SPE

Society of Petroleum Engineers

SPE 16908

Calcium Carbonate Scale in Oilfield Operations

by O.J. Vetter,* Vetter Research Inc., and W.A. Farone, Applied Power Concepts Inc.
*SPE Member

Copyright 1987, Society of Petroleum Engineers

This paper was prepared for presentation at the 62nd Annual Technical Conference and Exhibition of the Society of Petroleum Engineers held in
Dallas, TX September 27-30, 1987.

This paper was selected for presentation by an SPE Program Committee following review of information contained in an abstract submitted by the
author(s). Contents of the paper, as presented, have not been reviewed by the Society of Petroleum Engineers and are subject to correction by the
author(s). The material, as presented, does not necessarily reflect any position of the Society of Petroleum Engineers, its officers, or members. Papers
presented at SPE meetings are subject to publication review by Editorial Committees of the Society of Petroleum Engineers. Permission to copy is
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II
where and by whom the paper is presented. Write Publications Manager, SPE, P.O. Box 833836, Richardson, TX 75083-3836. Telex, 730989 SPEDAL.

ABSTRACT
Calcium Carbonate (CaCOJ) is one of the most common 3. The bubble point and pertinent flash behavior of
scales in oil field operations. Various fluids the three-phase oil/brine/gas system as a
(brine, oil and gas) can mix in the reservoir and/or function of pressure and temperature.
wellbores under drastically varying sets of 4. The distribution of C02 between oil and brine
thermodynamic, kinetic and hydrodynamic conditions phases and the drastic variations of this C02
that will affect the carbonate scale forming partitioning prior and during any production
tendencies. Many of these critical conditions are operation.
ignored in today' s oil field operations as far as 5. The constant variation of the water (brine) /oil
calcium carbonate scale is concerned. ratio (''WOR"), the gas/oil ratio ("GOR") and the
gas/water(brine) ratio ("GWR") during any
Presently, the mechanisms of CaC03 scale formation, production operation.
as conceived by the industry, considers only the
liquid brine phases. The flashing of gases from both These reservoir and production variables at various
the oil and the brine phases is critical for the locations in the production system may change
CaC03 scale formation. Pertinent aspects of this constantly as a function of location and time during
flash process are generally ignored. In addition, any type of production operation within a given
the complete mechanism of the CaC03 must also field. These critical variables are not considered
consider the partitioning of gases (particularly C02) in their entirety in the existing and most
between the liquid oil and brine phases during the frequently used CaC03 scale prediction models.
entire gas flash process. This means, the formation
of CaC03 can not be determined by considering only In the present paper, the problems of calcium
the brine phase as attempted by the industry. carbonate scale formation in oil field operations
Instead, the entire three-phase PVT behavior (primary, secondary, and tertiary production modes)
(oil/brine/gas) and associated C02 partitioning must are critically discussed. The various effects of
be considered to determine the CaC03 scale formation the gas distribution '(especially C02) between oil
in an oil field. The existing and published models and brine phases under reservoir and various
on the CaC03 formation consider only the basic production conditions are delineated as far as CaC03
thermodynamics of the brine phase and totally ignore scale is concerned. Same algorithms are given.
the critical effects of the oil phase behavior on Finally, the paper discusses a methodology which can
this scale formation. This automatically means that be used to predict CaC03 under all field conditions
the oil industry can not adopt any of the existing as a function of the water composition, pressure,
scale models without serious modifications to account temperature, ''WOR", "GO.R", "GWR", total C02 in the
for the unique effects of the oil phase. The main system and C02 partitioning between the various
variables dictating the location and amount of liquid phases.
calcium carbonate scale deposition in an oil field
are as follows: The methods and problems of obtaining all the
1. Pressures and temperatures at any location within required input information in order to apply this or
the entire system. similar models for site-specific oil field opera-
2. The brine and oil compositions prior, during and tions will be discussed in detail. PVT and C02
after the reservoir fluids have been exposed to partitioning data obtained through same recent work
temperature and/or pressure changes. with three-phase fluid systems from California oil
fields will be used to illustrate the complex CaC03
References and illustrations at end of paper. scale behavior in an oil field.
307
2 CALCIUM CARBONATE SCALE IN On. FIELD OPERATIONS
INTRODUCTION: HISTORY OF CaC03 PREDICT IONS
Predicting the formation of CaC03 from aqueous
solutions is a fairly old problem. Langelier [11
published in 193& one of the first water "stability"
indices to determine if CaC03 will precipitate from
water. This Langelier index predicted the CaC03
formation from water in a municipal water. Later,
Larson and Buswell [ 21 improved the reliability of
the Langelier index by adjusting their own index for
the temperature and salinity effects during the CaC03
precipitation at atmospheric pressure.
Stiff and Davis [31 adapted the previous published
indices for oil field operations. Still more
recently, Oddo and Tomson [41 made an attempt to
improve the reliability of a CaC03 stability index.
Their saturation index [ 41 represents a drastic
improvement over the Stiff-Davis index [31. The
method employed by Oddo-Tomson provides some
provisions to compute the "true" pH and the effects
of pressure and temperature on the C02 solubility and
on the formation of co3-- ions within the brine
phase.
As shown below, none of these indices can really and
correctly predict or mathematically describe the
various amounts of CaC03 scale formed in an oil field
operation. These indices will also fail to correctly
and reliably describe the CaC03 formation even in the
absence of an oil phase because of numerous
assumptions and/or simplifications regarding the
thermodynamic variables used for calculating these
indices. In addition, the calculation of a scaling
or water stability index is not sufficient to
effectively fight scale in oil field. The
computation of such an index may be convenient for
field operating personnel but is totally insufficient
to control any scale formation in the field.
Instead, the CaC03 scale formation should be
quantitatively determined as a function of existing
field conditions, cumulatively produced fluids and
location within the system.
Vetter and Kandarpa [ 5, 6 1 described the various
problems encountered for a more precise mathematical
handling of the CaC03 formation from an aqueous phase
(i.e., in the absence of an oil phase) under
otherwise typical oil field conditions. These
previous papers [5,61 also list and describe some of
the more recent attempts by others to calculate the
thermodynamics of CaC03 precipitations from aqueous
solutions but also in the absence of an oil phase.
Some of these attempts by others involved complex
mathematical and thermodynamic models which will tax
even mainframe computers. Many of these complicated
and complex models are more of scientific and
theoretical interest. None of these models can
fulfill the need of the oil industry for a practical
approach to predict CaC03 scale formations in order
to effectively and efficiently fight these scale
problems on a routine basis. A still more recent
paper by Vetter et. al. [ 71 points out some of the
basic but still unsolved problems related to a proper
mathematical treatment of CaC03 precipitations in the
presence of an oil phase. This paper [ 71 outlines
some of the problems due to the mainly unknown
partitioning of COz between the oil and aqueous
phases. However, no true solutions to the obvious
problems related to the correlations between the
general PVT behavior of oil field fluids and the
CaC03 scale formations were given in this recent
paper [71.
308
SPE 16 908
The main problem for a proper prediction of CaC03
precipitations is caused by the still rather unknown
partitioning ef feet s of C02 between the oil and
brine phases during the production process in a
typical oil field. Only a very few published papers
are concerned with this partition of C02 between oil
and brine [7,8,91. Thus, none of the previously
published papers considered all the pertinent
thermodynamic parameters which dictate the CaC03
scale formation in an oil field, i.e., in a system
where oil and brine are coexisting and where both
phases are produced simultaneously.
What is needed is a model describing the formation
of CaC03 scale in a "real world", i.e., in a typical
oil field operation. This model should consider, as
a minimum, all the pertinent thermodynamics that
dictat the basic mechanisms of any CaC03 scale
formation in such a field. The thermodynamics of
the entire system, i.e., not only the behavior of
the aqueous phase but also that of the coexisting
oil and gas phases should be considered. This model
should also take into account the specifics of any
fluid production process that is inherent to any oil
field operation.
An attempt is made in the remainder of this paper to
show some means required to generate such a model.
Some specific field applications using these new
model considerations will be presented in the near
future [101. In this present paper, we outline only
the very basic details related to this new model
approach.
THE FUNDAMENTALS OF CaC03 FORMATION
IN 0 n. FIELDS
In principle, it should not be too difficult to
identify and comprehend the basic thermodynamics
which have pronounced effects on any CaC03 scale
formations in an oil field. These fundamentals
should be rather clear and simple, whereas many of
the pertinent details related to a correct modeling
of CaC03 scale formations are everything else but
clear and simple.
Below, we use a rather straight forward approach to
delineate the very basic reactions that dictate the
formation of CaC03 scale in an oil field:
1. Prior to producing an oil reservoir, a number of
fluids (oil, brine and, possibly, gas) coexist in
the reservoir under given sets of thermodynamic
conditions. At least theoretically, the various
and pertinent thermodynamic equilibria could be
determined by knowing at least three of the four
basic thermodynamic variables:
a) Temperature (T).
b) Pressure (P).
c) Volume (V).
d) Amount (A).
Knowing the correct values of at least three of
