Anais da Academia Brasileira de Ciências (2018) 90(3): 3185-3196

(Annals of the Brazilian Academy of Sciences)

Printed version ISSN 0001-3765 / Online version ISSN 1678-2690
http://dx.doi.org/10.1590/0001-3765201820170728
www.scielo.br/aabc | www.fb.com/aabcjournal

Study of barium sulfate dissolution by scale dissolver based on solutions of DTPA

GEIZILA A.P. ABIB, GEORGIANA F. DA CRUZ and ALEXANDRE S.L. VAZ JUNIOR

Laboratório de Engenharia e Exploração de Petróleo/LENEP, Setor de Geologia e Geoquímica,

Universidade Estadual do Norte Fluminense Darcy Ribeiro/UENF, Av. Brennand, s/n,
Rodovia Amaral Peixoto, Km 163, Imboacica, 27925-535 Macaé, RJ, Brazil

Manuscript received on September 14, 2017; accepted for publication on April 4, 2018

ABSTRACT
In offshore oil wells it is very common to perform seawater injection through injection wells for
hydrocarbon recovery. When seawater, rich in sulfate ion, mixes with formation water, whose composition
can contain divalent cations such as barium and calcium, it often leads to sulfate salts formation due to
their chemical incompatibility. These salts can cause serious damage in production wells. The barium
sulfate (BaSO4) is the most problematic scale and may cause many complications. In order to solve this
issue, polycarboxylic acids, such as diethylene triamine pentaacetic acid, are used. Thus, the primary focus
of this work was to develop an experimental procedure to study the BaSO4 dissolution. Initially, through
static tests to understand the relationship between dissolver concentration, temperature and dissolution
time, and then through dynamic tests in sandstone reservoirs. Based on the results obtained, in the static
tests the best condition for barite to dissolve was at high temperatures (80 ºC) and contact time of 48 hours,
since from 50 °C there is an increase in dissolution rate, associated with a long contact time between
dissolver and barite. In the dynamic tests, after scale formation, barite could be removed, but the high
DTPA concentration should be avoided.
Key words: Mineral scale, barite, oil reservoir, formation damage.

INTRODUCTION water (FW), which contains ions such as barium

(Ba2+) and calcium (Ca2+) and, therefore, the mixture
During the oil production phase, the reservoir
between these waters within the rock porous can
primary energy needs to be supplemented, and so
promote the deposition of mineral scales, which
the secondary recovery process is necessary. The
consist of salt with low solubility in water (Dunn et
water injection through wells is the most common
al. 1999, Shaw et al. 2012, Bin Merdhah and Yassin
practice, and in offshore productions, seawater
(SW), which is rich in ion sulfate (SO42-) is usually 2008a). The most common scales in the petroleum
injected. The reservoir is saturated with formation industry are calcium sulfate (CaSO4), calcium
carbonate (CaCO3) and barium sulfate (BaSO4).
Correspondence to: Georgiana Feitosa da Cruz This latter is known as barite and has an important
E-mail: georgiana@lenep.uenf.br
Geizila Aparecida Pires Abib feature, remains practically insoluble in water
E-mail: geizilala@yahoo.com.br and acid, due to its low solubility, which gives it

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3186 GEIZILA A.P. ABIB, GEORGIANA F. DA CRUZ and ALEXANDRE S.L. VAZ JUNIOR

