the liquid phase. However, if a two or
more phase flow is encountered and if the C02 distri-
bution between the phases changes with the flow condi-
tions (mainly pressure and temperature), a new and more
complex situation is created. The C02 may travel from
the brine phase into the gas or oil phase, thus start-
ing a depletion of the C02 in the brine. This C02
depletion leads to critical chemical changes within
the brine which, in turn, can lead to accelerated
CaC03 precipitations. It is not unusual that these
CaC03 precipitations critically impair the brine flow
inside a well or a surface facility within hours or
days. For example, geothermal wells in the Westmorland
area can cease to flow within a matter of three or
four days. The sl.tuation shown in Figure 2 was en-
countered in the brine flow lines in an East Mesa
10cation. 7 ,S The CaC03 scale shown in Figure 2 was
formed in a 10 inch flow line after a production of
approximately 200,000 barrels of brine within approxi-
jmately 100 hours.,
 ...
PREDICTION OF CaC03 SCALE UNDER DOWNHOLE CONDITIONS
.---.--.---------------------------- --------------.--------
As indicated in Figure 2, the accelerated forma-
SPE 8991
------------------------------------------------------~

the correct calculation of the C02 partial pressure,

tion of CaC03 caused by an escape of C02 from the
aqueous phase (brine) can endanger an entire geother-
mal project or can severely affect the economics of
any oil or gas field operation. Therefore, the pro-
per recognition of the CaC03 problem may turn out to
be critical for any operation where aqueous fluids
are produced from subterranean reservoir, transported
through transmission systems or flown into process
equipment. Of particular interest is an understand-
ing of the thermodynamic conditions and chemical
reactions leading to the formation of CaC03 scale.
When the aqueous system containing the various
C02 species (dissolved C02, C032- and HC03-) is
subjected to changes in temperature and/or pressures,
the system may become supersaturated with dissolved
C02' Under these conditions, C02 is released from
solution. The C02 emission is normally accompanied
by an increase in pH. The increase in pH causes a
change in the distribution of various C02 species.
This pH increase causes an increase in the C032-
concentration and, as a consequence, increases the
ionic product of the CaC03 to such an extent that
CaC03 may precipitate. Thus, any prediction of CaC03
precipitation should take into consideration the
various reactions accompanying the pressure and temper-
ature changes. Any modeling of the CaC03 precipita-
tion should aim at answering the following questions:
1) What is the distribution of various C02
species downhole or at any other location
before pressure and temperature changes
occur?
the related C03- concentration and the pH at the
correct pressure and temperature. The next and
equally important step is the proper calculation of
the CaC03 solubility product based upon the entire
composition of the aqueous liquid as a function of
total pressure and temperature. If the calculated
ionic product exceeds the calculated or measured
solubility product of CaC03 in solution, a precipita-
tion of CaC03 can be expected.
The major difficulty in this mathematical treat-
ment is the dual effect of pressure on the solubility
of CaC03' Any change of pressure at any given
temperature can lead to a drastically changed
value of the CaC03 solubility product because of:
1) A change of the CO 2 partial pressure and with
that, a change of the C03-- concentration and
pH value. The resulting change of the CaC03
solubility product can be very large.
2) A change of the Gibbs Free Energy as a
function of total pressure at constant temper-
ature and brine composition ("fixed" distri-
bution of C02 species). The resulting change
of the CaC03 solubility product is similar to
that encountered in sulfate scale forma-
tions l - 3 ,6 and is normally much smaller
than the solubility change described above.
Therefore, proper thermodynamic treatment of the
CaC03 precipitation under actual flow conditions found
in the field must include:

2) What is the pH of the brine under such con- 1) Pressures (total and C02 partial)
ditions?
2) Temperature
3) What will happen to the pH or the distribu-
tion of the C02 derived species if only 3) Precise water composition (measured and/or
temperature and pressure changes occur with- calculated) including the concentrations of
out any C02 emission? all C02 species and pH value.

4) How is the pH changed as C02 is evolved? PREVIOUS CaC03 PRECIPITATION PREDICTION METHODS