these four basic thermodynamic variables (e.g.,
P, A and T) permits, again theoretically, the
calculation of the remaining basic variable (V)
and all other pertinent thermodynamic parameters
and equilibria. If A is known and kept constant,
the remaining PVT variables will be sufficient to
describe the thermodynamics of the system.
2. The CO2 and the Ca ++ ions dissolved in the
aqueous phase (brine) are the main culprits
causing the CaC03 precipitations from the aqueous
phase during any fluid production process in the
SPE 16 908 O.J. VETTER AND A.W. FARONE
field. However, under stagnant (i.e., static or
non-flowing) reservoir conditions, one can assume
that the entire fluid system is in thermodynamic
equilibrium. This means, the total amount of 002
dissolved in both the oil and brine phases is
fixed. The distribution of the total dissolved
C02, between the coexisting oil and brine phases
and the ca++ ion concentration in the brine are
also fixed. If the reservoir rock contains solid
CaC03 one can assume that the reservoir brine is
saturated in respect to CaC03.
3. At a given and fixed set of thermodynamic
parameters under static (i.e., stagnant or non-
flowing) reservoir conditions P, V, T and A are
fixed. This means, the pertinent thermodynamic
equilibria (including the amount of CaC03
dissolved in the brine phase) are established and,
in principle, no solid CaC03 can dissolve or
precipitate from this aqueous phase. The
reservoir brine under stagnant conditions may not
be saturated in respect to Ca003 even though heavy
CaC03 scale depositions may be encountered at some
specific locations within the field.
4. The moment any flow of any reservoir fluid is
induced by the field operator, certain pressure
and, possibly, temperature changes will occur
within the system. Thus, the thermodynamic
equilibria are disturbed and, consequentially,
numerous chemical reactions may start and chemical
as well as physical changes may occur within the
system. Of particular interest are the pressure
and temperature effects on the solubility of a few
pertinent or critical chemical species that are
dissolved in the oil and in the brine phase.
These changes will determine the formation of
carbonate ions and other thermodynamic conditions
within the brine phase which may lead to the
subsequent precipitation of CaC03 from this
aqueous phase.
5. Even if the induced reduction of the reservoir
pressure does not lead to a flashing of gases from
the two liquid phases, these pressure drops may
already lead to a CaC03 precipitation from the
aqueous phase. Assuming the aqueous phase
contains sufficient amounts of calcium ions and
already some carbonate ions prio~ to inducing any
flash process due to pressure changes, the
solubility product (saturation) of the CaC03 may
be exceeded due to these pressure changes. These
reactions in the absence of a gas phase are quite
similar to the pressure induced precipitations
which eventually lead to the common formation of
CaS04, SrS04 and BaS04 scales in oil fields
described earlier by Vetter et. al. [11,12,13].
This part of the CaC03 scale formed in an oil
field is generally very small and often negligible
for practical field operations because the co3 --
ion concentration in the aqueous phase prior to
any flashing of gases from the two liquid phases
is generally very low. Many oil reservoir waters
(brines) under reservoir conditions and prior to
any gas flashing show a rather low pH value and,
therefore, contain such low C03 -- ion concentra-
tions that no CaC03 precipitation can occur at
all. The vast majority of all CaC03 scale
formations and the formation of heavy CaC03 scale
depositions start when a gas phase is formed due
to flashing from the two liquid phases.
6. The moment any gas starts flashing from the two
liquid phases, i.e., as soon as the bubble point
pressure of the original two-phase system
(oil/brine) is reached, drastic and critical
309
3
thermodynamic changes are induced in the entire
liquid system. The common philosophy prevailing
in the industry is that only the gas flashing
from the oil phase has to be considered for
practical field operations. The gas flashing
from the aqueous phase is thought to be small and
negligible and, therefore, is commonly ignored.
This negligence leads to numerous "pitfalls for
the unwary" [7]. On the other hand, all
previously published papers on CaC03 scale
formations [1 through 6] totally ignore this gas
flashing from the oil phase and look only at the
gas flashing from the brine phase. This neglect
of the gas flashing from the oil phase led to a
totally wrong understanding of CaC03 scale
formation in oil fields. Ignoring the gas
flashing from both the oil and aqueous phase and
all induced and associated reactions in the
aqueous phase due to this gas flashing from both
liquid phases (i.e., as commonly ignored in the
oil industry) will lead to a totally wrong
concept and mathematical treatment related to the
CaC03 scale formations.
7. Flashing of gas from both the oil and brine
phases during the production process has numerous
effects on the CaC03 scale formation in any
typical oil field operation:
a) Prior to flashing of gas from the two 1 iquid
phases, the total C02 content of the reservoir
fluids is distributed at a certain ratio
between the oil and aqueous phases [7,8,9].
b) As the gas flashing starts and proceeds during
the production process, the COz becomes now
distributed between the oil, the brine and the
newly generated gas phase. This new 002
distribution between three phases (oil, brine,
gas) instead of only two phases (oil/gas or
brine/gas or oil/brine) will automatically
change not only the total amount of C02
dissolved in the two remaining liquid phases
combined but also the ratio of the C02 amounts
that remain dis solved in both the oil and
aqueous phases. Both the total amount of C02
dis solved in the two liquid phases and the
ratio of the dissolved C02 in the oil phase to
that which is dissolved in the brine phase
will constantly and continuously change as the
gas flash process due to the production of
fluids from the reservoir is proceeding.
8. The f 1 ash i ng of CO2 (and other chemically
reactive gases) [5,6,7] from the aqueous phase
and the associated depletion of 002 (and related
species) in this aqueous phase become the main
driving force for the formation of CaC03 scale
during the entire production process. The
following reactions now become pertinent:
a) Flashing of C02 and some other gases will
increase the pH value and, with that, the
concentration of 003-- ions in the remaining
brine phase. This increase of the C03--
concentration must not be confused with the
associated decrease of the C02 concentration
in the brine phase. This increase of the pH
as a function CO2 flashing from the brine
phase depends mainly on the chemical
composition of the brine. For example, if all
the 002 is flashed from pure water, the pH of
the remaining water can not exceed the value
which is determined by neutrality of the
remaining water (e.g., pH = 7 at standard
conditions). However, if the same amount of
C02 flashes from certain aqueous solutions
4 CALCIUM CARBONATE SCALE IN
such as a "typical" oil field brine, the pH can
easily exceed the value of 7. It is not
unusual that a flashed oil field brine has a pH
value of 9 or even higher while the pH of the
same brine under reservoir conditions prior to
gas flashing may have been only 5 or even
lower. The authors have measured pH values in
excess of 10 in some flashed brines as produced
in the field.
b) The increase of the pH value and the associated
increase of the C03-- ion concentrations in the
remaining brine phase during the production
process have a strong effect on the CaC03 scale
formation. Even if the solubility of the CaC03
in the brine phase would be independent of the
pH value, some CaC03 is generated in this
remaining brine phase (due to an increase of
the CO 3-- concentrations at the higher pH
values). Thus, the driving force for a CaC03
precipitation from the flashing brine can
become extremely strong.
Obviously, numerous concurrently and subseq uentially
occurring physical and chemical reactions are taking
place during the production process, thus leading to
a complex situation as far as the precise
mathematical treatment of the CaC03 precipitation is
concerned. Even though the general mechanisms of the
CaC03 scale formation may be rather simple, the
mathematical treatment of these react ions in their
entirety may become extremely complex.
BASIC C!.~ _M()DEL_li:Q_~SIDERl.TIOM~
Any relevant modeling of the CaC03 scale formation
from an aqueous phase in the presence of a coexisting
oil and, possibly, gas phase must be concerned, as a
minimum, with a mathematical description of the
following reactions:
1. The flashing of gas from the liquid phases and the
distribution or partitioning of C02 between the
oil, brine water and gas phases as a function of
the four basic thermodynamic variables (P,V,T,A)
under static (i.e., stagnant) and dynamic (i.e.,
flowing) conditions.
2. The chemical react ions in the remaining brine
phase which will lead to the precipitation of
CaC03 from this brine phase. These chemical
reactions as a function of PVTA can be divided
into two categories:
a) Reactions between the C02 and brine (including
the water it self and the other constituents
dissolved in this brine) leading to the
formation of various ionic species such as H+,
HC0.3- and C03-- type ions and to the
associated, pertinent changes of the pH value.
b) The formation of CaC03 species and their
solubility in the remaining brine phase.
Thus, any basic modeling of a CaC03 scale formation
from oil field brines must concern itself with
computations related to:
1. The effects of gas flashing from all liquid phases
on the phase behavior of the oil, brine and gas
phases.
2. The effects of C02 partitioning between all phases
existing in the system, in particular, on the C02
concentration in the remaining aqueous phase.
3. The effects of the C02 dissolved in the aqueous
phase on the transformation of the original C02
into the C02 hydration products and on the various
other C02 species which will eventually lead to
the formation of co3-- ions within the brine.
310
on. FIELD OPERATIONS SPE 16 908
4. The effects of the compositional variables in the
aqueous phase on the solubility of CaC03 in this
aqueous phase.
These four different and somehow related types of
thermodynamic effects must be known in great detail
for any precise mathematical handling of CaC03 scale
in oil field operations. One should keep in mind
that these four types of effects represent only the
major thermodynamic ef feet s dictating the CaC03
scale formation from oil field brines. Other and
minor thermodynamic effects such as the partitioning
of water into the oil phase and oil into the brine
phase are presently ignored.
