New Insights into the Removal of Calcium

Sulfate Scale
Authors: Dr. Mohammed H. Al-Khaldi, Ahmad M. Al-Juhani, Dr. Saleh H. Al-Mutairi and Dr. M. Nihat Gurmen

ABSTRACT
Calcium sulfate is one of the major scales that cause many
significant and serious operating problems in producing oil
and gas wells and in water injectors. Impermeable hard scale
deposits of calcium sulfate can severely impair the formation
permeability or lead to downhole equipment failure. Typically,
preventive treatments, such as the use of scale inhibitors, are
the most economical methods for calcium sulfate mitigation;
however, application of a cost-effective treatment is needed in
case of emergency, when calcium sulfate precipitation occurs.
A comprehensive lab investigation was conducted to assess
the effectiveness of several remedial methods for calcium
sulfate removal. This article shows the amount of calcium
sulfate dissolved after its exposure to different reactive fluids
at 25 C and 50 C. In addition, it discusses the effect of
different factors on the efficiency of each remedial treatment.
These factors include pH, temperature, reactive fluid
concentration and presence of magnesium/iron ions.
Based on obtained results, several new findings were
identified. The presence of gypsum (CaSO4.2H2O) has a
negative impact on the performance of mud acid treatments.
After the initial dissolution of gypsum in live mud acid,
dissolved calcium will precipitate as both calcium fluoride and
calcium sulfate in spent hydrochloric (HCl)/hydrofluoric (HF)
acid solutions. Gypsum has a higher solubility limit in live
HCl acid compared to its spent solutions, which results in the
reprecipitation of calcium sulfate in spent HCl. This solubility
of gypsum in acidic solutions could result in severe formation
damage. Live acids can initially dissolve any precipitated
calcium sulfate solids in wellbore areas, but the calcium sulfate
will reprecipitate in the formation rocks as the acid is spent.
Gypsum has a higher solubility limit in ethylene diamine
tetra-acetic acid (EDTA) solutions, compared to acidic
solutions. No reprecipitation of calcium sulfate occurred in
these solutions due to the fact that calcium ions exist as
complex ions and are not free to interact with other ions. The
dissolving power of EDTA was found to be a function of the
solution pH value. The dissolving power of EDTA for gypsum
was higher at high pH values. The presence of both magnesium and iron (III) ions had a negative effect on gypsum
dissolution in the EDTA fluid. Compared to magnesium, iron
(III) ions resulted in a significant decrease in gypsum solubility
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in EDTA. Dissolved magnesium ions in EDTA solutions can

reprecipitate as magnesium sulfate when gypsum is dissolved.
This reprecipitation is greater in lower pH EDTA solutions.

INTRODUCTION
Calcium sulfate has been cited in the literature as one of the
major scales that cause many significant and serious operating
problems in producing oil and gas wells and in water injectors.
Impermeable hard scale deposits of calcium sulfate can severely
impair the formation permeability, thereby decreasing the well
injectivity or productivity1-4. In addition, calcium sulfate can
also negatively impact the well economics when it precipitates
in downhole equipment, such as electrical submersible pumps
(ESPs). This precipitation leads to pump failure due to overloading that causes serious damage to the pump components,
and as a result, costly workovers are required.
Calcium sulfate has two main stable crystal forms.
Gypsum, CaSO4.2H2O, is formed at low temperatures (i.e.,
T < 98 C), while anhydrite, CaSO4, is the predominant form
produced at high temperatures5. Gypsum, the most common
oil field calcium sulfate scale, is very difficult to remove. This
is mainly because it has relatively low solubility limits in
water, almost 2.36 kg in 1 m3 of water at 25 C. At higher
temperatures, calcium sulfate becomes more insoluble in water
as low as 1.69 kg in 1 m3 of water at 90 C. Besides temperature, other factors affect gypsum solubility, such as the
solutions pH value and pressure. In general, calcium sulfate is
more soluble at low pH values and high pressures4, 6.
Many publications have reported on the precipitation of
calcium sulfate during different oil field operations, such as
water injection, acid stimulation and commingled hydrocarbon/water production. The main cause of calcium sulfate
scaling during these operations is the chemically incompatible
mixing of two fluids. For example, mixing injected seawater,
which is high in sulfate ions, with formation water, which
is high in calcium ions, will result in calcium sulfate precipitation once its solubility limit is exceeded. Similarly,
calcium sulfate precipitation can result from the incompatible
mixing of spent acid solutions with overflush fluids. It has
been reported7 that calcium sulfate precipitation occurred in
and around the ESPs of the Farida/Zelda reservoir wells
mainly after acid stimulation treatments. This was found to be

