Prediction of Scale potential in Ethylene Glycol containing solutions

Kristian Sandengen and Terje 0stvold

Norwegian University of Science and Technology (NTNU), 7491 Trondheim, Norway

Abstract
This work presents a method for scale prediction in MEG (Mono Ethylene Glycol / 1,2-ethane-diol)
containing solutions. It is based on an existing PVT scale model using a Pitzer ion interaction model
for the aqueous phase. The model is well suited for scale prediction in saline solutions, where the PVT
part is necessary for calculating CO2 phase equilibria being critical for carbonate scale. MEG
influences the equilibria contained in the model, and its effect has been added empirically. Thus the
accuracy of the model is limited by the amount of available experimental data. The model is
applicable in the range 0-99wt% MEG and includes a wide variety of salts. In addition to the aspects
of scale modelling in MEG+water solutions, this work presents new experimental data on CaSO4
solubility (0-95wt% MEG and 22-80°C). CaSO4 solubility is greatly reduced by MEG to an extent that
“Salting-out” is possible.

Introduction
During transportation of hydrocarbons and water in long subsea flowlines, gas hydrates can form as the
temperature decreases unless an inhibitor is present. Mono Ethylene Glycol (MEG) is commonly used as a
thermodynamic hydrate inhibitor, but it has the adverse effect of lowering the solubility of most salts.
Formation water produced together with hydrocarbons may contain various scale forming ions. Precipitation
of salts can occur if the concentration of the ions exceeds the solubility of the salt. The injection of MEG
may therefore cause more severe precipitation and scale problems than from an aqueous solution. A
common method to prevent corrosion in flowlines is to increase pH by adding caustic to the MEG stream. In
such cases, carbonate salts are particularly troublesome since an increase in pH by one unit, will reduce the
solubility by two orders of magnitude. Thus there will be a trade off between good corrosion protection
(high pH) and scale control (low pH). MEG has a complex influence on the solubility of carbonate salts
since it changes pH, gas solubility and the CO2 dissociation.

The concept of “Salting-out” is well known in crystallization processes1. It denotes the use of an antisolvent
that greatly reduces the solubility of a particular component. In this work, concerning aqueous solutions,
MEG is the antisolvent that affects the solubility of different salts. For oilfield purposes this concept is most
interesting, because it refers to the problem of commingling streams where one contains a high
concentration of MEG, and the other is a saline aqueous solution. This is typically the case on a well-head
where MEG is injected and encounters formation-water. Generally MEG is a less efficient antisolvent than
e.g. Methanol.

Theory
This work aims at predicting salt solubility in a mixed MEG+water solvent. Besides temperature and
pressure, solubility is dependent on other dissolved species than the salt at question and obviously also the
MEG concentration. We rely on a similar semi-empirical approach as used by Kan et.al2. The main
differences are that we use concentrations of mol/Kg solvent instead of mol/Kg ofwater and a different
interpretation of pH. For pH measurements we rely on calibration in the 0.05m KHPh (Potassium Hydrogen
Phtalate) buffer in MEG containing solutions as suggested by Mussini et.al3-5. This topic was briefly
presented in a previous publication6, but will not be discussed in detail in the present work. The term semi-
empirical is often used in thermodynamic textbooks, and simply implies that a model, although theoretically
well founded, includes parameters that have been fitted from experimental data. The basic idea of this work
is that an existing aqueous model shall take care of the large effects of temperature, pressure and salt
content/Ionic strength of the solution. On top of this model an empirical model for MEG dependence is
added, which is merely based on experimental data.
2 K. SANDENGEN AND T. 0STVOLD GEILO 2006

Aqueous model
Before regarding the solubility in a mixed solvent it is valuable to briefly look at solubility prediction in an
aqueous solution, where we use the Multiscaletm PVT scale model, which was developed several years ago.
Details can be found in the work of Kaasa7 and Haarberg8. A throughout discussion of thermodynamics of
electrolyte solutions can be found in chapter 2 and 9 of Prausnitz et.al9, but the concept of a Henrian
standard state is mentioned here for the purpose of further discussion. The solutes are usually expressed in
terms of molality and the activity of specie i, a, is defined as;

mi
ai ^ % _ mi% (1)
mi

y is the activity coefficient and m°=1mol/Kg solvent, which cancels the dimensionality of m. The solute
activity is referred to a hypothetical ideal solution9 of i at system temperature and pressure and at unit
concentration, which is known as a Henrian standard state. The term hypothetical is very often confusing
but although the thermodynamic notation may be confusing the practical use is not very complex. This
choice of reference simply implies that in an ideal solution the activity equals the molality i.e. y=1 at all
compositions. This solution does not exist in real life. For a real solution the activity is found by correcting
the ideal case by an activity coefficient yu as given in Eq. 1. In a real solution y^l as mj^0 i.e the solution
approaches ideality at infinite dilution. Several models that yield yt have been published over the years. The
Pitzer10 ion interaction model is probably the most popular and widely used equation for electrolyte
solutions. This model will not be dealt with in detail here but further information can be found in Pitzer10. It
is important to note that although the equation has a theoretical basis it contains parameters that must be
fitted from experimental data. Hence the final equation is at least partly empirical and the Pitzer model itself
must be regarded as a semi-empirical approach for modelling electrolytes.

Scale potential
In this work saturation ratio (SR) is used to describe scale potential, which is defined as the activity of a salt
divided by its thermodynamic solubility product, K°. For NaCl the expression becomes;

SR aSalt ^Na* aCl

~ K; “ Kip (NaCl) (2)

This definition of super saturation implies that:

SR>1: The salt is supersaturated and may precipitate.
SR=1: At equilibrium
SR<1: The salt is undersaturated. Dissolution occurs if solid is present.