Fla~-~~h.E-V i..Qr _a~ _C..Q.2 _P~r!_itioning
Determining the critical scale behavior and C02
partitioning effects represents the largest and most
difficult obstacle for any precise computation of
the CaC03 scale forming tendency [6]. All
calculations of the CaC03 phenomenon must rely on
knowing the correct amount of C02 dissolved in the
brine phase prior, during and after the flashing of
gas from the two liquid phases. This C02 amount in
the brine depends not only on the basic
thermodynamic variables as outlined earlier but also
on the partitioning of the total C02 dissolved in
both the oil and water phases [ 7]. Thus, the
varying amounts of C02 dissolved in the oil phase at
various pres sure s and t emperat ur es will have a
pronounced effect on the amount of CaC03 dissolved
in the brine phase at the same pressures and
temperatures. Obviously, knowing only the total
amount of C02 in the entire fluid system at any
pressure/temperature combination is not sufficient
to calculate the amounts of ca++ and C03-- which are
dissolved in the brine phase prior to @g_ after the
CaC03 p~ecipitation process occurs.
The critical amount of C02 dissolved in the brine
phase depends upon numerous thermodynamic, kinetic
and hydrodynamic factors. Even the common
assumption that "most" of the C02 is dissolved in
the oil and not in the brine can be dead wrong. At
a constant total amount of C02 in the fluid system
and at constant pressure and temperature conditions,
the concentration of C02 in both the oil and brine
phases will mainly depend upon the "water/oil" ratio
(WOR). As this ''WOR" is increased, more and more of
the total C02 amount contained in the system will be
dissolved in the liquid brine at the expense of C02
dis solved in the oil phase. Even at a fairly low
''WOR", the amount. of C02 dissolved in the brine
phase can be a multiple of the C02 amount dissolved
in the oil phase [7].
Under stagnant reservoir conditions, the
distribution of the C02 between the oil and brine
phase is fixed. As the gas flashing process from
the liquid phases starts and proceeds, the ratio of
the amount of C02 dissolved in the oil to that which
is dissolved in the brine will constantly change.
In addition, the fraction of the total CO2 which
remains dissolved in both 1 iq uid phases will
constantly decrease because more and more of the
total C02 will enter the gas phase as the gas flash
process is proceeding.
Obviously, the partitioning of the C02 between the
two liquid phases becomes somewhat of a "moving
tar g e t " be c au s e of t he numerous. and of t en
concurrently occurring reactions due to the ongoing
SPE 16 908 O.J. VETTER AND A.W. FARONE
flash process. During this flash process, the
temperature and pressure of the considered system may
constantly change, thus leading to a constantly
changing volume and composition of the three fluid
phases.
Some recent attempts were made by Nitsche et. al.
[14] and Kuan et. al. [15] to predict some of the
basic thermodynamics and the C02 behavior in the
three phase "oil/water/gas" system. These authors
used various types of an equation of state (EOS) in
their attempts to determine the phase behavior of the
oil, water and gas. HoWever, as mentioned in our
earlier paper on the subject of the pertinent phase
behavior of the C02 [7], the concepts and methods
proposed by Nitsche [14] and Kuan [15] will fail to
determine this C02 partitioning behavior. This
failure was only partially caused by a pronounced
lack of experimental data. Furthermore, Nitsche [14]
and Kuan [15] did not really use a true crude oil but
simple substitutes (decane [ 14] and a fairly simple
mixture of hydrocarbons [15]). They also did not use
a true-world oil field brine but pure water [14,15]
in their model considerations.
Kuan et. al. [ 15] encountered serious problems in
their EOS approach even in modeling of the phase
behavior of some fairly simple binary systems.
"lack of data" prevented them from modeling even a
simple binary system such as H20/C02 or as
H20/hydrocarbons. Only four ternary systems were
studied (CO2/ C4/ C1 0, CO2/ C1/ C 8, CO2/ H20 /C4, and
C02/H20/C10). The authors [15] admit that the
pertinent phase behavior of these ternary systems
could not be determined even by using two different
models, both based on an EOS approach. Only "trends"
could be predicted by using the two examined and
different models both based on different set of EOS'.
Pertinent Phase Behavior of the Brine Phase
Assuming one could precisely model and predict the
partitioning of the total C02 within all phases
existing in the system prior, during and after the
flash process, a second and rather formidable task
will still exist. The chemical thermodynamics of the
COz dissolved in the brine must be predicted before
one can start to predict the CaC03 precipitations.
This means, the formation and disappearance of the
various ionic "COz species" must now be modeled. The
predicted concentrations of all the various and
pertinent "co 2 species" (e.g. HC03-- and co3--) and
the associated pH values together with the ca++
concentration in the brine will eventually allow a
prediction of an actually occurring CaC03
precipitation.
Unfortunately, the solubility of COz in a brine
depends not only upon the temperature and pressure in
the system but also on the brine composition.
However, the solubility of C02 in water and in
various aqueous solutions has been extensively
researched [16 through 25]. Thus, finding reliable
solubility and density values based on true
experiments as required for a serious modeling effort
offers no real problems as opposed to Kuan's [15]
opinion.
The open 1 iterature contains numerous studies [26
through 29] related to experimental values describing
the solubility of CaC03 in aqueous solutions. The
references quoted in this paper represent only a
small fraction of the published 1 iterature on this
5
subject. However, what we find to our dismay is
that the published data base related to CaC03
solubilities as a function of pressure, temperature
and brine composition is not as extensive and
reliable as commonly assumed.
The basic thermodynamics related to the solubility
of both the C02 and CaC03 in aqueous solutions is
also fairly well understood even in the presence of
other components in the brine [32-34]. Finally,
numerous attempts have been made to predict the
precipitation of CaC03 from these aqueous solutions
as a function of numerous thermodynamic variables
[35 through 431. All of the calculations described
in these papers [35 through 43] are made for pure
water systems (i.e., oil is absent). Unfortunately,
all of these model attempts (see also [5 and 6]) are
based on rather complex and rigid computer codes
which try (a) to take into account the entire
composition of the brine and (b) to predict the
precipitation of every possible salt under the sun.
For various reasons [5,6], none of these
"theoretical" models can be easily adapted for an
all encumbering CaC0.3 scale model for practical oil
field operations [10].
EOS APPROACHES TO MODELING OF
A CaC03 PRECIPITATIONS
There seems to be a general trend in the oil
industry toward equation of state (EOS) based
approaches aimed at modeling the thermodynamic phase
behavior of various oil field related fluid systems.
Often, the very basic restrictions inherent to any
EOS approach are ignored. Therefore, it may be
advisable to recall some of these basic restrictions
when it comes to searching for an EOS which may be
suitable to predict and mathematically describe
certain critical reactions in an oil field.
Let's look again at the four basic thermodynamic
variables (pressure, temperature, volume, amount)
which determine the phase behavior of oil field
fluids and the formation of scale. If the amount
(A) in a given system is fixed, any two of the
remaining three variables can be used to determine
the remaining third variable. Any equation aimed at
describing mathematically the pressure/volume/
temperature (PVT) relationships at a fixed amount
(A) is called an equation of state (EOS). Any of
the EOS approaches may be used to describe the
thermodynamic behavior of the particular substances
in the system. In this case, the entire set of
relationships between P,V and T can be expressed
geometrically only by means of a surface as
indicated in fu~.JL.!. If more than one substance
are considered in a system (e.g., pure water, C02
and methane) and if the amount of each substance is
given and fixed, an EOS approach may still be
practical even though it may now involve some rather
complex mathematics.
As the number of substances in the considered system
is increasing, any EOS which can be fitted to
describe the actual and often complex behavior of
such a system becomes increasingly more complex.
The geometric description of the PVT relationships
in this multi-component system can also be expressed
as a surface. The complexity of this surface
reflects the complexity of such a system as
indicated in Figure 2. Finally, at an extremely
large number of substances in the system, the
complexity of the EOS describing the PVT behavior of
311
6 CALCIUM CARBONATE SCALE IN On. FIELD OPERATIONS
such a system will become mathematically non-
manageable.
One has to remember that this EOS approach correctly
describes the PVT behavior of such a system only if
the amount of each substance within the system
remains constant, no matter whether these substances
exist in a 1 iq uid or gas phase. However, a serious
problem will surface if any part of any of these
substances is converted into a new substance, i.e.,
if "old" substances are disappearing and "new"
substances are appearing within the considered
system. In this case, the amount of substances is
not kept constant and principal model problems will
occur if the computational approach is based on EOS
considerations. In simple terms, any of the EOS
approaches is conceptually wrong in such a case.
To illustrate this problem, we can use the chemical
behavior of the COQ dissolved in pure water as an
example:
1. Some of this dissolved C02 may still exist as
"true 11 C02 in the water phase.
2. Some of this dissolved C02 may chemically or
physically react with the water and may form
"hydrated" 002 which has a totally different PVT
behavior than the "true" C02. Thus, the "true"
amount of C02 in the system is not constant
because some of it becomes hydrated and,
therefore, disappears from the system.
3. To complicate things even further, the "old"
system does not exist any longer because a new
substance ("hydrated" C02) has entered this very
same system. Various hydrated C02 compounds can
form. Each type of hydrated C02 acts as new
substance in the system.
4. Finally, some more of the initially dissolved C02
may chemically react with the water molecules and
may subsequentially form various ionic species
such as HCOj-, C03-- and H+. These ionic species