due to the incompatible mixing of spent hydrochloric

(HCl)/hydrofluoric (HF) acid and seawater overflush fluid.
Dissolved calcium ions united with sulfate ions from the
seawater to form calcium sulfate scale. Similarly, the conduct
of a chemical simulation8 revealed that detrimental acidizing
treatments in limestone/dolomite Dalan and Kangan
formations could result in calcium sulfate precipitation.
Simulation results indicated that in addition to precipitation
due to incompatible mixing, calcium sulfate may precipitate in
spent acid solutions due to the rise in the solutions pH value.
Whereas, calcium sulfate initially is soluble in live acid
solutions, it reprecipitates as the solutions pH value
increases.
Typically, preventive treatments, such as the use of scale
inhibitors, are the most economical methods for calcium
sulfate mitigation2, 9; however, application of a cost-effective
treatment is needed when calcium sulfate precipitation occurs.
Chemical dissolvers offer alternatives to mechanical methods
for removing near wellbore calcium sulfate scaling. A
thorough literature survey reveals that chemical means rely on
the use of amino carboxylic acid salts. Ethylene diamine tetraacetic acid (EDTA) is one of the most effective dissolvers for
calcium sulfate, Fig. 110. In many reservoirs, EDTA has been
used to remove calcium sulfate formation damage11, 12. Severe
calcium sulfate damage experienced by a high temperature gas
condensate well in the Kalinovac field was removed12 using an
8 wt% tetrasodium EDTA treatment.

Fig. 1. Chemical and 3D structure of EDTA molecule10.

As can been seen, a number of studies have been performed

to investigate the solubility of calcium sulfate in HCl acid and
EDTA solutions; however, the studies have been conducted
within limited parameters. Therefore, the objectives of this
study are to: (1) Explore the solubility trend of calcium sulfate
in HCl acid and HCl/HF acids, (2) Investigate the dissolution
of calcium sulfate in EDTA solutions, and (3) Examine the
effects of pH, temperature and the presence of both iron and
magnesium on the solubility of calcium sulfate in HCl acid,
HCl/HF acid and EDTA.

THEORY
Equation 1 shows how calcium sulfate, gypsum, and scaling
can be expressed:

(1)
The potential for gypsum scaling measured thermodynamically
by the saturation index (SI). A positive SI value indicates that the
mixture solution is supersaturated and there is a potential for
scaling, while a zero or negative SI value shows that the mixture is
undersaturated and there is no scale tendency. The SI for gypsum
is the logarithm of the ion activity product of its two ion
components, calcium ions and sulfate ions, divided by its
solubility product, Eqn. 29:
(2)
where g Ca2+ is the activity coefficient of the calcium ion,
g SO42- is the activity coefficient of the sulfate ion, Ci is the
concentration of the specie i (mole/L), and Ksp is the solubility
product of calcium sulfate salt, which is a function of
temperature and pressure. The ion activity coefficient in
electrolyte solutions can be calculated using solution ionic
strength and ion interaction coefficients. For example, the
calcium activity coefficient can be calculated using Eqns. 3
and 413:
(3)
(4)
where Im is the ionic strength, z is the valence (or oxidation)
number of the calcium ion, B is the ion interaction coefficient
and mj is the molality of interacting ion j (mol/kg). In the case
of the calcium ion, the interacting ion in the HCl acid solution
will be the chloride ion. In calculating a specie activity
coefficient, the ion interaction coefficients are zero for ions
with the same charge or unchanged ions. Many studies have
reported ion interaction coefficients for various ion pairs14.
HCl acid and HCl/HF acids dissociate to produce H+ ions.
In these acidic solutions, calcium sulfate is dissolved due to H+
attack on sulfate crystal sites, Eqns. 5 to 7:
(5)
(6)
(7)
The interaction of dissolved calcium ions with fluoride ions
can result in the precipitation of calcium fluoride, Eqn. 8:
(8)
Calcium fluoride precipitation is dependent on the
solutions pH value as will be discussed later. The EDTA is
a weak acid that dissociates stepwise as follows, Eqns. 9
to 12:
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(9)
(10)
(11)