the chemical inertia property (Dunn et al. 1999, and removal processes by industry, laboratory test
Bin Merdhah and Yassin 2008b, Bin Merdhah et studies on static and dynamic barite deposition
al. 2010). However, it is possible to find solubility and subsequent removal are still little widespread
values between 2.0 and 2.5 mg L-1 at 25 °C in water and complex (Dunn et al. 1999, Bin Merdhah and
and solubility product (Ksp) values equal to 1.02 Yassin 2008b). Also, chemical factors affecting this
10-10 mol L-1 at 25 °C, which makes this salt more reaction are not fully known, leading to conflicting
difficult to remove (Wang et al. 1999, Harris 2001). results on treatment effectiveness (A.V. Shende,
The formation of insoluble salts, which are deposited unpublished data).
in rock pores and in production equipment, might Therefore, a methodology to study barium
reduce or block the rock pore throat and damage sulfate dissolution through static test with DTPA
several equipment causing subsequent financial and, subsequently dynamic test with injection of
loss. The region near production wells is the dissolver into a porous medium which simulates
most affected one (Economides and Nolte 2000, a reservoir rock, is of considerable importance.
Mackay 2003, Mackay et al. 2003, Kalfayan 2008), Despite that, there is still no work in the literature
therefore, when the scale potential is known, the use that compiles these methodologies in an integrated
of preventive and corrective methods is necessary manner to approach this matter. Hence, this work
to solve the mineral scale deposition issues. intends to offer a comprehensive methodology in
The scale control by chemical inhibitors the barium sulfate scale study, starting with the
application is normally used as a preventive static test and then through with the dynamic test.
method. It consists of injections of substances Chemistry knowledge on composition of waters
which are capable of controling the scale formation FW and SW and DTPA solution is necessary for this
by preventing crystal formation stages such as study. The ion chromatography (IC) has extensive
nucleation, crystal growth and dispersion. The scale analytical application and provides an alternative
prevention, normally, uses the squeeze treatments method to classical techniques (gravimetric,
in which inhibitors are injected into the production volumetric e.g.) to determine ions with speed,
well. However, there are scenarios in which scale efficiency and low effort. In the oil industry this
inhibition alone is not enough, and scale deposits technique can determine the concentration of ions
formation may occur. In some cases, a combination present in fouling water, providing information
of preventive and corrective methods is necessary. about the scale formation process and its trend rate
This latter consists of removing the existing and also about inhibitors efficiency (Atwood and
damage either by mechanical techniques (milling, Wallwey 1996, Collins et al. 2006, El-Said et al.
jetting, fracturing of scale) or chemical products 2009) since IC allows different cations and anions
(treatments by inorganic acids or polycarboxylic determination, including sodium (Na +), barium
acids) (Bellarby 2009, Tomson et al. 2003, Reis et (Ba2+), chloride (Cℓ-) and sulfate (SO42-), which are
al. 2011, Fink 2012). The barite scale is very hard present in the formation and injection water as well
and only polycarboxylic acids are able to remove as the mineral scale. So IC was used to quantifiy
it. The diethylene triamine pentacetic acid (DTPA), previous ions present in the solutions of both tests.
which is a strong cation chelating agent, is one of Thus, this work sets experimental procedures
the most used in the oil industry. This chelating to study the dissolution of the BaSO4 scale by
agent is injected into the production well and it is chelating agent. Initially, BaSO4 static dissolution
able to remove the salt by forming metal complexes. tests were performed varying temperature,
Although there are several studies in the literature dissolution concentration and dissolution time