5) When does CaC03 precipitate under the various One of the first CaC03 precipitation prediction
and constantly changing conditions? methods was based on the Langelier Saturation
Index 9 which was developed to characterize or deter-
In the present paper, we have dealt with answer- mine the CaC03 content of surface soils. This index
ing some of these questions in obtaining information calculation may yield useful data on the CaC03 con-
about CaC03 scale prediction. tent of soil under atmospheric pressure and tempera-
ture conditions but is totally inadequate for the
THERMODYNAMIC FACTORS LEADING TO CaC03 PRECIPITATIONS prediction of CaC03 precipitations under elevated
pressures and temperatures in fluids produced from
The temperature, total pressure, C02 partial pres subterranean reservoirs.
sure and water composition (including pH) determine
the type and concentration of C02 species (C02, HC03- Quite a few attempts were made to overcome the
and C03--) in the aqueous solution under any given set obvious shortcomings of the Langelier Saturation
of conditions. A change of any of these conditions Index and to adapt it for use in aqueous systems. 10- 13
may lead to a change of distribution of the C02 specie~ The Stiff-Davis Saturation Index13 was most frequently
in this aqueous solution. If either the C03-- concen- used in oilfield operations mainly because of (a) a
tration or the pH (these two parameters are interre1at lack of a better method and (b) its ease and conveni-
ed) increases due to removal of C02 from the solution ence of use. However, none of these indices (includ-
or due to an artificially caused increase of the pH at ing the Stiff-Davis Index) yields information of
a constant Ca++ concentration, the solubility product appreciable value for oil field and geothermal opera-
of CaC03 can be reached and the precipitation of CaC03 tions because of their total ignorance of the more
can start. Thus, a simple removal of C02 from the critical thermodynamic parameters leading to the CaC03
aqueous solution can start the precipitation of CaC03. precipitation such as total pressure and C02 partial
Therefore, the first step of any prediction of CaC03 pressure.
must include the proper mathematical treatment of
the distribution and concentrations of C02 species E11isl4 used experimentally determined C02 and
as a function of the thermodynamic conditions within CaC03 solubility data and applied these data to calcu-
the aqueous solution. This treatment must include late the CaC03 precipitation in the bore of a geo-