Mixed solvents
The partial Gibbs free energy for specie i is given by the difference in chemical potential between the
current state, and that of the chosen standard state, ui .

— a
u - u _ AG _ RT ln-G
ao _ RT ln at (3)

In an ideal system the activity of specie i will equal the concentration. The transfer from ideal to real case, or
excess Gibbs energy, AGE, can be expressed by an activity coefficient %
3 K. SANDENGEN AND T. 0STVOLD GEILO 2006

AG/ =AG/^-AG,'^ #r(lnar' -ln^)

(4)
= RT In = RT\nyi
V V

In aqueous solutions, the Pitzer model is very well suited for calculation of the activity coefficients but in a
MEG+water mixture the problem is more complex. First one has to consider the standard state. The solute
will obviously still be referred to the hypothetical ideal solution9 at concentration of lmolal at system
temperature and pressure. There exists, however, two good choices for this standard state, since the 1 molal
solution can either be in water or in the water+MEG mixture. The latter choice will in principle lead to a
different standard state for each concentration of MEG. In this work it was decided to use the water solution
without MEG as the standard state. This standard is well known, and the thermodynamic constants, K°, that
are valid in aqueous solutions will consequently remain constant during addition of MEG. The approach is
the same as used by Kan et al2, and is best explained by regarding an example. Eq. 5 gives the transfer of
NaCl from its standard state in water into a real water+MEG solution with an arbitrary salt concentration, m,
and MEG concentration x.

MzO/ ( A w) = AaO/ (m, ) (5)

(°,w) denotes the standard state of hypotetical ideal solution in water as described above. The total Gibbs
free energy of transfer for the reaction is given in Eq. 6 where changes in salt and MEG content have
individual terms.

—tot —ID —E —E
AG = AG + AG Sait + AGmeg (6)
Where the terms are
AG,D =RT\n(mvmcr)

&gL, = RTln(ysvyscr) (7;

AGE
uEG = RTln(y^lf

The process is illustrated graphically in Fig. 1 as the path going first to the right and then
down.

NaCl (°,m>) —ID —E NaC 1 (m.n)

A(j + AG Sail
NaC 1 in lmolal ideal ------------------------ ► NaC l dissolved in
aqueous solution water

AG meg
NaC 1 (°, xmeg) NaCl (m, xmeg)

NaCl in lmolal ideal NaCl dissolved in

mixed solution MEG+water

Fig. 1: Schematic of the transfer of NaCl from its standard state in water and into an arbitrary
NaCl+water+MEG solution.
4 K. SANDENGEN AND T. 0STVOLD GEILO 2006

The first step going from the standard state to the real aqueous solution can be modelled by the Pitzer model
since this process does not involve MEG. The AoMeg term corresponds to some of the solvent (water) being
replaced by MEG, while the salt concentration remains the same. AoMeg can not, however, be equal to the
change in standard state from water to a MEG+water solution as it is dependent on the salt concentration.
The reason for this can be explained by another possible transfer route going first down and then right in Fig.
1.

NaCl (o, w) ^ NaCl (o, )

NaCl { , xmeg )) NaCl {rn, xMeg )

The first step in this process, describes the change in standard state from pure water to the mixed solvent i.e.
from the hypothetical ideal solution9 at unit concentration in water (aqueous standard) to unit concentration
in a mixed solvent (medium standard). The second step, from left to right, describes the process of going
from the medium standard state to the actual solution, keeping the MEG concentration constant. This
process cannot be correctly modelled by the aqueous Pitzer model since the solvent has different properties
e.g the dielectric constant. Thus the two “horizontal” processes in Fig. 1 are unequal, and the two “vertical”
are consequently also unequal.

The second route is regarded as the thermodynamic “correct” method. It does, however, require a model for
activity coefficients in the mixed solvent. Upgrading the Pitzer model implies that a whole new set of
parameters for all MEG+water compositions will have to be constructed. This would have been an elaborate
job even if all necessary experimental data had been available. Mixed MEG+water data is lacking at present,
thus such an upgrade of the Pitzer model is virtually impossible. It was therefore decided to use the first
approach i.e the path going first to the right and then down in Fig. 1. The solubility for NaCl in a mixed
solution is expressed by Eq. 9, where the /±term describes the MEG dependence that will have to be curve
fitted from experimental data.

KSP (NaCl) = mNa+ ^

YNa (9)

The following procedure was used to construct the model;

• At each MEG concentration solubility data, with concentration unit mol/Kg solution, was entered
into the aqueous model, which returned yS values as if the solvent was water.
• /± was calculated from Eq. 9 using K°, the measured solubility m, and the activity coefficients from
above.
• A function for /± was curve fitted

There is also an important issue concerning the concentration unit. Kan et al.2 utilized a concentration
measure of mol/Kg of water in the solvent. The MEG dependence is in any case empirically fitted at
saturation. Hence the choice of mol/Kg water or mol/Kg solvent is merely based on what is practically most
convenient, and what is believed to give the best results when extrapolating outside of the experimental
range. For low concentrations of co-solvent, and for dilution of an aqueous solution by pure MEG, it is
reasonable to work with mol/Kg water as done by Kan et.al2. This typically corresponds to the mixing of a
MEG rich injection stream with formation water. In cases where salt accumulates in the system, however,
the mol/Kg water notation will lead to salt concentrations approaching infinite when the solvent approaches
pure co-solvent. In our opinion mol/Kg solvent is therefore better suited for a general model that will have to
cope with combinations of high salinity and high MEG contents. We want to go up to 99wt% MEG, where
e.g. a solution containing 0.5mol/Kg solvent of NaCl consequently has a concentration of 50mol/Kg of water.
The latter value will obviously lead to modelling difficulties using the Pitzer model.
5 K. SANDENGEN AND T. 0STVOLD GEILO 2006