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conditions, which are important factors for the The dynamic tests were performed using a
chemical reaction. Based on the preliminary confinement cell, type core holder, Labconte, and
results, it was possible to develop an experimental a constant flow pump, model PU-2087 plus- Jasco,
protocol for dynamic tests with monophasic and and a manual hydraulic pump model 700HTP1,
biphasic flow, including damage formation - BaSO4 FLUKE, for fluid injection. Pressure values
precipitation inside rock pores - and subsequent measured during this tests were collected using a
DTPA removal. computer, the software LabView, along with the
differential pressure transducer model EJA 130A/
MATERIALS AND METHODS
S1, Yokogawa, and gauge 316 SS, Swagelok. The
This work covers two steps, first the application dimensions of core material were measured with
of static tests to evaluate the effects of barite the digital caliper, DIGIMESS. The DTPA solution
dissolution by DTPA in bench tests, varying their was injected using the transfer bottle, Labconte.
concentration, temperature and reaction time Other equipments used were the drying and
between the barite and dissolver; and second the sterilizing oven New Ethics 200/2ND and the
use of dynamic tests with mono-phase and two- system saturation and vacuum filtration.
phase flow, including the damage formation and
MATERIALS AND REAGENTS
subsequent removal. Information about equipment,
reagents, samples and procedures are described in Analytical grade reagents were used to prepare
the respective sub-sections. all eluents, standard stock solutions, supplied
INSTRUMENTATION Merck. The eluents used for analysis with IC, were
dihydrate oxalic acid (C2H2O4.2H2O) – eluent for
The FW, SW and DTPA solutions were prepared cations; sodium carbonate (Na2CO3) and sodium
using ultrapure water obtained from Milli-Q bicarbonate (NaHCO3) – eluents for anions; sulfuric
Direct-Q 5 MILLIPORE water purification system. acid (H 2SO 4) 95-97% – regenerating solution.
The fouling salts and samples (barite and core The barium determinations were calibrated by
material) were measured by the analytical balance measuring five standard solutions. Standard
Shimadzu model AUY 220. The bench pHmeter solutions were prepared from BaCl2 solutions to
model 827 Metrohm was used to measure this build the calibration curve (coefficient correlation,
parameter. The ions quantification was performed R = 0.999807 and stadard deviation, SD = 1.8%). To
using the ion chromatography (IC) with sampler
prepare the SW were used sodium sulfate (Na2SO4)
and conductivity detection, model 850 Professional
and sodium chloride (NaCℓ), for the FW were used
IC, equipped with pump 833 Liquid Handling
barium chloride (BaCℓ2.2H2O) besides NaCℓ. The
Unite, 858 Professional Sample Processor, and the
composition of fouling water is shown in Table I.
chromatographic columns employed were Metrosep
C2 150/4.0 mm for cations, and Metrosep A Supp5 TABLE I
150/4.0 mm, for anions. To observe the pits on Composition of FW and SW waters used in dynamic tests.
the barite surface and rock sections the scanning Ions FW – (mg L-1) SW – (mg L-1)
electron microscopy (SEM) - TM3000 Tabletop Cℓ- 51779 21300
Microscope, HITACHI, and the energy dispersive Na+ 33500 14490.76
X-ray spectroscopy (EDS) EDS SwiftED3000 Ba2+ 229 -
2-
were employed. SO4 - 2834

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3188 GEIZILA A.P. ABIB, GEORGIANA F. DA CRUZ and ALEXANDRE S.L. VAZ JUNIOR

The DTPA solutions were prepared from radioactivity free. The dissolvers were prepared
following the commercial products Versenex K, in three different formulations with 10%, 15%
Dequest 2066A, Ultranex NP 100 and DTPA. The and 25% DTPA. The information about the
dissolver solution’s components and its respective base materials used in this preparation and their
functions are shown in Table II. respective functions are presented in Table II. The
The barite samples were obtained by tests occurred at temperatures of 23, 50 and 80 °C
precipitation of this salt within production wells and time periods of 12, 24 and 48 hours, and the
from the Campos basin, Brazil, during the production experiments were carried out at pH levels of 11–12
step. While in surface conditions, the barite received where the DTPA is effectively deprotonated (K.
cleansing and purification treatments (including free Wang et al., unpublised data, Putnis et al. 2008).
radioactivity). The samples were kindly provided by These tests evaluated the dissolution of natural
CENPES/Petrobras and are presented in an ellipsoid BaSO4 beads through mass variation (initial and
shape, as shown in Figure 1a. final barite mass); the Ba2+ concentration in the
The core material used for the dynamic supernatant was analyzed with ion chromatographic
core floods came from the Botucatu formation (IC); pits on the barite surface were analyzed
(Botucatu sandstone) in Brazil. The Botucatu with scanning electron microscopy (SEM) in
Formation comprises clayey rock, silt rock and order to observe the dissolver’s chemical attack.
sandy rock located in northeast of Paraná state and Initially, the barite was weighed and then placed
in southwest of São Paulo state (Montanheiro et al. into the vials and 1 mL of dissolver was added.
2011). The core material represents the reservoir After the dissolution time, a vacuum filtration was
rock in this experiment, that is, the scale location, performed and both filtrated and remaining barite
as shown in Figure 1b.
were analyzed with IC and SEM, respectively.
PROCEDURES
Dynamic tests
Static test with barite
Several tests were performed during the laboratory
Barite dissolution tests were made with precipitate step of this research to find the best methodology and
in spheroid forms (real scale), cleaned and best solution to remove mineral scale. Six dynamic