(14)
The calcium sodium EDTA complex is stable because of the
chelation bonds, Fig. 317. Similar to calcium, EDTA is also an
excellent chelating agent for both magnesium and iron, Eqns.
15 and 16:

(12)
(15)
The distribution of the acid species is dependent on both
the pH value and the dissociation constants, as shown in Fig.
215, 16. The dissociation constants of EDTA are: Ka1= 1.02
E-2, Ka2 = 2.14 E-3, Ka3 = 6.92 E-7, Ka4 = 5.5 E-1115, 16. The
first dissociation constant of EDTA, Ka1, is expressed in Eqn.
13 as:
(13)
The mechanism of calcium sulfate dissolution in the EDTA
solution is different from that in acidic solutions. Calcium
sulfate is mainly dissolved due to calcium chelation at pH > 4.
Equation 14 shows the reaction of tetrasodium EDTA with
calcium sulfate:

(16)
The chelating agent affinity for an ion is defined by the
formation constant, KF, Eqns. 17 and 18:
(17)
(18)
The larger the formation constant is, the stronger is the
chelating agent-ion complex. Table 118 lists the formation
constants of EDTA with calcium, magnesium and iron (III)
cations. The presence of magnesium and iron will affect the
calcium sulfate dissolution in the EDTA solutions as will be
discussed later.

Calcium, Ca2+

Formation Constant,
Log KF18 at 25 C
10.70

Magnesium, Mg2+

8.69

Ion

Iron (III), Fe

3+

25.7

Table 1. The formation constants of EDTA with different ions

EXPERIMENTAL STUDIES
Fig. 2. Distribution of EDTA species as a function of the solutions pH value at
25 C15, 16.

Materials

Calcium sulfate di-hydrate (CaSO4.2H2O) was obtained from

the Sigma-Aldrich company with a purity of more than 98%.
Magnesium chloride hexa-hydrate and iron chloride hexahydrate were acquired from BDH laboratory supplies and
Fisher Scientific companies with a purity of 99% and 97%,
respectively. Ammonium bi-fluoride salts were supplied by a
local service company and were used as is. Solutions of mud
acid (HCl/HF) at 9/1 wt%/wt% were prepared using
ammonium bi-fluoride and concentrated HCl acid solutions
at 37.5 wt%, Eqn. 19:
(19)

Fig. 3. Octahedral geometry of 1:1 metal EDTA ion complex17.

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The tetrasodium EDTA salt was obtained from the DOW

Chemical company. The average pH value of tetrasodium
EDTA salt is 14. HCl acid at 20 wt% was used to adjust the
pH value of the EDTA solution to the desired value. All

reactive solutions of HCl acid, HCl/HF acid mixture and

EDTA were prepared using distilled water with a resistivity
greater than 18 W .cm at room temperature.
Experimental Procedure

The solubility of gypsum in different reactive fluids was

investigated at 25 C and 50 C at atmospheric pressure.
Three sets of static solubility experiments were conducted
using 15 wt% HCl acid, 9 wt% HCl/HF acid, and 1 wt% and
8 wt% EDTA solutions. These experiments were carried out
using 10 ml of reactive fluid mixed with 1 g of calcium sulfate
di-hydrate and equilibrated at the desired temperature using a
hot water bath. Solutions of HCl acid and HCl/HF acids with
gypsum solids were incubated for four hours. This soaking
time is enough to reach an equilibrium state of gypsum
dissolution in acidic solutions19. The mixtures of EDTA and
gypsum were soaked for nearly eight hours to reach the
reaction equilibrium state12.
Several test tubes were used to conduct each set of reactive
fluid/gypsum solubility experiments. At the end of the desired
soaking time, unreacted solids in each test tube containing a
reactive fluid/gypsum mixture were filtered using 1.2 m filter
paper. Then the pH value of certain filtered reactive fluid
samples of HCl acid and mud acid was adjusted using a few
drops of 3N NaOH to reach the desired value. This was done
to investigate the effect of the solutions pH value on the
gypsum solubility. The pH value of the EDTA solutions was
adjusted using 20 wt% HCl acid to the desired value before
they was mixed with gypsum. Each series of solubility
experiments was conducted in duplicate at 25 C and 50 C.
In another two series of experiments, magnesium chloride
and iron chloride were added to the solutions of HCl acid and
EDTA at 1, 2 and 3 wt% before gypsum was added to the
final solution. These sets of experiments were performed to
investigate the effect of magnesium and iron (III) on gypsum
solubility in different reactive solutions.
The calcium, magnesium and iron concentrations in the
collected reactive fluid samples were measured using
inductivity coupled plasma. To measure the pH value of the
collected samples, an Orion model 250A meter and ColeParmer Ag/AgCl single junction pH electrode were used.
Fluoride ion concentration was measured using a fluoride
selective pH electrode. Collected solid samples were analyzed
using X-ray powder diffraction (XRD).