have a PVT behavior which is again different from
that of both the "true" and "hydrated" C02. The
formation of these ionic species further reduces
the amount of "true" C02 in the system.
Obviously, a simple EOS approach describing the PVT
behavior of the system water/C02 system and ignoring
these chemical reactions which lead to a disappearing
and generating of substances in the entire system is
theoretically and conceptually wrong and will
eventually yield a false description of the PVT
relationships in this water/C02 system. The errors
caused by this straight-forward EOS approach are
simply caused by ignoring the most critical criterion
for the EOS approach, namely, to keep the amount (A)
of all substances constant within the system.
The failure by Kuan et.al. to predict the phase
behavior of even "simple" oil field fluid systems
based on an EOS approach is not unusual. Coats and
Smart [ 44] noticed that even a cubic EOS will not
accurately predict measured laboratory data related
to the PVT behaviors of fairly simple oil/gas
mixtures. They used a regression method to adjust
the properties of the system components to fit the
experimental data. Agarwal et. al. [45] picked up on
this method of using mathematical regression methods
to minimize the discrepancies between accurately
measured PVT data and the related, calculated PVT
data as predicted by a cubic EOS. Agarwal et. al.
[ 45] themselves stress the fact "that the regression
procedures will not correct the deficiencies of the
312
SPE 16 908
EOS used". In principle, these regression methods
[44,45] represent an attempt to make the wrong tool
somewhat less wrong for the intended job.
If an attempt is now made to use such an EOS
approach for calculating the CaC03 scale formation,
an obvious and principal problem will exist. The
relevant CaC03 precipitations must then be described
by a number of unknown points describing unknown
surfaces within an envelope of unknown dimensions.
"Tuning 11 of the parameters used in such an EOS
approach to match existing experimental data by
regression methods [ 44, 45] would invariably end up
in disaster. Too many parameters would have to be
"tuned" for too many experimental data. Obviously,
an EOS approach of any kind aimed at predicting the
complex CaC03 behavior in a complex oil/brine/gas
mix t u r e of a t y p i c a 1 o i 1 f i e 1 d s y s t em will
invariably end up in a dead-end street.
A PRACTICAL APPROACH TO STATE MODELING OF
CaC03 PRECIPITATIONS
Instead of using an EOS approach, the approach used
by us is based on modeling of distinct states which
can be practically defined for any oi 1 field
operation. Any system is considered to be in a
particular "state" or thermodynamic equilibrium when
the particular values of P, V, T and A are constant.
In a "state model", we assume the system going from
one state to another state without considering the
path that one uses to arrive at these new states.
In actual calculations, this allows one to use @Y.
path for which data are known as long as the correct
states are calculated. This method of "state
modeling" does not have any inherently principal
errors (such as EOS approach). Furthermore, this
method will become extremely flexible for at least
two major reasons:
1. The states can be selected at will and so that
experimentally determined data can be utilized.
2. The states can be easily varied so that they
match the various sets of thermodynamic
conditions as they exist in truly an actual oil
field operation.
Thus, the state modeling approach fulfills one major
requirement for any oil field operation, namely, to
be extremely flexible in order to become adjustable
for any of the large multitude of thermodynamic
conditions which vary from field to field, well to
well and even from time to time.
In an oil field system, we shall define first a
distinct number of major states of interest and then
several other states that are useful in connecting
the pertinent data to the major states of interest.
Major states of interest are:
1. Static reservoir (RS), i.e., a reservoir under
non-flowing conditions.
2. Dynamic reservoir (RD), i.e., a reservoir under
flowing conditions near the wellbore.
3. Bottom of a well (BD), i.e., the bottom of a well
under flowing conditions.
4. Well head (WD), i.e., the top of a well under
flowing conditions.
5. Well test separator (SD), i.e., the interior of a
well test separator under flowing conditions.
6. Surface facilities (FD), i.e., any part of the
surface facilities under flowing conditions.
Any other major and other states can be defined at
will.
SPE 16 908 O.J. VETTER AND A.W. FARONE
Terminology, Nomenclature and State Definition
Due to some obvious problems caused by (a) the large
number of variables involved and (b) the use of these
variables in computer algorithms we shall avoid Greek
or other foreign characters. These Greek and other
foreign symbols were more useful in the pre-computer
ages than they are today. This replacement of
foreign symbols by a better manageable letter
designation system will make the translation of the
equations and writing of the computer codes easier.
The last two letters of all expressions used
throughout this paper will denote a major state. The
letters in front of these expressions will denote
properties relevant to the given major state. For
example, TRS will be used to denote the temperature
in the static reservoir (RS). Other letters in
parentheses in front or behind the major state
designation will denote the phase or components,
respectively. For example, C(0 )RS(C02) will denote
the concentration of CO2 in the oil phase under
static reservoir conditions.
We also need to define some other useful states.
Often, there exist only two fluid phases under RS
conditions (oil and brine). At some point during the
change of state between RS and SD, the pressure of
the fluid system may drop below the bubble point
pressure (PBP) at which a third phase (gas) forms.
This state will be called the bubble point (BP).
This BP state could be related to any of the other
states such as RS, RD, BD, etc.
Another useful state to understand could be the
TBPRS. In this state (BPR.S), the pressure of the
reservoir fluids is reduced from PR.S to PBRS at
constant temperature (TBPRS = TRS). It may also be
of interest to know the state of the BP at TRD
(BPR.D). In both states (BPRS and BPR.D), we assume
that a decrease of the pressure (PRS to PBRS and PRD
to PBPRD) can be achieved without a change of
temper at ur e, i e , TR S = TBPR S and TRD = TBPRD.
These two states represent two different states even
though they are both associated with a bubble point
pressure (PBP). Because (a) a certain PBP is common
to all major states (RS, RD,BD, WD, SD and FD) and
(b) the BP is the state variable which is widely
changing (usually its temperature in terms of
relevance to other states) we will denote:
1. PBPRS: The state at which the PBP replaces PRS
in the RS state.
2. PBPRD: The state at which the PBP replaces PRD
in the RD state.
3. PBPBD: The state at which the PBP replaces PBD
in the BD state.
For each of the major states, it is also useful to
think of a reference state that would bring the
volume and amount to a pressure of 1 atm or some
other reference pressure at a temperature equal to
the temperature of the state. The purpose of this
reference state is to allow the calculation of the
amount (as mass and/or chemical composition) for a
fixed volume at one atm or at saturation pressure (if
the temperature is high enough to cause a saturation
pressure larger than one atm).
The reference state will provide a tie-in to data
(e.g., solubility data) that exist in the public
domain 1 iterature. Using these reference states
makes it then possible to use the fixed volume data
at one atm (or any other reference pressure such as
313
7
saturation pressure) to calculate the mass and
chemical composition. Both the mass and chemical
composition at fixed volume and one atm or any other
reference pressure can then be converted into the
mass and chemical composition at the major state
conditions if the thermodynamic behavior of the
system as function of pressure and volume is known
at the reference state. Again, the reference states
have the same temperature as the corresponding major
states but a pressure of one atm or as desired. In
accordance with our designation system, we denote:
1. REFRS: The reference state for RS at TRS but
one atm.
2. REFRD: The reference state for RD at TRD but
one atm.
3. REFSRS: The reference state for RS at TRS but at
known saturation pressure.
4. REFSRD: The reference state for RD at TRD but at
known saturation pressure.
The multiplication sign in all equations is denoted
by an asterisk (*). All root signs are avoided and
are replaced by exponents.
Graphi~
With today's computer power, there is no reason to
avoid graphics. Proper graphics can help to
visualize the pertinent changes of any system over
all ranges of all parameters of interest. Most of
the graphs given in this present paper are based on
multi-color 3Ji) contour mapping. For example, the
two original graphs showing the partial data base
for the CaC03 solubility (Figures 3 and 4) give the
solubility of CaC03 as a function of the C02 partial
pressure and temperature for 0 and 0.5 molar NaCl
solutions in form of multi-colored 3D contour maps.
Unfortunately, the major advantage of these multi-
colored contour maps is lost if these graphs are
printed not in color but in a black and white mode.
The original color graphs show the contours of the
CaC03 solubility over the entire range of interest
in color bands which are easy to identify in the
original graphs. The only other way to graphically
show this partial data base or any similar
relationship is by plotting the data in the
conventional 2D manner and by showing the data in
sets of curves. However, instead of only two 3D
graphs we would then have to plot a total of
approximately ten 2D graphs, each showing no more
than three individual curves.
Some Algorithms
In the equations described below, each equation for
each state under consideration is identified by its
letter designation followed by a colon and the
number of the equation. Each equation for each
state is set in parentheses. The numbering of
equations begins anew for each state. Thus,
equation number (RS: 4) is the fourth equation for
the static reservoir considerations, whereas (WD:6)
is the sixth equation for all wellhead
considerations under flowing conditions. However,
it is not necessary to write all equations for all
states because the calculations will fall into two
natural categories for both model approaches (see
later):
1. Calculations considering only two phases (i.e.,
when P is greater than PBP).
2. Calculations considering three phases (i.e., when
P is smaller than PBP).
8 CALCIUM CARBONATE SCALE IN on. FIELD OPERATIONS SPE 16 908