Validity of model
It is most important to note that it is the product of ys and Y± that is used for solubility calculations, thus
their individual values are actually of secondary importance. Generally activity is expressed as molality
times an activity coefficient. To calculate it as a product of two parameters is merely a convenient choice,
where Y shall take care of “salt effects” and Y gives MEG dependence, as explained in Fig. 1;

.total
aNaCl mNa+
_ + m, - YNaCl
Cl
= mNa+ VNa+YCl
(10)

In Fig. 1 it was mentioned that the two horizontal processes are in principle unequal. This means that the yS
in Eq. 10 cannot alone model the “salt effect” correctly in a water+MEG solution. Experimental solubility
measurements gives the activity at saturation, thus the total activity coefficient will certainly be correct at
this point. If Y± is only a function of MEG content and temperature; Y can not have correct ionic strength
dependence. Thus the model will calculate either a too high or too low SR at conditions away from
saturation. The elaborate works of Manzoni et. al12 and Ceccattini et.al13 gives measurements of the Y in
water+MEG solutions for KCl and NaCl at 25°C. At 80wt% MEG the solubility limit of NaCl is about
1.75m. If the Y data are extrapolated to a NaCl concentration of 2.5m the actual SR should be about 2.5,
while our model gives SR=2.22. Thus in highly saline solutions the model may predict a too low solubility
limit of NaCl. Scale calculations for oilfield purposes will rarely concern such conditions, but the example
shows that ionic strength variations should be investigated. The literature data12,13 can obviously be used to
adjust the model. This is being examined at present but will not be described in further detail.

Because it is the total activity coefficient that is important, it is possible to include an ionic strength effect of
Y± to compensate the error in ys of Eq. 10. This is merely a question of obtaining enough experimental data
but there is actually an obvious limitation. When solubility data is used to determine Y±, it means that we
can not measure the MEG dependence at ionic strengths lower than the solubility of the salt at question.
Thus Y± is only measurable for ionic strengths at saturation and higher. For highly soluble salts this
constitutes a serious limitation, but for low soluble ones like CaSO4 it is no problem. For such cases ionic
strength variations can easily be investigated by performing solubility measurements with various additions
of e.g. NaCl.
The accuracy of the MEG dependence is limited by the amount of available data. Sufficient for data are
available for some salts but lacking for others.

NaCl solubility and Born equation

The thermodynamic “correct” route in Fig. 1 was first down and then to the right. Generally this route is
hindered by lack of data, but for KCl and NaCl measurements (0-80wt% @25°C) actually exist12,13. These
can also be used to show how the Born equation can be applied. The Born equation14,15 attempts to describe
the change in standard state i.e. the first step of going vertically down in Fig. 1. Several authors12,13,14,16
states that it fails to completely describe this energy transfer. Fig. 2 compares solubility17 of NaCl in
water+MEG mixtures with calculations; 1)the model in this work, 2)by use of data from Ceccattini et.al13
according to the “correct” route in Fig. 1 and 3) Using the Born equation for the first vertical step, and
Ceccattini et.al13 for the horizontal process.
6 K. SANDENGEN AND T. 0STVOLD GEILO 2006

♦ Literature
- - - Born
—*—Ceccattini
This work

Fig. 2: Literature data17 at 25°C compared to calculations; l)This work, 2) from data of Ceccattini
et.al13 3) Born equation+13.

It is seen that the Born equation gives a wrong type of function, and is useless for use in a predictive model.
The results from Ceccattini et.al13 gives a systematic too high prediction simply due to their equations for
activity coefficients not being fitted all the way up to saturation.
7 K. SANDENGEN AND T. 0STVOLD GEILO 2006

Experimental
Moisture can be a problem since MEG is hydroscopic. The MEG delivered by Merck(p.a 99.5%) was
analyzed with a Methrom 831 KF Karl-Fischer titration equipment, and found to contain less than 500ppm
(0.05wt%) of water.

CaSO4 solubility
The solid CaSO4 anhydrite starting material delivered by Aldrich(p.a 99%) was stirred in a saline aqueous
solution (0.5m NaCl, 50°C) for one day, filtered, washed with ethanol, dried at 200°C and checked for traces
of Hemi-hydrate by use of X-ray Diffraction (XRD). MEG + water + NaCl(p.a 99.5% delivered by Merck)
solutions were made gravimetrically in 1L flasks. Samples of these were added together with excess solid
CaSO4(1-2g) into 100-250mL bottles and put in a water bath for temperature control (25-85°C). The
solutions were vigorously stirred for 1-14days before being filtered through 0.2pm filters and analysed for
Ca2+ by EDTA(0.01M, Titriplex Ampoule, Merck) titration on a Mettler Toledo DL50 titration system. A
calcium sensitive electrode (Radiometer ISE25Ca) in combination with a Ag/AgCl reference electrode was
used for end point determination. The analysis was checked against Ca2+ standard solutions delivered by
Merck. Solids were collected by vacuum filtration, washed with ethanol, and run through XRD phase
analysis. In selected samples Ca2+ was measured regularly each day to establish the time needed to reach
equilibrium conditions.