mixture at 9/1 wt%/wt%, respectively, as a function of the

solutions pH value at 25 C. Initially, calcium and sulfate
levels in the live mud acid solution reached nearly 3,300 mg/L
and 20,000 mg/L, respectively, due to gypsum dissolution
after a soaking time of four hours at a liquid/solid ratio of

Table 2. Gypsum static solubility experiments conducted using different reactive

fluids at atmospheric pressure and a liquid/solid ratio of 10 ml/1 g

RESULTS AND DISCUSSIONS

The solubility of gypsum (CaSO4.2H2O) in HCl/HF acids, HCl
acid and EDTA solutions was studied at atmospheric pressure.
The effects of the solution pH value, the temperature and the
presence of both magnesium and iron (III) on gypsum solubility
were also investigated. Table 2 gives a list of the static solubility
experiments conducted using different reactive fluids.
Figure 4 shows the solubility of gypsum in the HCl/HF acid

Fig. 4. Gypsum solubility in 9 wt% HCl/1 wt% HF acid as a function of the

solutions pH value at 25 C and atmospheric pressure.

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Fig. 5. XRD analysis of solid material precipitated in spent mud acid/gypsum

mixture solutions. The solid precipitate was a mixture of both calcium fluoride
and gypsum.

Fig. 6. Distribution of HF acid species as a function of the solutions pH value at

25 C15, 16.

Fig. 7. Distribution of H2SO4 species as a function of the solutions pH value at

25 C15, 16.

10 ml/1 g, Eqn. 7. Consequently, when the pH value of the

mud acid solutions containing these levels of calcium and
sulfate was raised to a higher value, white solid particles
precipitated, and the concentration of calcium, sulfate and
fluoride ions sharply decreased. For example, the level of
calcium ions decreased from 3,300 to 1,000; sulfate ions from
20,000 to 6,450 and fluoride ions from 6,450; mg/L to 3,000
mg/L when the solutions pH value was raised from zero to
nearly 1.5 using a few drops of 3N NaOH. This decrease
continued until the concentration of dissolved calcium ions
reached almost zero at a pH value of nearly 3.5. This behavior
indicated a precipitation process involving calcium, fluoride
and sulfate ions. XRD analysis of the collected white solid
material precipitated in the spent mud solutions indicated that
it contained both calcium fluoride and calcium sulfate, Fig. 5.
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The reprecipitation of calcium ions as both calcium fluoride

and calcium sulfate when the pH of the mud acid solution
increased was due to the presence of free fluoride and sulfate
ions at relatively high pH values.
Figures 615, 16 and 715, 16 depict the distribution of
hydrofluoric and sulfuric acids, respectively. At low pH
values, both fluoride and sulfate ions are bound by hydrogen
ions, so they are not free to bind with calcium. Therefore,
when gypsum initially dissolves in a live mud acid solution,
the dissolved calcium cannot combine with either fluoride or
sulfate ions because they are not free. Subsequently, when
hydrogen ions are consumed due to acid spending, both
fluoride and sulfate ions become free and combine with
calcium ions to precipitate as calcium fluoride and calcium
sulfate, Eqns. 1 and 8. This finding clearly shows the potential
detrimental effects of calcium sulfate scale in association with
mud acid treatments. Similarly, the reprecipitation of calcium
sulfate in spent acid solutions was observed during the HCl
acid/gypsum solubility experiments.
It was reported19 that gypsum solubility in HCl acid
solutions increased as the acid concentration increased up to
nearly 15 wt% and then decreased with further acid
concentration increases. The report did not investigate the pH
value effect on gypsum solubility in HCl acid. Figure 8 shows
the effect of the solutions pH value on gypsum solubility in
15 wt% HCl acid at 25 C. Compared to live HCl acid
solutions, gypsum had a lower solubility limit in spent HCl
acid. Calcium and sulfate levels in the live 15 wt% HCl acid
solution initially reached nearly 4,400 ppm and 14,000 ppm,
respectively, due to gypsum dissolution after a soaking time of
four hours at a liquid/solid ratio of 10 ml/1 g. Consequently,
raising the HCl acid solutions pH value from zero to nearly
1 resulted in the reprecipitation of calcium sulfate as indicated
by a decrease in the concentration level of both calcium and
sulfate ions to nearly 1,800 ppm and 4,000 ppm, respectively.
XRD analysis of this precipitation indicated it was calcium
sulfate, Fig. 9. A similar gypsum solubility trend in concert
with the solutions pH value was also observed at high
temperatures.
Figure 10 shows the effect of the solutions pH value on
gypsum solubility in 15 wt% HCl acid at 50 C. From this
figure, three main conclusions can be drawn. First, from both