In our number 1ng scheme for each of the given Combining equations (1), (2) and (3), we arrive at:
equations, we will leave out the state designation if
generally applicable thermodynamic relations are a2(H+)*a(Co3--)
given. For example equation (1) as shown below, KS*K1*K2 = KEQ ( 4)
indicates a generally valid, common thermodynamic a(H20)*a(C02)
relationship, whereas (RS:1) indicates a relationship
for the state RS. where KEQ is the equilibrium constant.

The following calculations for RS assume that this The right hand side of equation (4) can be replaced
state has a pressure above PBP. It is also assumed by an effective ionization constant for the system
that all reservoir fluids are in thermodynamic
eq uil ibr ium. (5)

A(WTO )RS(C02) 1/ A(O'IW )RS(C02) (RS: 1) To simplify our presentation, we will temporarily
replace activities by concentrations even though
C(0 )RS(C02) activities are used in the actual calculation
A(O'IW )RS(C02) = - - - - - (RS: 2) whenever necessary. In this case, we can write
equation (4) as follows:

Where the letters A and C denote amount and [C(W)RS(H+)]2*C(W)RS(C03--)

concentration. What is needed for the remainder of' KEQ (RS: 3)
our model is a correct determination of C(W)RS(C02). C(W)RS(C02)
The data required to solve these two simple equations
for C(W)RS(C02) are measured [7] or must be where KEQ is the equilibrium constant, i.e., the
calculated. If a sufficient number of laboratory product of KS*Kl*K2 as indicated in equation (4),
measurements [7] are performed, then solving of both and where the activity of water in equation (4) is
equations (RS:1) and (RS:2) offers no problems. On unity.
the other hand, if sufficient data to solve both
equations are not available, the pertinent data must We also know that:
be calculated. This means, we have two basically
different types of state models: C(W)RS(Co 3 --)*C(W)RS(ca++) KSP (RS: 4)
1. Model I: Enough measured data exist to solve the
equations (RS:1) and (RS:2). where (Co3--) and (ca++) are the concentrations of
2. Model II:Not enough measured data exist to solve C03 -- and Ca ++ in the reservoir brine under
the equations (RS:1) and (RS:2). equilibrium conditions at the stateRS and KSP is
the solubility product for CaC03 also at RS.
In the Model II approach, we have chosen to use
initially C(W)RS(C02) parametrically and then to At equilibrium, the concentration of C03-- in the
determine the correct value for C(W)RS(C02) at a brine is determined by:
subsequent step in our model (see later).
C(W )RS(C03 --) (XC03 + Z) - Y (RS: 5)
Let's first concentrate on using C(W)RS(C02)
parametrically to develop the remainder of our where
system: XC03 the initial concentration of 003-- before
any precipitation occurs.
z the concentration of C03-- in the brine
KS (1) which is generated by the reaction between
CO2 and H20 as indica ted in equation
(RS:3).
Which is the equilibrium expression for the y the concentration decrease of the initial
solubility of CO2 in aqueous media where a (x) is the C03 -- concentration (XC03) due to the
activity of the xth species and KS is the solubility precipitation (of CaC03) as determined by
of C02 in brine. (RS: 4).

Obviously, Y represents the precipitation of CaC03

K1 (2) from the brine at the state RS.

Let's now elaborate one more time on the

This equation (2) describes the equilibrium determination of C(W)RS(C02) If a gas phase would
expression for the first ionization constant of exist at this state RS and assuming Henry's Law
carbonic acid (i.e., K1). holds true, we could easily calculate either
C(W)RS(C02) or C (0 )RS(C02) as shown later for the
We also know: state RD. However, until BP is reached anywhere
within the system, we can temporarily determine the
a(H+)*a(Co3--) CaC03 concentration as a function of only one
K2 (3) parameter even though at least two parameters are
a (HC03-) required for a final determination of C(W)RS(C02) as
indicated in equation (RS:2). Again, the CaC03
This equation (3) gives us the equilibrium expression precipitation from the brine can not be correctly
for the second ionization constant of carbonic acid determined unless C(W)RS(C02) is known. This
(i.e., K2). problem can be solved by temporarily and
parametrically determining the CaC03 concentration

314
SPE 16 908 O.J. VETTER AND A.W. FARONE
as a funct1on of e1ther C(O)RS(C02) or C(W)RS(C02).
As mentioned above, we have chosen to determine the
CaC03 concentration parametrically as a function
C(W)RS(C02) This will allow us to find the correct
point on the curve representing the CaC03 vs.
C(W)RS(C02) relationship through a subsequent
determination of the mass balance for C02 in the
total system.
C(W)RS(H+) in equation (RS:3) can be related to Z in
equation (RS:S) through:
(XH) + 2Z
where (XH) is the concentration of H+ in the absence
of C02 (i.e., the H+ concentration that is due to all
water constituents which are not related to the C02
species) and Z1 is the additional concentration of H+
which is generated due to the dissociation of
carbonic acid (RS:S).
The equilibrium concentration of ca++ ions under
reservoir conditions is given by equation (RS:4). If
any precipitation of CaC03 occurs (e.g., due to
pressure drops) prior to reaching PBP, the Ca ++ ion
concentration can be calculated by:
C(W)RS(Ca) = XCa - Y
where XCa is the initial concentration of ca++ and Y
is the concentration decrease of the initial ca++
concentration (XCa) after the proper amount of CaC03
is removed from the system by precipitation (see
RS:4). Yin (RS:4) andY in (RS:7) are identical.
Equations (RS: 3) through (RS: 7) can be combined and
reduced to:
(XH)2
z3 + [XH + XCOJ - Y] *
z2 + [ _ _ + (XH *
XC0 3 ) - Y
* XH] *
Z 4
[(XH)2 * XC03 - KEQ * C(W)RS(C02)]
+ 0
4 species are mainly contained in the brine phase.
and
y2 - (XCOJ + Z + XCa) Y + (XCOJ * XCa) + (Z
KSP = 0
Equation (RS: 8) and (RS: 9) can be
simultaneously for Z andY.
It should be noted that equations (RS: 8) and (RS: 9)
are cubic and quadratic, respectively. In any method
of formulating the solution of multiple sets of
equations (such as this set of cubic and quadratic
equations) there will be the possibility of multiple
solutions. A number of these possibilities will
arise because of the necessary algebraic
manipulations or the numerical solutions of computer
algorithms. The modeling efforts for the system must
allow for the selection of the true and physically
meaningful solutions from among the artifacts. Only
one of t he p o s s i b 1 e s o 1 u t i on s is ph y sica 11 y
meaningful.
The Z and Y values obtained through a simultaneous
solution of equations (RS: 8) and (RS: 9) can now be
substituted in equations RS:S through RS:7 to
calculate the quantities of interest such as
C(W)RS(COJ--), C(W)RS(H+) and C(W)RS(ca++).
9
C(W)RS(H"~") is the combination of all H+
concentrations in the brine phase at equilibrium
condition stemming from various reactions.
(W )RS (pH), i.e., the pH value of the reservoir
brine, can now be calculated from C(W)RS(H+).
We can also state:
C(W )RS ( CaC03) C(W)RS(Ca++) (RS: 1 0)
This equation (RS:lO) is valid even under non-
equimolar concentrations of CaC03 and Ca ++ in the
(RS: 6) brine if the proper stoichiometric conversion is
considered. This means, if C(W)RS(ca++) is given in
units of moles per 1 iter brine, then C (W )RS(CaCOJ)
would be correct as written in equation (RS:ll).
One major problem with this type of calculation is
given by the need to know the correct values of KEQ
and KSP at TRS and PRS. These values can be
obtained from available 1 iterature references even
allowing for the presence of other salts in the
brine. References [26 through 31] represent only a
portion of the required literature references
describing the pertinent CaC03 solubility
characteristics in. the aqueous systems which
resemble actual oil field brines. If these required
(RS: 7) data are available only at pressures different from
those of interest but at the same temperature, the
proper correction can be calculated as described
later in our consideration of the state REFRS.
Still, one additional point has to be made. As
mentioned earlier, the calculation of C(W)RS(C02) or
C(O)RS(C02) represents a number of problems. One of
the two variables must be known to calculate the
other. To determine C(W)RS(C02) parametrically as
mentioned earlier is useful only if one of the two
missing variables is known as indicated in equation
(RS:2). The missing equation required to calculate
the missing variables can be determined through mass
balance considerations concerning all the CO2
related species in the brine such as C02, HC03-,
(RS: 8) H2C03, C03-- and CaC03. Except for C02, these
Lumping all the C02 species in the brine phase
together into one expression allows us to express
* XCa)- them in units of C02 equivalent moles. Assuming
(RS: 9) these C02 equivalent moles are known, we can then
state:
solved
A(O)RS(C02) + A(W)RS(C02) = ARS(C02) (RS: 11)
where ARS(C02) is the total C02 content in the
reservoir fluids (oil and brine) expressed in COz
equivalent moles.
At first glance, it may seem that an equation
similar to equation (RS:l1) could easily be
developed and solved for all parameters in the
system. Analyzing of oil, gas and water samples
from a field separator and determining the flow
rates of oil, water and gas in the separator at the
SD state would allow us a determination of ARS(C02)
All major COz related species except for extremely
small amounts are accounted for in the well test
separator fluids. These extremely small and missing
C02 amounts are due to the carbonate precipitations
upstream of the separator. These small portions of
the total CO2 related amount can be neglected
because they are normally much smaller than the
error caused by (a) the chemical ana~ysis of the
315
10 CALCIUM CARBONATE SCALE IN on. FIELD OPERATIONS SPE 16 908