156
 SPE 8991 O. J. VETTER AND V. KANDARPA
thermal well. The method used by Ellis14 could be
made the basis for a computerized CaC03 scale predic-
tion method. Unfortunately, Ellis' approach has a
number of shortcomings:
1) The upper limit of the NaCI concentrations
in Ellis' data base is only 1 molar, where-
as many field brines have much higher NaCI
concentrations.
2) The critical effects of ionic species other
than Na+ and Cl- are not considered.
3) Effects of total pressure on the C02 species
and CaC03 solubilities have been ignored.
NEWER METHODS OF CaC03 SCALE PREDICTION
There are a number of newer scale prediction
methods which are not specifically geared to CaC03
scale prediction but somehow contain carbonate scale
prediction as an integral part. These methods are
based on equilibrium thermodynamic modeling through
computer programming. It is not the intention of this
paper to review the various existing scale prediction
models. However, it may be mentioned here that the
various scale prediction models are based either on
the computation of equilibrium constants or on the use
of the principle of minimization of Gibbs Free Energy
of an aqueous system.
The initial efforts on the application of chemi-
cal equilibrium thermodynamics to scale prediction
resulted in a series of publications. 15- 18 The use
of these methods showed that severe discrepancies
exist between the calculated equilibria data and the
observed equilibria data. 19 ,20 Some new efforts
were made by many researchers to correct for the
reported discrepancies. Also, attempts were made in
reducing the computational time required in utilizing
these methods. These various efforts resulted in a
monument of literature on computer chemical model-
ing. 20 - 23 Only a few of these are cited in the
references. In spite of the intense efforts of
various investigators, the complex problem of predict-
ing scale formation in general and CaC03 scale forma-
tion in particular from concentrated brines is still
an open problem.
Most of the chemical models cited above and most
of the ones which are not mentioned are based on
sound thermodynamic principles. A host of elegant
mathematical techniques are available in obtaining
solutions to the equilibrium problem. However, there
is a complete lack of reliable data on the thermodyna-
mic parameters that are needed in executing these
models.
'There are two principal hurdles in utilizing
chemical computer models in predicting the scale forma- NATURE OF COMPUTER 'MODELS
tion when a subterranean reservoir brine is brought
to the surface. One of the hurdles arises from the
lack of required input data about the chemistry of
the subterranean brine; the second arises from the
nature of the model itself.
INPUT DATA REQUIREMENTS FOR MODELS
The successful utilization of models in calcula-
ting the amount of any scale formed in a field situa-
tion requires a minimum amount of data about the brine
in question. If the scale in question is CaC03'
there are more stringent requirements about the re-
qui red information. Any chemical model to predict
CaC03 precipitation from subterranean reservoir re-
quires the following input data: (1) The complete
chemical composition of the water including pH; (2)
the temperature and pressure of the subterranean
reservoir; (3) the total dissolved carbon dioxide; and
(4) the temperature and pressure profile to which the
brine is subjected.
AVAILABILITY OF INPUT DATA
The required input information about the subter-
ranean reservoir is not possible to obtain. The water
samples of the reservoir are taken at the surface and
are kept under atmospheric pressure and ambient
temperature. That means the water composition of the
samples is possibly altered from their downhole compo-
sition. The sampling problem is even more critical
in the case of geothermal operations, particularly
with respect to the prediction of calcium carbonate
precipitation. If the C02 flashing has occurred some-
where in the wellbore, chances are that CaC03 has
precipitated near the flashing zone. As a result of
this, the water analyses of the water samples collect-
ed at the surface sampling pOint do not represent the
brine under downhole conditions.
By carefully manipulating the field situation,
one can obtain the following input data:
1) The water analYSis of the brine sample
brought to the surface under known operating
conditions.
2) The pH measurement of the brine at a location
at which the pressure and temperature are
known.
3) The C02 concentration of the gases, if a
gas phase exists upstream or at the point
where the liquid sample is taken and the pH
is measured.
4) The amount of flash if a gas phase exists
upstream or at the point of sample collec-
tion.
5) A reasonable estimate of the temperature and
pressure to which the brine is subjected
under reservoir conditions.
6) A reasonable estimate of the temperature
and pressure profiles to which the brines
are subjected.
A CaC03 scale prediction model should utilize
only this available information to describe the CaC03
scale formation.
The nature of the chemical computer models to
predict scale formation has several limitations and
they may be listed as follows: 4- 5
1) The models consider only the precipitation.
In general, the scale formation arises due
to a combination of precipitation (thermo-
dynamics and,kinetics), the flow mechanics of
the fluid (hydrodynamics) and the nature of
the solid (adherence) on which scale may form.
157
 PREDICTION OF CaCO~
2) Some of the chemical models are too complex.
Their usefulness is questionable from an
economic point of view. Some of these models
are unavailable to field operators.
3) There are three kinds of models. In one
extreme, some models are completely theoreti-
cal and their usefulness is only of academic
interest. On the other extreme, some models
are purely empirical. The usefulness of the
completely ~pirical model is restricted to
the situation for which the model is develop-
ed. A model which uses a semiemperical
approach is valuable. Such models can be
made available to a field operator at a
reasonable cost.
4) The solubility data of scale forming com-
pounds in aqueous media containing various
ionic species are very limited. This situa-
tion is even more restricted for the case of
CaC03 solubility.
NEED FOR TEST CASES
There are some claims that some of the prediction
models described above have been tested with actual
precipitation cases. We do not believe these claims
for a number of reasons. In order to test a model,
sophisticated laboratory and field experiments have
to be conducted. Only if the field and laboratory
experiments are conducted under rigorously defined
conditions and only if the laboratory results have
been compared with the data obtained from complex
field experiments, a definite proof of the reliability
of any prediction model can be obtained. A thorough
literature search and countless discussions with
numerous researchers involved in this type of work
indicated (a) that these field and lab experiments
have not been performed and (b) that a comparison be-
tween predicted and measured data has not been made.
A WORKABLE APPROACH FOR CaC03 SCALE PREDICTION
The value of a workable method for the predic-
tion of CaC03 precipitation is undisputable. This
does not mean that the prediction method has to yield
perfect data. A reasonable approximation of the cal-
culated values could be sufficient if the reliability
and limitations of the prediction method are known
after some test cases. A first attempt to accomplish
this goal was made by the authors.
DESCRIPTION OF THE PRESENT MODEL
The present model predicts the CaC03 scale forma-
tion at any location within the field as a function of
temperature and pressure. There are essentially two
steps in the operation of the model.
STEP 1: In this step, the input information to
the model is used in the calculation of the brine
composition at the reservoir temperature and pressure.
STEP 2: In this step, the information generated
in Step 1 is used to calculate the CaC03 precipitation
as the brine is brought from the reservoir condition
to the ambient condition through predetermined
temperature and pressure profiles.
As an aid in the operation of the model, a data
base consisting of the thermodynamic information on
the NaCl-H20-C02-CaC03 system is used.
SCALE UNDER DOWNHOLE CONDITIONS SPE 8991
INPUT INFORMATION TO THE MODEL
The input data for the model are the field
measurements and they consist of the follOWing
information:
1) The analysis of the brine.
2) The pH measurement at any location and the
temperature at which the pH is measured.
3) The C02 concentration of the gases if a gas
phase exists upstream or at the point where
the liquid sample is taken and the pH is
measured.
4) The amount of flash (if a gas phase exists
upstream or at the point of sample collection)
DATA BASE
The data base used in the model consists of the
following information:
1) The solubility of CaC03 as a function of
temperature, partial pressure of C02 and the
molarity of sodium chloride. 14 ,24-27
2) The solubility of C02 in aqueous medium as
a function of temperature and NaCl molar-
ity.28-3l
3) The thermodynamic equilibrium constants of
the reactions involving the various ionic
species of carbon dioxide. 32 - 35
4) The thermodynamic parameters needed to
calculate the pressure effects on the
equilibrium of the various reactions. 26 ,3l,36
1) SOLUBILITY OF CaC03
The solubility of CaC03 in an aqueous medium is a
function not only of temperature, pressure and ionic
activity of various dissolved species, but, more im-
portantly, of the distribution of the different C02
species. The complex nature of the CaC03 solubility is
illustrated in Figure 3. The figure shows the sur-
face of CaC03 solubility as a function of temperature
and PC02 in pure water. A similar plot is needed for
various ionic species of different concentrations.
Quite a few publications 14 ,24-27 report the CaC03
solubility. However, they cover only a very narrow
range of thermodynamic conditions. This published
information is combined and plotted as is shown in
Figures 4-8. Based on this information, the following
conclusions may be made regarding CaC03 solubility:
a) The solubility of CaC03 decreases rapidly
with increase in temperature.
b) At a constant temperature and NaCl molarity,
the solubility of CaC03 increases with in-
crease in C02 pressure. A definite relation
between the CaC03 solubility and C02 partial
pressure is given by equation (1):
(1)
where SCaC03 is the solubility of CaC03,
Y is a constant,
PC 0 2 is the partial pressure of C02.
158
SPE 8991 0. J. VETTER AND V. KANDARPA