If Anhydrite is dissolved under conditions were Gypsum is actually the stable phase, the X-ray pattern
should yield traces of Gypsum. It was also anticipated that precipitation is the rate determining step50, thus
slower than the dissolution process. In such a case Anhydrite will dissolve until its solubility limit is reached.
At the same time Gypsum will precipitate, but so slowly that the calcium and sulphate concentrations remain
on the solubility limit of Anhydrite.
8 K. SANDENGEN AND T. 0STVOLD GEILO 2006

Results and Discussion

Thermodynamic Solubility Product
The basis of all solubility calculations is the thermodynamic solubility product, K°sp. If not already
contained in the aqueous model7, Ksp° was calculated as in the work of Marion17. Solubility data were used
together with activity coefficients from the Pitzer ion interaction model7,10, which leads, circularly, to a
perfect fit of the model with the experimental data. Solubility is highly temperature dependent and the
solubility products were fitted to the function in Eq. 11.

Kl K
ln K sp + K2 + K3 ln T + K4T + (11)
T T

T denotes absolute temperature (K), while K1-K5 are curve fitted constants given in Table 1 for all salts. This
type of equation is “physically correct” and can be deduced from thermodynamics by consulting common
textbooks. One or more of the K parameters can be omitted to produce a simpler function, but the fitting
should at least include parameters Kj and K2, which corresponds to reaction enthalpy and entropy
respectively. For the highly soluble KCl Eq. 11 gave a poor fit, which can be caused by a different
temperature function for the heat capacity. Hence in this case a common fourth order polynomial was used
to fit the data;

KI (KOf) = K + K2T + K3T2 + K4T2 + K5T' (12)

This work does not provide any details about K°sp of each salt nor give any data on the pressure dependence.
Table 1 does, however, give K°sp functions that are compatible with the Pitzer model and also provides a
convenient list of literature references for solubility data.

CaSO4 solubility
After careful investigation of the solubility data in a previous publication6 it was found that the measured
values of anhydrite solubility in aqueous solutions were systematically too high. It was believed to be caused
by Hemi-hydrate in the starting material and we consequently decided to perform the new experimental
measurements given in Table 2. The error was estimated as ±3% but never less than ±0.3mmol/Kg. The
latter is due to the analysis being troublesome at high MEG contents where solubility is very low, thus % is
not a suitable measure. Data for gypsum solubility in water + MEG can be found in a previous publication6.
Using the experimental data, Y±, was calculated from Eq. 13-14 in an equivalent manner as discussed in
detail for NaCl. It should be noted that the water activity Y in Eq. 14 is the activity calculated as if the
solvent was water i.e. adjusting only for the decrease due to salinity. The dependence of water activity upon
MEG addition is included directly in the Y±term. This is an arbitrary choice, which has the positive effect
that the model will not approach infinity as the solvent approaches 100% MEG.

K, W = ^ Y^o2- f (13)
s 2+ y 2'
C (G ) = " '2+ "so2- YOn (0 Mr"
YOnS04 v (14)

The more general approach, however, would be to have the water activity dependent on MEG, and let the
yN± function be equal for anhydrite(A) and gypsum(G). This gave good results up to about 50wt% MEG, but
reproduced experimental data poorly at high MEG contents.
9 K. SANDENGEN AND T. 0STVOLD GEILO 2006

------ Model-Gypsum
-------Model-Anhydrite
A Gypsum
♦ Anhydrite

Wt% MEG

Fig. 3: Gypsum6(25°C) and CaS04 anhydrite (22°C from Table 1) solubility in solutions containing
0.5m NaCl.

Fig. 3 compares the model calculations with experimental data. It should be noted that the stability shift
occurs at about 40wt% MEG(~25°C), which corresponds well with the XRD data in Table 2 that gives
transformation between 30 and 50wt%. At 0 and 30wt% the experiments with anhydrite as start phase are
seen to lie on the gypsum line, which indicates that the start phase has dissolved and gypsum precipitated.
The terms of the sulphates were modelled by the equation;

y Sulphates
= (sj + s4I1L')x
MEG
= +(^2 + S5I )xMEG + 3
(15)

/ denotes ionic strength, x molfraction of MEG in solvent, while st_5 are constants given in Table 3. The 1/3
exponential was included to lessen the effect at very high ionic strengths, such that the function did not
return improbable extrapolations. Because there was no data for SrS04 solubility available this function was
simply set equal to that of CaS04.

Solubility ofpH independent species

Table 3-4 gives the MEG dependence y^" of all the pH independent salts included in the model. It is noted
that NaAc in principle is pH dependent since Ac" is the negative ion of acetic acid, but the solubility is so
high that for any practical use NaAc will only form at high pH. At this point HAc concentration is negligible
compared to Ac". A special case is the NaAc-3H20, which contains crystal water. For this salt the water
activity is not included in the y^" term, thus it must be introduced separately by multiplying with the water
activity to the third power. A good estimate for this activity is simply the molfraction of water in the salt free
solvent.

The /^functions of Table 3-4 can be utilized to calculate solubility in water + MEG solutions using any
aqueous scale model. The procedure is best explained by an example;

or> _ mNa+ mcr yNa* ^'Cl~ VNaCI j

KiNaa) (16)
10 K. SANDENGEN AND T. 0STVOLD GEILO 2006

K° is the common thermodynamic equilibrium constant, ys is the activity coefficient calculated as “if the
solvent was water”, m gives salt concentration in mol Kg solvent, and y':± i s the above mentioned MEG
dependence. The SRwater parameter corresponds to the calculated saturation ratio “as if the solvent was
water”. Hence any scale model can calculate SR in water+MEG solutions by the following procedure:

• Enter salt concentrations as mol Kg solvent into the aqueous scale model
• Let the model calculate SRwater
• Use yN±from Table 3-4 to obtain the actual SR in the water+MEG solution

If it is possible to manipulate the data in the scale model, the best approach will be to calculate a new
equilibrium constant, AMEG, from the y':± values as:

K^NaCl)
= *M£°=VcrUU (17)
tel

The right hand side is exactly the same as for calculation in water, thus any scale model can do calculations
in water+MEG solutions simply by changing the equilibrium constant from K° to KMEG.