separator tluJ.ds and ~b) the tlow rate determlnatJ.ons
under actual field conditions.
Let,. s now consider the state REFRS in some more
detail. In the REFRS state, the pressure and
temperature (PREFRS and TREFRS) are selected so that
a useful state exists at which the KEQ and KSP values
are known or can be calculated from available
solubility and other, related data.
The transformation from REFRS into RS can be
accomplished by using the Gibbs Free Energy
relationship between these two states. For example,
KSP(PREFRS) DV*DP
ln ( ) (RS: 12)
KSP (PRS) R*TRS
where KSP(PREFRS) and KSP(PRS) are the solubility
products of C02 or CaC03 at PREFRS and PRS,
respectively. The DV represents partial molal
volumes and reflects the changes in brine volume when
the system goes from PREFRS to PRS at TRS. DP simply
is the difference between PREFRS and PRS.
Similarly,
KEQ ( PREFRS) DV*DP
ln ( ) (RS: 13)
KEQ (PRS) R*TRS
Equations (RS:12) and (RS:13) represent simplified
expressions as described earlier [11,12,13]. More
exact versions of equations (RS:12) and (RS:13) may
be used by introducing terms of DV which hav~ a
higher order. Obviously, DV by itself is a function
of T, P and the composition of the brine at both
states REFRS and RS [11,12,13]. These various DV
values become available when the densities of the
brine and/or the various K values are experimentally
determined for various other reference states as
quoted in the open literature.
After devel op1ng the model as described above, we
now have to consider that PBP will be reached
somewhere in the flowing system. For the sake of
describing the model, we assume that the actual
state pressure becomes larger than the PBP for the
fluid system. We also assume that PBP is reached
somewhere between the state RS and RD. This means,
a gas phase has been formed between RS and RD.
The calculations concerned with determining the RD
state become now only slightly more complicated than
those used for determining the RS state if we assume
that the observations described by Ellis and others
[26-31] are correct. These observations are related
to the solubility behavior of CaC03 as a function of
the C02 partial pressure of the gas phase.
Ellis [26] reports that the CaC03 solubility in the
brine can be described by a simple function of the
C02 partial pressure over a wide range of
temperature and pressure:
(6)
where Q is a function that can be determined from
experimentally determined values and where P(C02) is
the partial pressure of C02 in the gas phase. Some
parts of the CaC03 solubility data base are shown
in graphical form in Fi&!,!.~g_1!_:2__an<!__4. Q can also be
developed by using of the correct values of the
Henry's Law coefficient as follows:
P (CO2 ) *F (CO2) (7)
KH
A(W)C02
where KH Henry's Law coefficient
F(C02) fugacity of C02
A(W )C02 moles of C02 in the water phase
Another useful relationship can be determined by
using the Ostwald coefficient:

The actual DV values in equations (RS:12) and (RS:13} ( 8)

vary from reaction to reaction. The DV values given KO- - - -
by Vetter [11,12,13] for various sulfates
precipitating from oil field brines can be extended
to the CaC03 precipitation reactions based on where KO Ostwald coefficient
experimental data from density measurements of L(C02) C02 in the liquid phase (in g/cc)
CaC03/brine solutions. However, to calculate KEQ for V(C02) C02 in the vapor phase (in g/cc)
the solubility of C02 in water a different DV value
is needed. Parkinson and de Nevers [ L6] studied the Usually, the empirical Henry's Law expression is
system C02/water and investigated some of the written as:
pertinent partial molal volumes of C02 in these
systems. They found that this partial molal C02 ( 9)
tvolume is almost independent of pressure and
temperature. This situation is similar to the where KHH represents the experimentally determined
partial molal volumes of the sulfate scales as combination of KH and F(C02) which agrees with
reported by Vetter [11,12,13]. However, the partial equation (7).
molal C02, volume is strongly dependent on the C02,
concentrations in the water phase. Grogan and Thus, we can use equation (6) in the following form:
Pinczewski [ 48] realized this C02 behavior reported
by Parkinson and de Nevers [ L6] and estimated the [KSP (Caco 3 ) ]3/ 2
mean value of the partial specific C02 volume to be (10)
on the order of 0.0014 Nm3/Kg (or 0.022 ft3/lbm) at y
129F, 1900 psi and a C02 concentration of 0.05 Kg
C02 per Kg water phase (mass fraction of C02 in water If C(W)RD(CaC03) is known, we can then use equation
phase). Other DV values can be calculated from (10) to calculate
numerous published experimental data in a fashion
described earlier by Vetter [11]. [C(W)RD(CaC03)]3
(RD: 1)
y