Equation (1) is used to estimate the CaC0 3 Two steps are involved in the computation of the
solubility at various C02 partial pressures. downhole brine composition, namely (1) the calculation
of the single-phase brine (upstream fluids represented
c) The solubility of CaC03 increases with in- by F in Figure 9) and (2) the calculation of the brine
crease in NaCl molarity of the aqueous composition under reservoir conditions using the data
medium. calculated in the step mentioned above.
2) SOLUBILITY OF C02 IN AQUEOUS MEDIUM Both these computations use the H20-C02 flash
model as described by Vetter and Kandarpa. 8
The solubility of C02 is determined using Henry's
Law. The dependency of the constant (H) in Henry's Calculation of the Single-Phase Brine
Law on temperature, pressure and equivalent sodium
chloride molarity has been taken into account through The calculation of the composition of the single-
the use of thermodynamics and the solubility data of phase brine (F) requires the composition of the sing1e-
C02 reported in the literature. 32 - 35 Also. the non- phase reservoir brine (L), the concentration of C02 in
ideal behavior of the gaseous phase has been accounted the vapor phase (V), and either the flash fraction
for through the use of the modified Benedict, Webb and or the flow rates of the liquid vapor phases after
Rubin equation of state. their separation (see Figure 9). The model combines
the liquid and vapor phases to form a Single-phase
3) THERMODYNAMIC EQUILIBRIUM CONSTANTS brine at the flash temperature through the application
of an appropriate external pressure. The composition
The equilibrium behavior of the CaC03-C02-H20 of the single-phase brine is computed by simple balance
syst~m is primarily determined by the various reactions considerations. That is, the mass of each ionic
taking place in the system. The principle reactions species in the single-phase brine is equal to the
to be considered are: sum of the masses of the same species in the liquid
phase and in the vapor phase. The appropriate pres-
CO2 (g) .. C02 (aq) (A) sure needed to make the single-phase brine is calcu-
lated through the use of the C02 flash model. 8
C02 (aq) + H20 a H+ + HC03- (B)
Calculation of the Brine Composition Under Reservoir
HC03- .. g+ + CO~- (C) Conditions

H20 .. H+ + OH- (D)
Here (g) refers to C02 in the gas phase and (aq)
refers to CO2 dissolved in the aqueous phase.
The constants H, Kl. K2 and Kw
define the equili-
brium of the reactions A, B. C and D, respectively.
The data base uses the well known temperature depend-
ency of these constants. 32- 35
4) CONSTANTS TO ACCOUNT FOR PRESSURE EFFECTS
The total pressure on the CaC03-H20-C02 system
effects the equilibrium constants of all the reactions
mentioned above. The change in equilibrium constants
with increasing pressure can be estimated provided the
volume changes associated with the reactions are known. equilibrium of the reactions (E), (B), (C) and (D)
Reasonable values of the various volume terms are
available from the literature. 26 ,31,36
CALCULATION OF THE BRINE COMPOSITION AT RESERVOIR
TEMPERATURE AND PRESSURE
In this step the brine composition, including the about such complex reactions effecting the true pH
concentrations of the various ionic species, is calcu- value.
lated for reservoir conditions. The input data for this
calculation are provided through chemical analyses of
samples collected in the field. Figure 9 schematically (C), and (E) may be combined to obtain equation (2):
indicates how the measured and calculated data are
interrelated. Samples can be collected from the steam
and single-phase flashed brine lines at any given set
of thermodynamic conditions (represented by L and V
in Figure 9). Knowing L, V and chemical compositions
of the single-phase effluents (steam and brine) allows
(a) to perform a material balance and (b) the calcu-
lation of the chemical composition of the upstream
fluids assuming these upstream fluids are single phase.
The fact that these fluids may not be single phase is
taken into account below.
The single-phase brine formed in the above step
is brought to the temperature and pressure correspond-
ing to the downhole conditions. Then the reSUlting
brine is equilibrated with calcium carbonate under
downhole condition. The equilibria of importance may
be summarized by the following reactions:
CaC03 (aq) = Ca 2+ + CO~­ (E)
H2C0 3 = HC03- + g+ (B)
(C)
(D)
The constants Kc. K1, K2, and Kw define the
respectively. The model conSiders only the above
reactions at the downhole conditions. There may be
other reactions in the complex system of the formation
rock-brine combination at the downhole conditions
which may drastically alter the pH of the system.
At the present time, there is not enough information
The equilibrium constants of the reactions (B),
KlKc (H2 C0 3)
(2)
K2 (HC03 )2
where (Ca 2+) = activity of calcium ions
(H 2 C0 3) = activity of dissolved C02
(HC03-) = activity of HC03- ions
Kl ,K2,Kc = equilibrium constants of the
reactions (B), (C). and (E).