Fig. 8. Gypsum solubility in 15 wt% HCl acid as a function of the solutions pH

value at 25 C and atmospheric pressure.

Fig. 9. XRD analysis of solid material reprecipitated in filtered HCl acid solutions
after reaction with gypsum. Reprecipitation occurred when the pH value was raised.

Fig. 10. Gypsum solubility in 15 wt% HCl acid as a function of the solutions pH
value at 50 C and atmospheric pressure.

Figs. 8 and 10, it is obvious that the increase in reaction

temperature from 25 C to 50 C resulted in more gypsum
dissolution in the live HCl acid solution, such that the
dissolved calcium concentration increased from 4,400 to
nearly 8,000, respectively. Second, the effect of temperature
on gypsum dissolution in the HCl acid diminished when the
pH value of the acid solution exceeded 1. Finally, the increase
in the solutions pH value resulted in the reprecipitation of
calcium sulfate, also at high temperatures. Calcium sulfate
reprecipitation also occurred in live HCl acid solutions when
they reached room temperature. The amount of the
reprecipitation was accounted for in the calculation of the
calcium sulfate solubility in the HCl acid solutions at 50 C.
Due to the fact that magnesium sulfate has a higher
solubility than that of calcium sulfate, the presence of
magnesium in reactive solutions should increase the gypsum
solubility in these solutions due to the so-called common ion
effect20. Figures 11 and 12 show that the presence of both
magnesium and iron (III) had no effect on the gypsum
solubility in the live HCl acid at 25 C and 50 C, up to
concentration levels of 4,000 ppm and 6,000 ppm,
respectively. These solutions also experienced a reprecipitation
of calcium sulfate when their temperature values reached
room temperature, Figs. 13 and 14.
It was reported21 that the solubility product of gypsum in
water is nearly constant at different temperatures up to 60 C
and at 25 C, it is 2.4E-5 M2. Figure 15 shows the solubility
product of gypsum in HCl acid, at different pH values, calculated
using Eqns. 2 to 4. Compared to water, it is obvious that the
solubility product of gypsum in live HCl acid is higher at
almost 3.79E-5; however, the solubility of gypsum in spent
HCl acid (pH > 2) approaches its solubility limit in water. In
contrast to the solubility behavior of gypsum in water, its
solubility limit in live HCl acid solutions increased with the
increase in temperature. For example, the gypsum solubility
product in HCl acid (pH = 0) increased from 3.79E-5 to
9.9E-5 M2 when the solution temperature was increased from
25 C to 50 C. This solubility trend of gypsum was not
observed in the EDTA solutions.

Fig. 11. Gypsum solubility in live 15 wt% HCl acid as a function of dissolved
magnesium ion concentration at atmospheric pressure.

Fig. 12. Gypsum solubility in live 15 wt% HCl acid as a function of dissolved iron
(III) ion concentration at atmospheric pressure.

Fig. 13. Calcium sulfate reprecipitation in live 15 wt% HCl acid containing (a)
iron, and (b) magnesium ions, at different concentrations as a result of the
decrease in the solutions temperature value.

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Fig. 14. XRD analysis of solid material reprecipitated due to temperature change
in live HCl/gypsum mixture solutions containing (A) 1 wt% MgCl2.6H2O and
(B) 1 wt% FeCl3.6H2O.

Fig. 16. Gypsum solubility in 8 wt% EDTA as a function of the solutions pH

value at atmospheric pressure.

Fig. 15. Solubility product of gypsum in 15 wt% HCl acid as a function of the pH
value.