Solubility ofpH dependent salts

The modeling of carbonate and bicarbonate salts in water+MEG mixtures is much more complicated than
for the pH independent salts. All four reactions in Eq. 18-21 must be included to describe the solubility of
CaCOa

CO,(g) = Ca(a?) (18)

ccEW+fuo = /r (19)
#CO-=#++CO;- (20)
+CO; =CoCO, (21)
Because the CO2 pressure in the gas phase influences precipitation of carbonate salts, a scale model must
include a PVT part, as described in detail by Kaasa6'7. In this work each of the equilibria in Eq. 18-21 were
given a MEG dependence fitted from experimental data, as described previously6. Their values, however,
are dependent on the definition of pH i.e. how the pH electrode is calibrated in water+MEG solutions. Hence
a discussion of carbonate and bicarbonate solubility must include a throughout description of pH in such
solutions. This is outside the scope of this work, but the solubility of CaCCE in water+MEG is shown in Fig.
4.

0 20 80 100
wt% MEG
11 K. SANDENGEN AND T. 0STVOLD GEILO 2006

Fig. 4: Measured CaCO3 (Calcite) solubility6 in solutions saturated with CO2 at ptot=1atm (0.5m NaCl).
Compared to model (solid lines).

CaCO3 is among those salts that have decreasing solubility with increasing temperature. The MEG
dependence with a minimum in solubility and a steep increase at the high MEG end has been observed for
other carbonates and bicarbonates. It can not be explained by a Ca2+-MEG complex since this behavior was
not observed for CaSO4 (Fig. 3).

Practical use
The simplest case where the model can be applied is for description of “salting out” effects. In oilfield
applications this is interesting in a mixing point where saline waters meet MEG. Water saturated with NaCl
has a concentration of about 6mol/Kg water. When pure MEG is added to this water the concentration per
Kg water remains constant at 6. If the solubility is decreased to a value of less than 6, the solution is
supersaturated and there is a possibility for precipitation of NaCl i.e. “salting out”. Fig. 5 shows relative
change in solubility rather than its actual value. Thus solubility less than 100% means that there is a
possibility for “salting out”, while above 100% there is obviously no chance of precipitation.
200

150

wt% MEG

Fig. 5: Relative solubility (mol/Kg water) at 25°C. x, NaCl; □, KCl; ▲, BaSO4; ♦, CaSO4

All salts have a relative solubility higher than 100% at high MEG contents, which is simply due to a much
larger amount of solvent (water+MEG) being present. Thus the solubility per Kg water becomes very high,
as described earlier. It is seen that MEG has a severe adverse effect on the solubility of CaSO4, while the
topmost curve of NaCl has an insignificant solubility reduction. MEG is in other words an efficient
antisolvent for sulphates but not for NaCl.

To present the models ability to calculate scale potential of carbonate salts under practical conditions regard
an example; Assume a gas well is producing 9million Sm3 of natural gas(1% CO2), which at a certain point
(120bar, 80°C) meets a hydrate inhibitor stream (100m3/day) containing 90wt% MEG and 4200mg/Kg of
NaHCO3. Sodium bicarbonate is present due to pH stabilisation53 of the pipeline. At a certain time the well
starts to produce the formation water given in Table 5. Fig. 6 shows the saturation ratio (SR) versus amount
of produced formation water for CaCO3 and for Hydromagnesite (3MgCOyMg(OH)2-3H2O).
12 K. SANDENGEN AND T. 0STVOLD GEILO 2006

Calcite
Hydromagnesite

0 0.2 0.4 0.6 0.8 1

Formation water [m3/day]

Fig. 6: Example for gas well. SR for □, Hydromagnesite; ♦, CaCOs

It is seen that CaC03 becomes supersaturated with a rate of formation water of about 0.35m3/day and
Hydromagnesite at about 0.6m3/day. The latter does not have a straight line relationship in Fig. 6 due to the
complex structure of the solid phase. It is noted that the model is strictly thermodynamic and does not
provide any information about kinetics i.e. how high SR that can be tolerated before precipitation occurs.

Because the MEG dependence has been added to an already existing aqueous scale model, the model has
good flexibility. It can do exactly the same type of calculations as the aqueous model, with a simple user
interface. MEG is commonly introduced in the aqueous phase, but the model will also accept MEG input in
the gas or oil phase.