TABLE II
Components of dissolver solution and its respective functions.
Solution A (10% DTPA) Solution B (15% DTPA) Solution C (25% DTPA)
Components
Vol (mL) pH de (g mL-1) Vol (mL) pH d (g mL-1) Vol (mL) pH d (g mL-1)
Versenex Ka 51.0 76.0 123.0
Dequest 2066Ab 0.75 0.75 0.75
c
11.01 1.03 11.08 1.07 11.13 1.12
Ultranex NP 100 0.25 0.25 0.25
Ultrapure water d SQTf SQT SQT
a
DTPA active substance / scale dissolver.
b
preventer emulsion.
c
wetting agent.
d
diluent. Ultrapure water was used to prepare the solutions of static test. But in the injection flow tests the diluent used was 35 000
mg L-1 saline solution.
e
density.
f
in sufficient quantities to prepare 250 mL of solution.

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 REMOVAL OF MINERAL SCALE IN OIL RESERVOIR BY DTPA 3189

Figure 1 - Samples used in the tests: (a) barite samples (BaSO4) used in static test; (b) core
material used in the dynamic test (side view).

tests were performed – 5 mono-phase flow tests and q = flow rate (m3 s-1)
1 two-phase flow test – but only one test of each was k = permeability (mili Darcy)
shown to represent the methodology proposal. A = area (m2)
These tests were subdivided into procedure ΔP = pressure differential (Pa)
A, mono-phase flow (brine injection only) and μ = viscosity (Pa.s)
procedure B, two-phase flow (injection of brine L = length (m)
and diesel). Core material measurements used were Then, the FW and seawater (SW) brines were
4.1 cm length and 2.5 cm diameter with average injected through separated lines, simultaneously,
porosity of 21%. IC analysis and SEM, combined at 0.5 mL min-1 each solution, in order to promote
with dispersive X-ray energy spectroscopy (DES), formation damage within the rock porous. Effluent
were also used. samples were collected along the injection. A
damaged permeability (kdam) was measured with
Procedure A – test 1
FW, after the simultaneous injection. Then, around
Initially, the core material was saturated with 100 mL of 15% DTPA in solution was injected at 1.0
formation water (FW) under vacuum and then it mL min-1 order to promote the scale removal and,
was assembled in a cell with a confining pressure of after 24 hours (soak time) the third permeability
1500 psi. The core was shut in and heated in an oven was measured to evaluate the original permeability
at 50 °C for 16 hours, and the original permeability recovery, the final permeability (kfinal). The effluent
(korig) was measured by FW injection at four flow samples collected during the tests (FW and SW
rates, 2.0 mL min-1, 1.5 mL min-1, 1.0 mL min-1 and injection) were analyzed with IC and core sections
0.5 mL min-1, through the use of Darcy’s Law, since were analyzed with SEM. It is important to point
it is the most used equation for flow measurement out that the DTPA solution used in this procedure
in porous medium (Rosa et al. 2006). The Darcy’s was prepared with saline instead of ultrapure
Law (Equation 1) is: water, otherwise it could cause fines migration
kA∆P due to low salinity and, consequently, porosity and
q=
µ L (1) permeability drop.

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3190 GEIZILA A.P. ABIB, GEORGIANA F. DA CRUZ and ALEXANDRE S.L. VAZ JUNIOR

Procedure B – test 2

The same steps used in Procedure A were employed

until the first permeability (korig) measurement.
Then, a consecutive oil-water-oil injection at 1.0
mL min -1 was performed, in order to measure
the oil and water relative permeability (kro and
krw), residual oil saturation (Sor) and irreducible
water saturation (Swi). The FW and SW brines
were injected simultaneously (at 0.5 mL min-1
each solution) to induce damage within the rock.
During the damaging stage, effluent samples were
collected. Second oil and water injections were
performed with flow rate of 1.0 mL min-1 each, in
order to measure kro, krw, Sor and Swi after induced
damage formation. Then, around 100 mL of 25%
DTPA in solution at 1.0 mL min-1 was injected and,
after 24 hours (soak time), a third water and oil
injection was performed to measure new values of
kro, krw, Sor and Swi after dissolver application.