Figure 16 shows the solubility of gypsum in an 8 wt%

EDTA solution as a function of the pH value. Both dissolved
calcium ions and sulfate ions, due to gypsum dissolution,
increased as the solution pH increased. This is mainly due to
the fact that at higher pH values, the EDTA molecule exists as
a dissociated form, which means it has more chelation sites
(carboxylic groups), Fig. 2. From measurements of the calcium
and sulfate concentrations, it is clear that the temperature
change from 25 C to 50 C did not affect the gypsum solubility in the EDTA solutions with a soaking time of 8 hours. In
addition, gypsum reprecipitation as a result of temperature
change did not occur in these solutions. Along with the
advantage of the EDTA solutions over HCl acid, gypsum has
higher solubility in these solutions compared to HCl acid; the
dissolved calcium in the EDTA solutions and the spent HCl
acid is nearly 8,000 ppm and 1,900 ppm, respectively.
The presence of both magnesium and iron affected the
gypsum solubility in the EDTA solutions, Figs. 17 and 18.
Compared to magnesium, iron (III) had a significant effect on
calcium sulfate dissolution in the EDTA solutions. This is mainly
due to the fact that EDTA has a higher affinity for iron than for
calcium, while it has a comparable affinity for both calcium
and magnesium, Table 2. In other words, in the presence of
iron (III), there will be fewer chelation sites for calcium
compared to those available in the presence of magnesium.
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Fig. 17. Gypsum solubility in 8 wt% EDTA as a function of dissolved magnesium

ion concentration at 50 C and atmospheric pressure.

containing iron (III) ions, Fig. 20. This was clearly indicated,
Fig. 17, where the concentration of iron (III) in the EDTA
before gypsum dissolution (theoretical) is equal to gypsum after
soaking for 8 hours.

CONCLUSIONS
The interaction between gypsum and different reactive fluids
(HCl/HF acid, HCl acid and EDTA) was studied in detail. The
effects of different parameters, such as solution pH value,
temperature and presence of iron (III) and magnesium ions were
investigated. The following conclusions can be drawn:
1. The presence of gypsum (CaSO4.2H2O) has a negative
impact on the performance of mud acid treatments. After
the initial dissolution of gypsum in the live mud acid,
dissolved calcium will precipitate as both calcium fluoride
and calcium sulfate in spent HCl/HF acid solutions.
2. Gypsum has a higher solubility limit in live HCl acid
compared to its spent solutions. This will result in
reprecipitation of calcium sulfate in spent HCl acid.
3. The reprecipitation of calcium sulfate in spent solutions of
HCl acid and HCl/HF acids could result in severe
formation damage. Live acids initially can partially
dissolve any precipitated calcium sulfate solids in the
wellbore area, but the dissolved calcium and sulfate ions
will reprecipitate in the formation rocks as the acid is spent.

Fig. 18. Gypsum solubility in 8 wt% EDTA as a function of dissolved iron (III)
ion concentration at 50 C and atmospheric pressure.

4. Gypsum has a higher solubility limit in the EDTA

solutions, compared to acidic solutions. No reprecipitation
of calcium sulfate occurred in these solutions due to the
fact that calcium ions exist as complex ions and are not
free to interact with other ions.
5. The presence of both magnesium and iron (III) ions had a
negative effect on gypsum dissolution in the EDTA fluid.
Compared to magnesium, iron (III) ions resulted in a significant decrease in gypsum solubility in the EDTA solutions.

Fig. 19. Magnesium reprecipitation in 8 wt% EDTA containing MgCl2.6H2O at

1, 2, 3 wt%. The solutions pH values are (a) 4, (b) 8 and (c) 14.

6. Dissolved magnesium ions in the EDTA solutions could

reprecipitate as magnesium sulfate when the gypsum is
dissolved. This reprecipitation is higher in low pH EDTA
solutions.

ACKNOWLEDGMENTS

Fig. 20. No ions reprecipitation in the solution of 8 wt% EDTA containing

FeCl3.6H2O at 1, 2, 3 wt% after gypsum dissolution. The solutions pH values
are (a) 4, (b) 8 and (c) 14.

The presence of magnesium ions did not only decrease the

EDTAs ability to dissolve gypsum, but the ions also
reprecipitated as magnesium sulfate. The amount of this
reprecipitation of magnesium ions increased at low pH values,
Fig. 19. No reprecipitation occurred in the EDTA solutions

The authors would like to thank the management of Saudi

Aramco and Schlumberger for their support and permission to
publish this article. Special thanks go to the Chemistry and
Advanced Instruments Units of the R&D Center for their
analysis of different solutions and solids.
This article was presented at the SPE European Formation
Damage Conference, Noordwijk, the Netherlands, June 7-10, 2011.