316
SPE 16 908 O.J. VETTER AND A.W. FARONE
The appropriate value for C(W)RD(CaC03) at the state
RD can be obtained from the appropriate reference
state (REFRD) for which the CaC03 solubilities are
known. These data are available from the literature
as a function of temperature and pressure (usually,
for a pressure of 1 atm or saturation pressure).
PC0 2RD
C (W )RD (CO2)
KHHHRD
where KHHHRD is the empirical Henry's Law expression
at the state RD after an appropriate rearrangement
for KHH in equation (9) has been made to account for
the differences in units.
With these parameters known, one can now follow the
methods outlined previously for the state RS in order
to determine the remaining parameters. Furthermore,
if the Ostwald distribution coefficient or the
Henry's Law values for the C02 in the oil are known,
one can also calculate C(O)RD(C02)
It should be further noted that the existence of a
gas phase in thermodynamic equilibrium with both the
oil and brine phases provides some additional
information about the system if the Gibbs phase rule
is considered. When three phases coexist in
equilibrium, there are no degrees of freedom left.
This means, the system is fixed and can be totally
described.
In practical terms, we do not have to concern
ourselves with a parametric method for determining
the C(W)RD(CaC03) for calculations in the
oil/brine/gas system as opposed to the determination
of C(W)RS(CaC03) in the oil/brine system. This is
due to the fact that the system is totally determined
according to the Gibbs phase rule:
F=C-P+2
where F number of degrees of freedom
c number of components
p number of phases
This Gibbs phase rule nicely supports our model
approach. It seems that the number of components (C)
in our system is very large. However, the C02
related species are not mutually exclusive. If we
consider the species COz, HC03-, H2C03 and
co3--, we know the equations:
COz + H20 H2co 3
H2 co 3 n+ + nco 3 -
Hco 3 - n+ + co 3 --
Because these species are not mutually exclusive,
they can be lumped together as one system component.
As shown in equation (RD: 1), these species can be
organized into a single equation which will relate
the C02 and C03--. If the pH is known (H+ is related
to the CO2 species but is, by it self, not a C02
species), the system is then totally described
according to the Gibbs phase rule. Thus, these
various many and different species can be considered
as only on component for phase rule considerations.
If we know the CO2 as CO2 in the gas phase, the
concentration of CO2 species in all phases is then
automatically fixed. This by itself is one proof
that our model approach is correct.
11
'!:_H]:_:NEW _ ~_12~_1\.j>PR__Q!CH
The new model approach is broken down as follows:
1. Predicting the gas flash behavior of the two
liquid phases (oil and brine) including shrinkage
factors, changes of compressibilities and other
thermodynamic parameters.
2. Describing the partitioning of C02 between the
oil and brine phases prior, during and after
(RD: 2) flashing.
3. Calculating the pH value and the pertinent ion
concentrations of the C02 "species" in the
remaining brine phase.
4. Predicting the CaC03 precipitations based upon
the pertinent ionic concentrations in the
remaining brine.
Any practical approach to any CaC03 scale problem in
any given and specific field must start with a
precise definition and quantifies tion of the CaC03
scale depositions as a function of location and time
as well as numerous reservoir characteristics and
field operational conditions and procedures.
The simple collection of any water sample in the
field and the subsequent analysis of this water
sample followed by the calculation of a stability
index as done presently and in the past will
definitely not allow a field operator to correctly
define and quantify his CaC03 scale problem. A
somewhat more sophisticated approach is definitely
required to delineate and quantify at least some of
the pertinent characteristics of the CaC03 scale
existing or formed in a given field.
The two modeling approaches as described earlier are
very similar. In the first case, the approach is
based on the availability of a complete set of
experimental and measured data required for a
complete calculation of all thermodynamic variable
in the system which will dictate the CaC03
precipitation. This includes all pertinent field
data (i.e., all relevant pressures, temperatures,
volumes and amounts) as well as laboratory data
related to the bubble points and the C02
partitioning effects under simulated field
conditions [ 7, 8, 9]. In the second approach, again
all pertinent field data are required. However, no
C02 partitioning data measured in a laboratory exist
for the considered field system.
DA!_4_.!_f&!UJ~.E~NT S _FQR_~UJ~_}f_Q))~k_ING
The required input information for this new model
approach is as follows:
1. Well test separator data:
a) Pressure, PS
b) Temperature, TS
c) Flow rate of gas, RSG
d) Flow rate of oil, RSO
e) Flow rate of water, RSW
2. Compositional data:
a) C02 content of separator oil, C(O)SD(C02)
b) Chemical composition of separator gas,
C(G)SD(C02), C(G)SD(Hydrocarbon), etc.
c) Chemical composition of separator water,
C(W)SD(C02), C(W)SD(NaCl), etc.
3. Other field data:
a ) S t a t i c r e s e r v o i r p r e s s u r e , PR S , a n d
temperature, TRS.
b) Dynamic reservoir pressure, PRD, and
temperature, TRD.
c) Flowing bottomhole pressure, PBD, and
temperature, TBD.
317
12 CALCIUM CARBONATE SCALE IN OIL FIELD OPERATIONS
d) Flowing wellhead pressure, PWD, and
temperature, TWD.
e) Flowing surface facility pressure, PFD, and
temperature, TFD.
4. C02 partition and "PVT" data:
a) Bubble point pressure, BPB of separator fluids
at TRS.
b) Specific volume of oil, V(O), water, V(W), and
gas, V(G), at the states RS BPRS, RD, BD, WD,
SD and FD.
c) C02 distribution between oil, water and gas at
RS, RD, RW, RS and FD.
Calculating the CaC03 solubility in a brine and the
associated CaC03 precipitations as a function of
varying pressure and temperature but at constant
brine composition is fairly straight-forward. Prior
to forming a gas phase, the total C02 content of the
brine at decreasing pressure and/or temperatures is
only negligently affected by CO2 partition effects.
Knowing the total C02 content in the brine allows us
to calculate the pertinent ionic equilibria in this
brine including pH and C03-- concentrations.
As soon as the PBP is reached, a complicating factor
must be considered. The total C02 content in the
brine starts changing as a function of decreasing
pressure and temperature. C02 will flash from both
the oil and brine phases. The C02 content in the
brine is now changed by gas flashing from the liquid
phases and by a subsequent establishing of the new
partition equilibria. The pertinent equilibrium
conditions for both the flash and partition processes
were described earlier.
Thus, the newly established total C02 content in the
brine after a predetermined pressure and/or
temperature change into a region below the PBP can be
mathematically described. Knowing the total C02 in
the brine after the new pressure and temperature
conditions are established (e.g.,
pressure/temperature changes from PRD/TRD to
PBD/TBD), one can now repeat the calculations related
to the ionic equilibria in the brine and the
subsequent CaC03 precipitation.
These calculations of the flashing and partitioning
CO !z and the subsequent pr ecipi tat ions are then
repeated in predetermined steps (e.g., from PRD/TRD
to PBD/TBD to PWD/TWD to PSD/TSD to PFD/TFD). There
is no limit to the numbers of steps, i.e., any known
or desired pressure/temperature combination of the
fluid system under field conditions can be included
into these modeling efforts.
A typical case of CaCOj formation in a California
well is shown in ~igur~~_!P~ough ~ In this case,
the predicted CaCOj precipitation data are plotted in
a 2D form in Figu:t_~--~~d ___.2.. The CaC03
precipitation in terms of mg precipitate per 1 iter
brine are given for a number of temperature/pressure
combinations in this well. Figures_]_~nd~ show the
entire CaC03 scale tendency as a general function of
temperature and pressure in a system that covers the
same WOR of 0.2. However, a wide range of pressure
and temperature is covered. Any of the pressures and
temperatures shown in Figures 7 and 8 could occur in
this well. The sealing tendency for any
pres sure /t emperat ur e combination given in these
~igures l_~d 8 can be directly read from these two
graphs. The graph shown in fuure 7 is shown in a
rotated position again in Figure 8.
318
SPE 16 908
More detailed information related to a practical use
of this model with and without measured PVT and C02
partitioning data will be described in a future
paper [10].
MO~EL 1 PR_.9_~EMS
Rm.4_TED TO
ORIGIN OF SEPARATOR GAS
To calculate (i~st;;d- of me;s-~ri~g)-the true three-
phase PBP (oil/brine/gas), we actually use the model
approach described above. However, in this case the
model is run in a back-ward direction. All well
test s epa rat or data ( T , P and rates) and
compositional data from the analyses of the
separator fluids (oil, gas and water) are used to
calculate the PBP for the entire system under
increasing temperatures as encountered downhole.
These increasing temperatures used for these
calculations should represent downhole temperatures
as described earlier.
These three-phase PBP calculations will determine
the PBP for each downhole temperature, including the
static reservoir temperature. These calculations
are "safe" as long as the calculated PBPRD and PBPRS
are lower than the measured PRD and PRS.
If the calculated PBPRD or even the PBPRS is larger
than the PRD or even the PRS, we will know that
"free" or "excess" gas exists within the reservoir.
This "excess" gas will also be determined during any
experimental determination of the three-phase PBP as
outlined by Vetter et. al. [7].
This ratio of the two different types of gas in the
produced separator fluids becomes irrelevant for the
calculation CaC03 precipitations as long as both
gases stay in thermodynamic equilibrium with the two
liquid phases. However, it is possible that the
liquid phases are produced from a certain reservoir
horizon and the "excess" gas from a totally
different horizon. In this case, all produced gas
may be equilibrated during the ongoing production
process within the wellbore but not within the
reservoir while all fluids are flowing t award the
wellbore. Thus, the presence of "excess" gas in the
separator may not invalidate our calculations of the
CaC03 scale within the wellbore but certainly those
of the CaC03 scale within the reservoir. Obviously,
serious errors may be introduced into our
calculations if the "excess" gas is not excluded
from that part of the fluid system which contains
the oil and water phases.
These problems related to the "free" or "excess" gas
exist for any and all prediction methods or models
aimed at calculating the CaC03 precipitation in the
reservoir. Therefore, certain corrections or
adjustments have to be made to account for the two
different types of gas potentially existing within
the reservoir. Time-sequence analysis calculations
together with a history matching will overcome these
uncertainties.
SOME_ l'_lliN_CIP&_P!U)Jll,j:MS
REL4_'l'J!;]) TO Cac_g 3 _P].:gHCT_lQ_~
There exists a principle fallacy with this model as
well as with any other model which is based on using
as input information any low pressure/temperature
brine compositional data. Assuming some CaC03
precipitation has occurred during the fluid
product ion process up-stream from the well test
separator (i.e., within the well, perforation holes
SPE 16 908 O.J. VETTER AND A.W. FARONE
or reservoir), any model effort will not determine
the correct CaC03 precipitations but only the
pres sure/temperature conditions at which the CaC03
saturation has already occurred. Obviously, any such
model effort will fail to predict the correct all
CaC03 precipitations in the system unless the actual
brine composition m:-_:lor to the occurrence of any
precipitation is known in sufficient detail. If we
assume that the brine was originally not saturated in
respect to the CaC03, a CaC03 scale precipitation may
still occur after the brine has passed through the
perforation holes of a given well. In this case, no
scale may form within the reservoir and perforation
holes. On the other hand, if we assume that the
reservoir brine reached CaC03 saturation within the
reservoir, we could then also predict the scale
within the reservoir and/or perforation holes.
In our model, the separator fluids are "exposed" to
increasing instead of decreasing pressures and
temperatures. Assuming the CaC03 saturation
concentration is reached at a certain
pressure/temperature combination below or downstream
of the BPP/TRS combination, one has now determined
the location at which the CaCOj precipitation comes
to an end. This means, CaC03 precipitations started
and occurred upstream of this location. In addition,
this, by itself, is valuable information. The model
can calculate the CaC03 saturation concentrations all
the way upstream to the RS state. In this case, not
the actual CaC03 precipitations but the maximum CaC03
precipitations that can possible occur within the
system will be determined. Both the calculation of
the last downstream location of the actual CaC03
precipitation and the maximum CaC03 precipitations
anywhere within the system provide a set of
in ormation which is sufficient for most field
operations.
We believe that this principal problem can be
overcome if the separator brine contains also traces
of barium and strontium ions. In this case, a.
combined carbonate scale model similar to the
combined sulfate scale model described by Vetter [13]
can be constructed. However, this new model will not
calculate the carbonate scale in a downstream
direction like the sulfate model [13] but in an
upstream direction. The common ion concentration
( C03-) and the ratios of either two of the three
cations (Ba++, sr++ and ca++) can then be used to
determine the correct location where the brine became
first supersaturated in respect to CaC03. This model
approach is subject to one of our future publications
on the subject of scale predictions in oil fields.
K_INET ~JL:t-lCERTA.1_NJ IE UELAT:IID._ T 0 G~_FL AS HI!iG_~D
PRECIPITATIONS
So far, we discussed only thermodynamic factors which
lead to gas flashing, C02 partitioning and associated
CaC03 precipitations. Obviously, these three types
of reactions do not start, proceed and come to an
eq uil ibr ium instantaneously. Each one of these
reactions proceeds at a certain rate, thus bringing
the time factor into the system.
Numerous types of kinetics will theoretically affect
the formations of CaC03 scale in an oil field. The
flashing of COz from the liquid phases is definitely
time-dependent. The partitioning of C02 between the
oil and brine phase is mainly based on rather slow
diffusion reactions [ 48]. The CaC03 precipitation
reactions may also be rather slow [49-52]. Also, the
319
13
effects of other ions in the brine may ef feet the
kinetics of the CaC03 precipitations [32-33].
Finally, the adherence of the precipitating material
to the internal walls of the system and the
pertinent crystal growth reactions are time
dependent. In principle, ignoring these kinetics
will lead to errors in the calculation of the
pertinent CaC03 precipitations if these calculations
are based only on thermodynamic considerations.
Two obvious questions will now surface:
1. How much effort will it take to consider all
kinetics of all pertinent reactions?
2. If these efforts are not reasonable for a given
oil field operation, how large and critical will
the resulting errors become assuming the kinetic
effects are ignored?
In part, our "ignorance" or neglect of the pertinent
kinetics are based on the results of previous
calculations for some wells followed by actual
measurements of the CaC03 scale deposits within
these wells [6]. These comparisons between
calculated and measured CaC03 depositions have
indicated that the actual CaC03 deposits which
actually occurred within some given wellbores are
only a few feet above or downstream of the
calculated locations. Actually, these minor errors
could have been easily caused by the errors of the
field and laboratory measurements aimed at
generating the data which represent the input
information for these calculations.
Assuming the kinetics are ignored, two different
sets of problem may occur:
1. Less CaC03 scale forms in reality than predicted
by considering only the thermodynamics of the
system.
2. The actual location of the CaC03 scale deposit
occurs downstream of the predicted location.
Both problems lead to somewhat pessimistic
predict ions if these predict ions are based on only
thermodynamic considerations. This means, a
somewhat larger CaC03 precipitation is calculated
for a given location than that which actually
occurs. Many oil field operators consider
pessimistic predictions more valuable than
optimistic predictions. In other words, our
predictions using the described model may be called
"worst case" predictions.
CON_g..JJJHQ_NS
1. Of all common oil field scale predictions, the
predict ion and modeling of CaC03 scale offers by
far the most difficulties.
2. CaC03 scale in oil fields can be correctly
predicted only if the pertinent PVT behavior of
all oil, water and gas phases are taken into
account. Considering only the CaC03
precipitation from the aqueous phase and ignoring
the presence of the oil and/or gas phase will
yield wrong information.
3. Modeling of the CaC03 precipitation by using an
equation of state is not possible due to the
chemical complexity of the oil/water/gas system
in a typical oil field.
4. The computation of a CaC03 scaling index or water
stability index is convenient but is not
sufficient to effectively control any scale
formation in the field. Instead, the CaC03 scale
formation should be quantitatively determined as
14 CALCIUM CARBONATE SCALE IN OIL FIELD OPERATIONS
a funct J.on of cumulatJ.vely produced fluJ.ds and
location within the oil field system.
5. Any useful CaC03 scale model must quantitatively
predict the CaC03 scale in an up-stream an~ down-
stream direction.
6. Any of these models must be extremely flexible to
be of any practical use for oil field operations.
It must be flexible enough to easily adapt to the
various site-specific sets of conditions that
exist in an individual oil field.
7. An approach based on state modeling can be used to
correctly predict CaC03 precipitations which will
eventually lead to the formation of scale.
8. Various model approaches for the prediction of
CaC03 precipitations are possible and described
for the oil/brine/gas systems. The chosen model
approach should vary with the availability of
input data for the computations of CaC03 scale
tendencies under a given set of site-specific
field conditions.
9. It is commonly assumed that the reservoir brine
under static conditions is always saturated in
respect to CaC03 if a CaC03 scale tendency is
encountered anywhere in the system. This
assumption can be wrong and should not be made a
priori.
10 .One of the most critical problems for a correct
and precise modeling of the CaC03 precipitations
is caused by a pronounced lack of certain
experimental PVT data.
ll.Any model approach must fit the available
experimental data. Assuming these experimental
data are considered correct, mathematical tricks
and manipulations aimed at "tuning" the basic
parameters in the applied equations should be
avoided.
12.The published data base on experimentally
determined CaC03 solubilities as function of total
pressure, C02 partial pressure, temperature and
brine composition is internally rather
contradictive and is not as extensive as commonly
assumed.
13 .To overcome the lack of data related to some
aspects of the PVT behavior of the oil/brine/gas
system, any model describing the CaC03 scale
formation must be extremely flexible. The model
must be sufficiently flexible to fit the
experimental data which are presently existing or
can easily become available.
14. All correct model approaches rely to a great
extent on the data generated by the proper use of
a well test separator in the field and on the
chemical analyses of all separator fluids in the
laboratory.
lS.Any compositional brine data generated by
a n a 1 y z in g wat e r sam p 1 e s co 11 e c t e d f r om s 1 i p
streams became highly suspected if the fluid in
within the system contains more than on~ phase.
16 .We believe that our principal model approach
fulfills all basic requirements for a suitable
CaC03 model to be used in oil fields.
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SPE 16 908
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 P-V-T Diagram P-V-T Diagram
Oleterlcl EquoUon
Ideal Goa Equollon of State for 1 Uole