Conclusion
Experimental solubility data, together with thermodynamic data taken from literature, have been utilized to
construct empirical functions for the influence of MEG (Mono Ethylene Glycol) on mineral scale formation.
These functions enabled the expansion of an aqueous scale model into a model valid for MEG+water mixed
solutions. The model can handle MEG concentrations of up to 99 weight %.
New experimental measurements at temperatures of (22 to 80)°C showed a severe decrease of CaSCE
solubility with MEG concentration.
13 K. SANDENGEN AND T. 0STVOLD GEILO 2006

Symbols
asHO Aqueous activity of water
A Anhydrite
G Gypsum
NGE Satt Excess Gibbs energy due to change in salt content
(J/mole)
agMeg Excess Gibbs energy due to addition of MEG
(J/mole)
Y Activity coefficient
Z1 Activity coefficient due to MEG
yS Aqueous activity coefficient
K° Thermodynamic equilibrium constant
Jui Chemical potential of comp i (J/mole)
m Molality (mol/Kgsolvent)
T Temperature (Kelvin)
R Gas constant (83.14 bar-cm3/K)
w Water
x mole fraction
o Infinite dilution
° Standard state. lmolal of hypothetical ideal
solution

References
1. Oosterhof, H., Witkamp, G.J., van Rosmalen, G.M. “Some antisolvents for crystallisation of sodium carbonate”, Fluid Phase
Eq. 155, 219-227, (1999)
2. Kan, A.T, Fu,G., Tomson, M.B, ’’Effect of Methanol and Ethylene Glycol on Sulfates and halite Scale Formation” Ind. Eng.
Chem. Res. 42, 2399-2408, (2003)
3. Mussini, P. R., Marcolungo, I., Rondinini, S., Longhi, P.”Acid-base equilibria and acidity scales in ethylene glycol/water
solvent mixtures: recommended reference-value pH-metric standards and ionization constants for o-phthalic acid at normal
and subzero temperatures” Chim. Ind.(Milan), 73, 262-8, (1991)
4. Mussini, P.R., Mussini, T., Rondinini, S. “reference value standards for pH measurements in D2O and aqueous-Organic
solvent mixtures: New accessions and assessments” Pure & Appl. Chem.69(5), 1007-1014, (1997)
5. Mussini, T.,Covington, A. K., Longhi, P., Rondinini, S.” Criteria for Standardization of pH measurements in Organic-
Solvents and water+Organic solvent”, Pure Appl. Chem. 57(6), 865-876, (1985)
6. Kaasa, B., Sandengen, K. and 0stvold, T. ” Thermodynamic Predictions of Scale Potential, pH and Gas Solubility in Glycol
Containing Systems”, SPE 95075, Int. Symposium on Oilfield Scale, Aberdeen, (2005)
7. Kaasa, B., Prediciton ofpH, Mineral precipitations and multiphase equilibria during oil recovery, Dr.Ing thesis, Norwegian
University of Technology and Science-NTNU, (1998)
8. Haarberg, T. Mineral deposition during oil recovery Dr.Ing thesis, Norwegian University of Technology and Science-NTNU /
NTH, (1989)
9. Prausnitz, J.M, Lichtenthaler, R.N, Azevedo, E.G, Molecular Thermodynamics of Fluid-Phase Equilibria, chapter 9, 3rd ed.
Prentice Hall (1999)
10. Pitzer, K. S, Brewer, L. Lewis, G.N., Randall M., Thermodynamics 2.ed., (1961), McGraw-Hill,
11. Mussini, T., Mazza, F.” Medium effects as key electrochemical variables for corrosion and electrochemistry studies in non-
aqueous and mixed solvents”, Electrochimica Acta. 32(6), 855-862, (1987)
12. Manzoni, A., Mussini, P.R., Mussini, T. “Thermodynamics of the amalgam cell {KxHg1-x|KCl(m)|AgCl|Ag} and primary
medium effects upon KCl in {ethylene glycol + water}, {acetonitrile + water}, and {1,4-dioxane + water} solvent mixtures” J.
Chem Thermodynamics 32, 107-122, (2000)
13. Ceccattini, P.D., Mussini, P.R., Mussini, T. “Thermodynamics of NaCl in aqueous ethylene glycol, acetonitrile, and 1,4-
dioxane mixtures from Emf measurements at 25°C” J. Solution Chemistry, 26(12), 1169-1186, (1997)
14. Bates, R.G, Determination ofpH, 2nd ed. (1973) John Wiley & Sons
15. Tester, J.W., Modell, M. Thermodynamics and Its Applications, 3rd ed. (1997) Prentice Hall
16. Zerres, H., Prausnitz, J.M., “Thermodynamics of Phase Equilibria in Aqueous-Organic Systems with Salt”, AIChE Journal,
40(4), 676-91, (1994)
17. Marion, M.G.; “Carbonate mineral solubility at low temperatures in the Na-K-Mg-Ca-H-Cl-SO4-OH-HCO3-CO3-CO2-H2O
system”; Geochim. Cosmochim. Acta, 65(12), 1883-1896, (2001)
14 K. SANDENGEN AND T. 0STVOLD GEILO 2006