159
 PREDICTION OF CaC03 SCALE UNDER DOWNHOLE CONDITIONS
Using the data base described in the previous
sections, the equilibrium constants at the reservoir
condition are computed and, hence, the concentration
of Ca 2+ ions are calculated. Once the concentration of
Ca 2+ ions are known, the concentrations of CO~-, HC03-,
H2C03 and, hence, the pH of the brine are calculated
for reservoir conditions. The details are given in a
previously published report. 8
H20-C02 FLASH CALCULATION
The H20-C02 flash calculation model uses the
schematic representation shown in Figure 9. The model
essentially applies a heat balance, a mass balance and
the thermodynamic equilibrium relations between the
liquid phase and gas phase in the system. The result-
ing equations are solved to describe the C02 flash
behavior for any set of thermodynamic conditions.
The model treats the gaseous phase as non-ideal
With the modified Benedict, Webb and Rubin equation
of state and computes the fugacity of C02 for any
temperature and pressure. The solubility of C02 is
determined by use of Henry's Law constant. The Henry's
Law constant dependency on temperature, pressure and
equivalent sodium chloride molarity has been taken
into account through the use of thermodynamics and
experimental data. Also, the effect of temperature
and pressure on the equilibrium constants of the vari-
ous ionic species of carbon dioxide have been consid-
ered. The mathematical details of the model have been
adequately described in a previously published
literature. S
CALCULATION OF CaC03 PRECIPITATION
The CaC03 precipitation due to pressure and
temperature changes is computed in this step. A small
pressure decrement is numerically applied in the model
to the actual value of the downhole pressure. Then,
the H20-C02 flash model determines whether a C02 flash
occurs. If C02 flash occurs, the dissolved C02 con-
centration in the brine is adjusted for the C02 re-
moved in this flash process. The concentrations of the
various ionic species and the pH of the brine are now
calculated. From the concentrations of coj- and Ca 2+
ions and from the solubility data, the amount of CaC03
precipitation is computed. In this step all the equil-
ibrium reactions, namely, (A) to (C) are used. The
solUbility constants for the CaC03 are also adjusted
for temperature and pressure as outlined in the section
on the data base.
If no C02 flash occurs, there can still be a
redistribution of the C02 species in solution. In
addition, a change of the CaC03 solubility product as
a function of this pressure change can still occur.
This means CaC03 can precipitate even though no C02
flash is experienced. However, the amount of this
precipitation is quite small compared to that encount-
ered during C02 flash.
The process of applying small pressure decrements
is repeated until the water flash starts. As soon as
this water flash occurs, any further calculations
take into account the concentrating effect of this
"Water "removal".
ILLUSTRATION OF MODEL APPLICATION
The usefulness of the model can be illustrated by
its application to a geothermal field in Westmorland.
The type of report generated by the model is shown in
160
SPE 8991
Tables 1, 2 and 3.
INPUT DATA
Actual field data from the geothermal well in
Westmorland are used as input data for the model. The
procedure used in obtaining the field data is describ-
ed below. The total fluid produced from the well is
flashed into a separator. The separator conditions are
such that a water flash of 23.8% was obtained (temp.
218°F, press. 18 psi). Several samples from the
effluent brine and the steamline were collected. The
samples from the brine and steamlines were analyzed
for their chemical constituents; especially for the
total C02. Table 1 shows the input data used for this
particular well.
OUTPUT DATA
The model uses the above input information and
calculates the chemical composition of the reservoir
fluid under reservoir conditions. The calculated
compositions of this reservoir fluid are shown in the
heading of Table 1. The pH of the reservoir brine
is calculated to be 5.31 assuming the brine is at
equilibrium with calcium carbonate, which is reason-
able because of the CaC03 in the drill cuttings.
Another assumption is that the temperature stays
constant until the water flash starts at 427 psi.
Down to this pressure (from the original reservoir
pressure) the temperature may slightly decrease due to
heat losses through the wellbore. The small tempera-