00 1.30

0 80
1.38 1.28 1.20 1.12 1.04 0.96 0.88 0.80 0.72 0.84 0.56 0.48 0.4o "
18 22 28 30 34 38 42 48 50 54 58
Reduced Volume
Volum~- litera
Fig. 1-P-V-T diagram Ideal gas equation of state for 1 mole. Fig. 2-P-V-T diagram Dleterlcl equation.

Solubility of Calcium Carbonate Calcium Carbonate Solubility

Parllol Datoba .. - Opn Ulerature Partial Datoboae - 0.5 m NoCI

I
Tamperature - deg C Prel!llure- otm

Fig. 3-Solublllty of calcium carbonate partial data base-open literature. Fig. 4-Calclum carbonate solubility partial data base-0.5 m NaCI.

Calcium Carbonate Scaling Tendency Calcium Carbonate Scaling Tendency

220 220

200 200

Numb.,. 1 Temporaluro (dq F)

110 110
~ 160
121
E 160

140 112 140 Ill

i 120 120
4114
100 100

60 60
17
40
12~
20 20
21 411
121 01
0
200 75 15 95 101 Ill 125
Preuure- p1la Tamperature - deg F

Fig. 5-Calclum carbonate scaling tendency 77 to 123"F temperature. Fig. 6-Calclum carbonate scaling tendency 15 to 705 psla pressure.

Calcium Carbonate Scaling Tendency Calcium Carbonate Scaling Tendency

WOR = 0.2 WOR = 0,2.

300 II

i
I

100
j
411 495 175 655 120 115 110 101 100 n eo 11 10 75

Fig. 7-Calclum carbonate scaling tendency WOR=0.2. Fig. 8-Calclum carbonate scaling tendency WOR=0.2.

322