18. Konigsberger, E.; Konigsberger, L.; Gamsjager, H.; Low-temperature thermodynamic model for the system Na2CO3-MgCO3-
CaCO3-H2O; Geochim. Cosmochim. Acta, 63(19/20), 3105-3119, (1999)
19. Wood, J R.” Thermodynamics of brine-salt equilibriums. II. The system sodium chloride-potassium chloride-water from 0
to 200°C.” Geochim. Cosmochim. Acta. 40, 1211-20, (1976)
20. Linke, W. F. Solubilities, Inorganic and metal-organic compounds 4th ed. (1965) Am. Chem. Soc. Washington D.C
21. Dean, J.A., Lange, N. A. Lange’s handbook of Chemistry 15th ed. (1999) McGraw-Hill
22. Stephen H., Solubilities of inorganic and organic compounds Vol.1, (1963) Pergamon Press
23. Lide, D. R. CRC Handbook of Chemistry and Physics, 84th ed. (2003)
24. McCoy,H.N. Test, D. “Equilibrium between Alkali-earth Carbonates, Carbon Dioxide and Water” J.Am.Chem.Soc 33, 473-6.
(1911)
25. Hill, A.E., Bacon, L.R. “Ternary systems. VI. Sodium carborate, sodium bicarbonate and water.” J.Am.Chem.Soc, 49, 2487.
(1927)
26. Seiersten, M., Institute For Energy technology, Norway Private communications.
27. Charykova, M. V. “Calculation of Phase equilibria in water-salt systems simulating the natural carbonate brines”,
Geochemistry international, 38(s2), s206-s213, (2000)
28. Wegscheider, R., Mehl, J.“ The system sodium carbonate-sodium bicarbonate-water and the region of existence of trona,
Na2CO3.NaHCO3.2H2O“ Monatshefte fur Chemie, 49, 283-315, (1928)
29. Monnin, C., Schott, J. “Determination of the solubility products of sodium carbonate minerals and an application to trona
deposition in Lake Magadi (Kenya).” Geochim. Cosmochim. Acta , 48, 571-581, (1984)
30. Waldeck, W. F., Lynn, G.; Hill, A. E. “Aqueous solubility of salts at high temperatures. II. The ternary system Na2CO3-
NaHCO3-H2O from 100° to 200°C” J.Am.Chem.Soc, 56, 43-7 (1934)
31. Pietsch, E., Gmelins Handbook der anorganischen Chemie, (1938), Vol 55
32. Trypuc, M., Kielkowska, U., Stefanovic, D. “Solubility Investigations in the KHCO3 + NH4HCO3 + H2O System” J. Chem.
Eng. Data. 46, 800-804, (2001)
33. Moore, R.C., Mesmer, R. E., Simonson, J. M. “Solubility of Potassium Carbonate in Water between 384 and 529 K Measured
Using the Synthetic Method.” J. Chem. Eng. Data, 42, 1078-1081, (1997)
34. Apelblat, A., Manzurola, M., ” Solubilities and vapour pressures of saturated aqueous solutions of sodium tetraborate, sodium
carbonate, and magnesium sulfate and freezing-temperature lowerings of sodium tetraborate and sodium carbonate
solutions. ” J. Chem. Thermodynamics, 35, 221-238, (2003)
35. Wells, R. C., McAdam Jr, D. J.“ Phase Relations of the System Sodium Carbonate and Water.“ J. Am. Chem. Soc. 29, 721­
727, (1907)
36. Busenberg, E., Plummer, L.N., Parker, V.N “The solubility of Strontianite in CO2-H2O solutions between 2 and 91 °C, the
association constants of SrHCO3+(aq) and SrCO3°(aq) between 5 and 80°C, and an evaluation of the thermodynamic
properties of Sr2+(aq) and SrCO3 at 25°C and 1 atm total pressure” Geochimica et. Cosmo. Acta 48, 2021-2035, (1984)
37. Busenberg, E., Plummer, L.N. “The solubility of BaCO3 (witherite) in CO2-H2O solutions between 0 and 90°C, evaluation of
the association constants of BaHCO3+(aq) and BaCO3°(aq) between 5 and 80°C and a preliminary evaluation of the
thermodynamic properties of Ba2+” Geochimica et. Cosmo. Acta 50, 2225-2233, (1986)
38. Muller, N, “The prediction of mineral solubilities in natural waters: A Chemical equilibrium model for the Na-Ca-Cl-SO4-
H2O system, to high temperature and concentration”” Geochimica et. Cosmo. Acta 52, 821-837, (1988)
39. Posnjak, E. “The system, CaSO4-H2O”, Amer. J. Sci. 35A, 247-272, (1938)
40. Innorta, G., Rabbi, E., Tomadin, L. ”The gypsum-anhydrite equilibrium by solubility measurements”, Geochimica et. Cosmo.
Acta 44, 1931-1936, (1980)
41. Partridge, P., White, A.H., “The solubility of calcium sulfate from 0 to 200°C” . J. Am. Chem. Soc. 51, 360-370, (1929)
42. Blount C.W., Dickson, F.W. “The solubility of anhydrite in NaCl-H2O from 100 to 450°C and 1 to 1000bars” Geochimica et.
Cosmo. Acta 33, 227-245, (1969)
43. Blount C.W., Dickson, F.W.’Gypsum-Anhydrite equilibria in systems CaSO4-H2O and CaSO4-NaCl-H2O” Amer.
Mineralogist, 58, 323-331, (1973)
44. Booth, H.S, Bidwell, R.M, “Solubilities of salts in water at high temperatures”, J. Am. Chem. Soc. 72, 2567-2575, (1950)
45. Bock, E. “On the solubility of anhydrous calcium sulphate and gypsum in concentrated solutions of sodium chloride at 25, 30,
40 and 50°C” Canadian J. Chem. 39, 1746-1751, (1973)
46. Millero, F.J., Milne, P.J., Thurmond, V.L., Geochim. Cosmochim. Acta, 48, 1141-1143, (1984)
47. Lambert, I. Clever, H.L Solubility Data Series vol.52, 57-109, (1992), Pergamon Press
48. Yanat’eva, O.K. “The metastable equilibrium in the system CaCO3-MgCO3-H2O”, translation of Izvestiya Akademii Nauk
SSSR 1, 180-182, (1960)
49. Kraus, K.A., Raridon, R.J. and Baldwin,W.H. “Properties of organic-water mixtures.” J.Am.Chem.Soc., 86(13), (1964)
50. Mullin, J. W. Crystallization 4th ed., (2001), Butterworth Heinemann,
51. Masoudi, R., Tohidi, B., Anderson, R., Burgass, R.W., Yang, J.’Experimental measurements and thermodynamic modeling
of chlathrate hydrate equilibria and salt solubility in aqueous ethylene glycol and electrolyte solutions” Fluid Phase
Equilibria, 219, 157-163, (2003)
52. Rasmussen, P. Chiavone-Fihlo, C.O. “Solubilities of salts in mixed solvents.”, J.of Chemical and engineering data 38(3) 367­
369, (1993)
53. Olsen, S., Lunde, O., Dugstad, A., “Stabilizing pH in Troll pipelines solves glycol-regeneration problems”, Oil & Gas
Journal, 97(26), 59-62, (1999)
15 K. SANDENGEN AND T. 0STVOLD GEILO 2006