ture decrease could be considered in the model, but is
neglected in the described case.
The calculated CaC03 precipitation data illustrate
the dual effect of pressure as outlined before. Even
though there is no C02 flashing above a total pressure
of 1130 psi at 450°F (see Table 2), there is still a
CaC03 precipitation encountered as shown in Table 1.
This effect is due to the effect of pressure of Gibbs
Free Energy.
As soon as the total pressure in the wellbore
drops below 1130 psi, C02 will start to flash. As
shown in Table 3, the majority of the flashable C02
is removed from the brine down to approximately 550
psi and a pH of 6.0 (see Table 1). The CaC03 precipi-
tation is still fairly small. The majority of the
CaC03 precipitation will be observed as the total
pressure approaches the water saturation pressure.
This confirms our field observations of CaC03 scale
deposition in a wellbore as illustrated in Figure 10.
The bubble point calculations shown in Table 2
using the same model also indicate some interesting
brine and gas behavior. If a single-phase brine of
a given chemical composition is produced from different
locations having different temperatures, the gas flash
behavior and the bubble point pressures will be
drastically different. For example, if the brine
comes from a reservoir having 500°F, the water will
flash before the C02. On the other hand, if this same
brine is produced from a reservoir having a tempera-
ture of 450°F, the C02 will flash ahead of the water,
i.e., the flash behavior is reversed. This proves
that the common assumption that the C02 must flash
before a steam phase is formed must be considered a
misconception. The gas and steam flash behavior is
dictated by the chemical composition of the single-
phase fluids, the reservoir and downhole pressures
and temperatures.
SPE 8991 O. J. VETTER AND V. KANDARPA
CONCLUSIONS
1) It is possible to calculate the amount of
CaC03 precipitation in aqueous fluids pro-
duced from subterranean reservoirs.
2) Simple CaC03 saturation indices such as the
Stiff-Davis Index are not suited for adequate
calculations of the CaC03 precipitation or
even for an approximate scale tendency.
3) Precise calculations of the CaC03 must in-
clude all thermodynamic factors leading to a
CaC03 precipitation. The minimum variables
required are: (a) total pressure, (b) C02
partial pressure, (c) temperature, and (d)
brine composition including pH value and con-
centrations of the major C02 species.
4) A workable model capable of calculating the
C02 behavior and the CaC03 precipitation
has been developed. This semi-empirical
model is based on analytical data measured
in field-collected samples and also on a
published data base of CaC03 solubilities.
5) This model allows us to calculate the effects
of pressure, temperature and water composi-
tion on the distribution of the C02 species
and their effects on the CaC03 precipitation.
In addition, the direct effects of these
variables on the Gibbs Free Energy, and with
that, their effects on the CaC03 solubility
as a pressure function at constant tempera-
ture, is also included in the model.
6) In order to calculate the CaC03 precipitation
one must first compute the distribution of the
C02 species under the thermodynamic conditions
of interest.
7) If C02 flashing occurs, a large amount of
CaC03 precipitation per volume unit of brine
can be encountered.
8) Even if no C02 flashing occurs, a farily small
CaC03 precipitation can be calculated because
of the pressure related changes of the Gibbs
Free Energy in the system.
9) Field and laboratory test cases for this
present and any other models are desperately
needed.
ACKNOWLEDGEMENT
Some of the work leading to this paper was
sponsored by the U.S. Department of Energy/Division
of Geothermal Energy. We would like to express our
thanks to the technical personnel of the Division of
Geothermal Energy for their constant support. We
would also like to thank Mr. D.A. Campbell (Republic
Geothermal, Inc.) and Mr. D. Slagle (Mapco Geothermal,
Inc.) for their constant help and constructive dis-
cussions.
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16) Helgeson, H.C., and Kirkham, D.H., "Theoretical
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 TABLE 2
TABLE 1
CALCULATED C02 BUBBLE POINTS
CALCULATED pH VALUES AND CaC03 IN A WESTMORLAND GEOTHERMAL WELL
PRECIPITATION IN A WESTMORLAND GEOTHERMAL WELL
NACL MOLARITY BEFORE FLASHING, 0.40
C02 IN STEAMLINE AFTER THE SEPARATOR AT 218 F ,0.8299E+05PPM
FLASHABLE C02 IN SINGLE PHASE FORMATION BRINE,O. 1975E+05PPM