REFERENCES
1. Fulford, R.: Effects of Brine Concentration and Pressure
Drop on Gypsum Scaling in Oil Wells, SPE paper 1830,
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49

presented at the SPE 42nd Annual Fall Meeting, Houston,

Texas, October 1-4, 1967.
2. Smith, C.F., Nolan, T.J. and Crenshaw, P.L.: Removal
and Inhibition of Calcium Sulfate Scale in Waterflood
Projects, Journal of Petroleum Technology, Vol. 20,
No. 11, November 1968, pp. 1,249-1,256.
3. Shen, J. and Crosby, C.: Insights into Strontium and
Calcium Sulfate Scaling Mechanisms in a Wet Producer,
Journal of Petroleum Technology, Vol. 35, No. 7, July
1983, pp. 1,249-1,255.
4. Delorey, J., Allen, S. and McMaster, L.: Precipitation of
Calcium Sulfate during Carbonate Acidizing: Minimizing
the Risk, Petroleum Society of Canada paper
96-84, presented at the 47th Annual Technical Meeting,
Calgary, Alberta, Canada, June 10-12, 1996.
5. Ramsdell, L. and Partridge, E.: The Crystal Forms of
Calcium Sulfate, J. American Mineralogist, Vol. 14,
1929, pp. 59-74.
6. Carlberg, B.L. and Matthews, R.R.: Solubility of
Calcium Sulfate in Brine, SPE paper 4353, presented at
the SPE Oil Field Chemistry Symposium, Denver,
Colorado, May 24-25, 1973.
7. Oddo, J., Smith, J.P. and Tomson, M.B.: Analysis of and
Solutions to the CaCO3 and CaSO4 Scaling Problems
Encountered in Wells Offshore Indonesia, SPE paper
22782, presented at the 66th Annual Technical
Conference and Exhibition, Dallas, Texas, October 6-9,
1991.
8. Farrokhrouz, M. and Asef, M.R.: Production
Enhancement via Scale Removal in Nar Formation, SPE
paper 135854, presented at the SPE Production and
Operations Conference and Exhibition, Tunis, Tunisia,
June 8-10, 2010.
9. Kan, A.T., Fu, G., Fan, C., Tomson, M.B. and Shen, D.:
Quantitative Evaluation of Calcium Sulfate Precipitation
Kinetics in the Presence and Absence of Scale Inhibitors,
SPE paper 121563, presented at the SPE International
Symposium on Oil Field Chemistry, The Woodlands,
Texas, April 20-22, 2009.
10. http://www.3dchem.com.
11. Shaughnessy, C.M. and Kline, W.E.: EDTA Removes
Formation Damage at Prudhoe Bay, Journal of
Petroleum Technology, Vol. 35, No. 10, October 1983,
pp. 1,783-1,791.
12. Cikes, M., Vranjesevic, B., Tomic, M. and Jamnicky, O.:
A Successful Treatment of Formation Damage Caused
by High-Density Brine, SPE Production Engineering,
Vol. 5, No. 2, May 1990, pp. 175-179.
13. Pitzer, K.: Theory: Ion Interaction Approach, Activity
Coefficients in Electrolyte Solutions, Chap. Boca Raton,
Florida, CRC press, 1979.
50

FALL 2011 SAUDI ARAMCO JOURNAL OF TECHNOLOGY

14. Ciavatta, L.: The Specific Interaction Theory in

Equilibrium Analysis: Some Empirical Rules for
Estimating Interaction Coefficients of Metal Ion
Complexes, Annali Di Chimica, (Rome), Vol. 80, 1990,
pp. 255-263.
15. Serjeant, E.P. and Dempsey, B.: Ionization Constants of
Organic Acids in Aqueous Solution, Oxford, U.K.,
Pergamon Press: 1979.
16. Perrin, D.D.: Dissociation Constants of Organic Bases in
Aqueous Solution, London, U.K., Butterworths, 1965.
17. Permyakov, E. and Kretsinger, R.H.: Calcium Binding
Proteins, New Jersey, USA, John Wiley & Sons Inc.,
2011, pp. 85-90.
18. Martell, A.E. and Smith, R.M.: Critical Stability
Constants, Vol. 1-4, New York, USA, Plenum Press:
1974.
19. Li, Z. and Demopoulos, G.: Solubility of CaSO4 Phases
in Aqueous HCl + CaCl2 Solutions from 283 K to 353
K, Journal of Chemical & Engineering Data, Vol. 50,
No. 6, 2005, pp. 1,971-1,982.
20. Barba, D., Brandani, V. and Di Giacomo, G.: Solubility
of Calcium Sulfate Dihydrate in the System Na2SO4MgCl2-H2O, Journal of Chemical & Engineering Data,
Vol. 29, 1984, pp. 42-45.
21. Shaffer, L.H.: Solubility of Gypsum in Seawater and
Seawater Concentrates at Temperatures from Ambient to
65 Degrees, Journal of Chemical & Engineering Data,
Vol. 12, No. 2, April 1967, pp. 183-189.