Table 1: Parameters for calculation of Kp°

Salt K1 K2 K3 K4 K5 T[°C]a Ref.c
KClb 494.26b -5.8585b 2.4552E-2b -4.2553E-5b 2.6066E-8b 0-300 19-21
NaAc-3H2O 1.5994 117.49 -26.359 0.12141 1.1220E-2 0-58 20-22
NaAc -9653.9 185.40 -24.242 -2.5292E-2 0 0-120 20-22
NaHCO3 -3.6367 -77.250 14.575 -2.2468E-2 0 -3-95 20,24-30
KHCO3 2.2403 69.658 -17.016 9.2964E-2 0 0-70 17,20-23,31-32
K2CO3-1.5H2O 6.6460 191.93 -44.847 0.23565 0 0-250 20-23, 33
K2CO3 -39.805 -1160.4 244.78 -0.68681 0 0-250 20-23, 33
Na2CO3-10H2O -8006.9 25.093 0 0 0 -2-40 1,20,26,34,35
Na2CO3'H2O 3016.7 -274.98 55.483 -0.16629 -0.082013 30-100 1,20,30,34-35
NazCO, -17483 462.07 -70.047 -1.5459E-3 -4.2439E-3 100-300 1,30
BaCO3 -46077 1399.1 -236.68 0.28289 0 0-90 37, U
SrCO3 -16669 362.71 -57.996 8.3170E-3 0 0-90 36,46, U
CaSO4 -9536.5 239.87 -38.258 0 0 20-250 38-45, TW
Mg(OH)2 -10621 240.71 -40.444 0 0 18-300 20,22,47,U
MgCO3d 3555.62 -85.022 0 0 0 0-80 17,18,48, U
aTemperature range of experimental data
bParameters for Fourth order polynomial given in Eq. 12
"Literature references. TW denotes This Work, U denotes data that have not yet been published.
dSolid phase included in model is Hydromagnesite with formula 3MgCO3<Mg(OH)2^3H2O

Table 2: Experimental results with CaSO4 (A) as starting material. A indicates Anhydrate and G Gypsum. Concentration
given per Kg solvert(water+MEG)
T Time" MEG NaCl [Ca2+]
[°C] days wt% mol/Kg mmol/Kg XRD
22 7 0 0.5 36.40 G
22 3 0 0.5 36.50
22 1 0 0.5 41.26 A+G
22 7 30 0.5 19.16 A+G
22 11 50 0.5 12.10 A
22 11 70 0.5 6.86 A
22 11 90 0.5 3.67 A
22 8 95 0.5 3.01
21 2 0 0 24.09
50 2 0 0.5 34.30
50 3 30 0.5 15.64
50 3 50 0.5 8.70
50 3 70 0.5 4.60
50 11 90 0.5 2.51
50 5 95 0.5 2.08
50 7 95 0.5 1.89
50 4 100 0.5 1.62
50 2 0 0 14.57 A
50 4 50 0 1.72 A
50 4 90 0 0.35 A
50 2 0 0.1 21.50
50 2 50 0.1 4.23
50 4 90 0.1 1.15
80 2 0 0.5 24.46 A
80p 3 0 0.5 25.21
80 2 30 0.5 11.53
80p 2 50 0.5 6.46 A
80p 2 50 0.5 6.48
80p 2 90 0.5 1.52 A
80 2 95 0.5 1.46
“Elapsed time before final Ca2+ analysis.
^precipitation experiments

Table 3: Parameters for calculation pf lnyVJ for sulphates in Eq. 15.

Salt s1 s2 s3 s4 s5 Tempa Ref.b
CaSO4-2%O 7.9421 -8.3573 0.99658 -2.7225 1.8547 22-65 6
CaSO4 7.9753 -7.2016 2.1404 -1.9139 1.7072 22-85 TW,6
SrSO4 7.9753 -7.2016 2.1404 -1.9139 1.7072 -
BaSO4 6.8799 -10.064 4.3410 0 0 25 2
“Temperature range of experimental data [°C]
bReferences for solubility data. TW denotes This Work.
16 K. SANDENGEN AND T. 0STVOLD GEILO 2006

Table 4: Curve fit equations for !nyV± of chlorides and NaAc

Specie Equation3 Tempb Ref.c
NaCl 2.110w 10-90 26,49,51
KCl 1.589w + (-0.114 + 0.00158T)w2 0-80 20,26,49,52
NaAc 2.113x 0-90 26
NaAc-3H2Od 4.467x - 3.806x2 0-40 26
aw and x denotes weight and mole fraction of MEG in solvent respectively. T denotes absolute temperature (K). bTemperature
range of experimental data[°C]. cReferences. dwater activity not included.

Table 5: Sample of typical formation water

Ion mg/l Ion mg/l
Na+ 58000 Cl- 91900
K+ 730 Br- 0
Mg"+ 520 SO/' 0
Ca2+ 300
Ba2+ 6
Sr2+ 0
Fe2+ 0
Organic acid 0 mg/l
Total alkalinity 410 mg/l
Pressure 1 bar
Temperature 15 °C
pH NA