INPUT DATA:
TEMP(oF) PC02(PSI) PH20(PSI) PTOTAL(PSI)
WATER ANALYSIS (IN PPM):
200.00 649.49 11.78 661.27
210.00 678.76 14.42 693.19
NA= 7050.00
CL: 14180.00 220.00 705.83 17.54 723.37
CAo 280.00 230.00 730.55 21. 18 751.73
240.00 752.79 25.43 778.23
HC03, 550.00
C03, 0.00 250.00 772.50 30.36 802.86
260.00 789.62 36.03 825.65
OOWNHOLE TEMPERATURE (OEG F),450.0 270.00 604.13 42.54 646.67
280.00 816.04 49.97 866.01
OOWNHOLE PRESSURE (PSI) '3400.0
FLASH TEMPERATURE (OEG F) ,217.8 290.00 625.38 58.41 883.80
300.00 832.21 67.97 900.18
FLASH FRACTION ,0.238
C02 IN STEAMLINE (PPM) ,83000.0 310.00 836.51 78.73 915.32
320.00 838.5f 90.82 929.40
330.00 838.3, 104.34 942.67
340.00 835.91 119.41 955.32
OUTPUT DATA:
350.00 831. 46 136.15 967.62
360.00 825.10 154.69 979.80
CALCULATED RESERVOIR .CONDITIONS:
370.00 816.96 175.16 992.12
360.00 807.17 197.69 1004.86
390.00 795.67 222.43 1018.29
RESERVOIR TEMPERTURE (OEG F),450.03 400.00
RESERVOIR PRESSURE (PSI), 3400.0 783.19 249.51 1032.69
410.00 769.27 279.08 1048.36
H2C03(MOL ),0. 45E.GOHC03( MOL ),0. 24E-02 420.00
C03(MOL),0.42E-C9,CA(MOL),0.53E-02,PH , 5.31 754.25 311. 31 1065.56
430.00 738.26 346.34 1084.60
SAT. WAT PRESSURE (PSI),426. 95
440.00 721. 42 384.3" 1 lOS. 77
450.00 703.87 425.47 1129·34
460.00 685.71 469.91 1155.62
DECREASE OF PRESSURE AT CONSTANT TEMPERATURE 470.00
CAUSES THE FOLLOWING CONDITIONS: 667. 06 517.82 1184.88
480.00 648.05 569.39 1217.43
P (PSI) 490.00 628.74 624.79 1253.53
PH CAC03 PRECIPITATION 500.00 609.25 684.23 1293.48
(MG/KG OF BRINE)
3326.5 5.31 0.373E-07
3253.0 5.31 0.741E-07
3179.6 5.31 0.110E-06
3106.1 5.31 0.1"6E-06
3032.6 5.31 0.181E-06
2959.1 5.31 0.216E-06
2885.6 5.31 0.251 E-06
2812.2 5.31 0.285E-06
2738.7 5.31 0·318E-06
2665.2 5.31 0.351 E-06
2591. 7 5.31 0.383E-06
2518.2 5.31 0.415E-06
2444.8 5.31 0.447E-06
2371. 3 5·31 0.478E-06 TABLE 3
2297.8 5.31 0 .• 509E-D6
2224.3 5.31 0.539E-06
2150. B 5·31 O.569E-06
2077.4 5.31 o.598E-06 CALCULATED C02 EMISSION IN A WESTMORLAND GEOTHERMAL WELL
2003.9 5.31 D.627E-06
1930.4 5.31 0.656E-06
1 B56. 9 5.31 0.684E-06 FLASiiABLE C02 IN SINGLE PHASE FORMATION BRINE: 2. 00E+04 MGIKG OF BRINE
17B3.4 5.31 0.711E-06
1710. D 5.31 0.739E-06
1636.5 5.31 0.766E-06
1563.0 5.31 0.7920-06
1489.5 5.31 0.B1BE-06 P (PSI) PC02(PSI) AMOUNT Of C02 FLASHEO
1416.0 5.31 O. B44E-06 (MG/KG Of BRINE)
, 3't2.6 5.31 0.869E-06
1269.1 5.31 0.B94E-06
1195.6 5.31 0.919E-06 3326.5 NO GASEOUS EM!';SION POSSIBLE
, 122. 1 5.31 0.943E-06 3253.0 NO GASEOUS EMISSION POSSIBLE
1048.6 5.36 0.916E-05 3179.6 NO GASEOUS EMISSION POSSIBLE
975.2 5.42 0.192E-04 3106.1 NO GASEOUS EMISSION POSSIBLE
901. 7 5.49 0.323E-04 3032.6 NO GASEOUS EMISSION POSSIBLE
828.2 5.56 0.500E-04 2959.1 NO GASEOuS EMISSION POSSIBLE
754.7 5.65 0.755E-04 2885.6 NO GASEOUS EMISSION POSSIBLE
681. 2 5.77 0.115E-03 281?2 NO GASEOUS EMISSION POSSIBLE
607.8 5.92 0.187E-03 2738.7 NO GASEOUS EMISSION POSSIBLE
534.3 6.15 0.358E-03 2665.2 NO GASEOUS EMISSION POSSIBLE
460.8 6.65 0.126E-D2 2591.7 NO GASEOUS EMISSION POSSIBLE
455.6 6.73 0.151E-02 2518.2 NO GASEOUS EMISSION POSSIBLE
l152.6 6.77 0.169E-02 2444.8 NO GASEOUS EMISSION POSSIBLE
449.7 6.83 0.191E-02 2371.3 NO GASEOUS EMISSION POSSIBLE
446.8 6.89 O.220E-02 2297.8 NO GASEOUS EMISSION POSSIBLE
443.8 6.96 0.260E-02 2224.3 NO GASEOUS EMISSION POSSIBLE
440.9 7.04 0.316E-02 2150.8 NO GASEOUS EMISSION POSSIBLE
437.9 7. ,,, 0.402E-02 2077.4 NO GASEOUS EMISSION POSSIBLE
435.0 7.28 0.551 E-02 2003.9 NO GASEOUS EMISSION POSSIBLE
432.1 7.48 O. B70E-02 1930.4 NO GASEOUS EMISSION POSSIBLE
429.1 7.85 0.205E-Ol 1856.9 NO GASEOUS EMISSION POSSIBLE
427.1 9.11 0.381E+00 1783.4 NO GASEOUS EMISSION POSSIBLE
1710.0 NO GASEOUS EMISSION POSSIBLE
1636.5 NO GASEOUS EMISSION POSSIBLE
1563.0 NO GASEOUS EMISSION POSSIBLE
14B9.5 NO GASEOUS EMISSION POSSIBLE
1415.0 NO GASEOUS EMISSION POSSIBLE
1J1t2.6 NO GASEOUS EMISSION POSSIBLE
1269.1 NO GASEOUS EMISSION POSSIBLE
1195.6 NO GASEOUS EMISSION POSSIBLE
1122.1 NO GASEOUS EMISSION POSSIBLE
1048.6 621.7 O.2237E+O!.J
975.2 548.2 O.2167E+04
901. 7 474.7 O.2147E+04
828.2 401. 3 O.2127E+04
154.7 327.8 O.2108E+04
681. 2 254.3 0.2088£+04
607.8 180.8 0.2069E+04
534.3 107.3 O.20S0E+04
460.8 33.9 0.2031E+04
455.6 2B.6 0.1436E+03
452.6 25.7 O.8077E+02
449.7 22.7 0.8074E+02
446.8 19.8 0.8071£+02
443.8 16.9 0.8068E+02
440.9 13.9 O.8065E.02
437. 9 11.0 O.8062E+02
435.0 8.1 0.8059E.02
432.1 5.1 O.80S6E+02
429.1 2.2 0.8053E+02
427.1 0.1 0.5635£+02
 \ STATIC
\ PRESSURE
PRESSURE IN fORMATION
SKIN OR
ZONE Of
DAMAGE