BIOGRAPHIES
Dr. Mohammed H. Al-Khaldi joined
Saudi Aramco in 2001 as a Research
Engineer working in Saudi Aramcos
Exploration and Petroleum
Engineering Center Advanced
Research Center (EXPEC ARC).
During this time, he was responsible
for evaluating different stimulation treatments, conducting
several research studies and investigating several
stimulation fluids. In addition, Mohammed was involved in
the design of acid fracturing treatments. As an award for
his efforts, he received the Vice Presidents Recognition
Award for significant contributions to the safe and
successful completion of the first 100 fracturing treatments.
Mohammeds research interests include well stimulation,
formation damage mitigation and conformance control.
He received his B.S. degree in Chemical Engineering
(with First Class Honors) from King Fahd University of
Petroleum and Minerals (KFUPM), Dhahran, Saudi Arabia.
Mohammed also received his M.S. and Ph.D. degrees in
Petroleum Engineering (with First Class Honors) from
Adelaide University, Adelaide, Australia.
He is an active member of the Society of Petroleum
Engineers (SPE). Mohammed has published more than 15
SPE papers and seven journal articles, and has two patents.
In 2011, he received the SPE Best Technical Paper Award,
winning first place in the 2nd GCC SPE paper contest.
Ahmad M. Al-Juhani is a Chemical
Engineering student at King Fahd
University of Petroleum and Minerals
(KFUPM), Dhahran, Saudi Arabia. He
is scheduled to graduate in August
2011.
Ahmad did his training with the
Formation Damage and Stimulation Unit, Operation
Support Division, at the Exploration and Petroleum
Engineering Center - Advanced Research Center (EXPEC
ARC). During this period, he worked on several studies
involving pipe dope removal, calcium sulfate scale removal
and H2S scavenger evaluation.

Dr. Saleh H. Al-Mutairi is a

Researcher with the Stimulation Group
in the Operations Services Division at
Saudi Aramcos Exploration and
Petroleum Engineering Center Advanced Research Center (EXPEC
ARC). His research interests include
well stimulation, formation damage, tubular corrosion
problems and rheology of fluids. Saleh has 11 years of
experience in well stimulation operations and research, and
he has published several pieces of work in this area.
He received his B.S. degree in Chemical Engineering and
an MBA degree, both from King Fahd University of
Petroleum and Minerals (KFUPM), Dhahran, Saudi Arabia.
Saleh also received a M.S. degree in Petroleum Engineering
from the University of Texas at Austin, Austin, TX. He
received his Ph.D. degree in Petroleum Engineering from
Texas A&M University, College Station, TX.
Dr. M. Nihat Gurmen is a Technical
Manager at Schlumberger for the
Arabian Market covering Saudi
Arabia, Kuwait and Bahrain. Based in
al-Khobar, Saudi Arabia, he is a
company Subject Matter Expert for
stimulation products, fluids and
services. Nihat started his Schlumberger career in the Client
Support Laboratory in Sugar Land, TX, in 2004. In his
next assignment, Nihat transferred to Alice, a field location
in South Texas, as the District Technical Engineer. In his
current role in the Arabian Market, Nihat ensures that
correct technologies are applied in stimulation operations
and introduces new products and services as necessary.
Nihat received his B.S. degree in Chemical Engineering
from Bogazici University, Istanbul, Turkey, and earned a
Ph.D. degree from the University of South Florida, Tampa,
FL. He was a postdoctoral fellow at the University of
Michigan, Ann Arbor, MI, in the Fogler Research Group.
Nihat is an active member of the Society of Petroleum
Engineers (SPE) and coauthor of various journal, SPE and
patent publications.

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