ACROSS SKIN

~-L- _ fLOWING PRESSURE

Fig. 1 - Pressure distribution in a reservoir with a skin.

Fig. 2 - CaC03 scale in the Brine Flow Lines in an East Mesa

CaC03 SOLUBILITY Geotherma 1 lie 11 .

3500

3000

,..
2500

2000
'01
.§
:>.
t:
ca
==
3
~ ~IOO°C
... ~125°C
8 ,r'" 250°C
u'" ~200 ° C

10 20 30 40 50 60 70 80 90 100
~~~~i;;t:~
Pe02 (ATM).
CaC03 SOLUBILITY
(I!lke. SOLUTION)
Fig. 4 - Calcite solubil ity in system H20 - C~.
Fig. 3 - Calcite solubility in system: C~ - H20.
 3500 3500

3000 3000

.
....
'-
2500
!
2500

....
.§
2000 ~2000
.§
>-
5
CII
§
0
...
11.1
~150·C ,..-200·C
u
~

20 30 40 50 60 10 80 90 100 10 30 40 50 60 10 80 90 100
PC02 [ATMJ" PC02 [ATM)"

Fig. 5 - Calcite solubility in system H20 CD2 0.5 mNaCl. Fig. 6 Calcite solubility in system H20 - C~ 1 mNaC!.

3500 3500

3000 300

2500

10 20 30 40 50 60 10 80 9 100 10 20 30 40 60 10 ao 100

PC02 [ATM)" P [ATMJ"

C02

Fig. 8 - Calcite solubility in system H20 - C~ - 3 mNaC!.

Fig. 7 - Calcite solubility in system H20 C~ 2 mNaCI.

.
Froduction

Pi • Partial Pressure Of jth Component Overburden

Xi Mole Fraction Of ith Component In liquid
Vi Mole Fraction Of ith Component In Vapor
~ Frac'don Of Flash
~

t=
F
1-~
Rate Of Feed
.
l
V
Rate Of liquid After The Flash
Rate Of Vapor After The Flash ProducinS! Zone .
Fig. 9 - Thermodynamic model for flash in ~O - C~ system.
Fig. 10 - CaC~ scale in wellbore.