RESULTS AND DISCUSSION

STATIC TEST

The static tests were performed in triplicate

for each condition assessed involving different
temperatures (23 °C, 50 °C and 80 °C), time periods
(12h, 24h and 48h) and concentrations (10%, 15%
and 25%). The barite mass presented a decrease
in all tests; dissolved barite mass percentage was
obtained by gravimetry along the time period of
each concentration and it is shown in Figure 2.
Temperature effect in static tests, without the
saline water presence, could show a proportional
relationship between temperature and BaSO 4
dissolution, because salt solubility increased
with temperature increase for all solutions. Since
the activation energy is directly associated with
temperature, it can be said that temperature is the
control factor of the reactions that occur on the
Figure 2 - Dissolved barite mass (%) versus residence time
barite crystal surface leading to its dissolution (h) for static test at 23 °C (a), 50 °C (b) and 80 °C (c) for
(Bin Merdhah et al. 2010, Jordan et al. 2000). 10%, 15% and 25% DTPA in solution, respectively.

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So then, at high temperatures, a larger dissolved

barite mass was obtained. Similar results were
observed with time influence, since longer contact
time between barite and solution caused higher
solubility. M.M. Jordan et al. (unpublished data)
reported that the BaSO4 dissolution at temperatures
below 40 °C is poor, and that from 50 °C there is
an improvement in the dissolution rate. It was also
observed in this work, that the highest dissolved
mass percentage values was from 50 °C. Thus, for
the static tests performed in this work, the highest
barite dissolution value was at 80 °C with contact
time of 48 hours at high pH (11–12), for all DTPA
concentrations.
The results concerning the effect of DTPA
concentration in solution show no proportionality
between the dissolver concentration and barite
dissolution once the significant increase of dissolved
barite mass was noticed only from 50 °C, for all
three DTPA concentrations. As DTPA molecules
are large, a high concentration may cause a
shielding layer formation (agglutination of DTPA
molecules) on the surface of barite, interfering in
the removal efficiency. This shielding layer may be
broken by increasing the dissolution temperature
since this process is endothermic (K. Wang et
al., unpublished data, Putnis et al. 2008). Thus,
these results suggest that at low temperatures, in
the absence of interferences and without taking
into account the effects of pressure, excess DTPA
becomes detrimental to the precipitated salt
dissolution. In this case, a better employment of
DTPA could be achieved if the dissolver solution
was less concentrated. However further tests are
still necessary to confirm this hypothesis.
Figure 3 shows the Ba2+ concentration from
the dissolved barite mass, which was present in
the supernatant. Then, dilutions were made and the
resulting solutions were analyzed with IC. These
Figure 3 - Concentration (mg L-1) of total Ba2 + and free
results present the values for free Ba2+, the scale Ba2 + in supernatant at 23 °C (a), 50 °C (b) and 80 °C (c),
ion, not complexed with DTPA and the total Ba2+, analyzed by ion chromatography IC.

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3192 GEIZILA A.P. ABIB, GEORGIANA F. DA CRUZ and ALEXANDRE S.L. VAZ JUNIOR

which is Ba2+ ion existent into supernatant in free shape of the barite is relatively regular, smooth and
and complexed forms. homogeneous.
Although the stoichiometry of the reaction is Figure S1b, c and d also indicates corrosion
not completely known, the literature presents the points and grooves on the surface of the barite,
equimolar ratio between DTPA and Ba2+ as 1:1, which became deeper under more severe conditions.
according to Equation 2. This chemical equation The images obtained with SEM were important
shows the dissolution reaction and the stability to observe and check the action of the dissolver
constant (Kst) of chelate formed between barium solutions on BaSO4 dissolution, and it can be seen
ions and DTPA (Ba-DTPA3-) (Wang et al. 1999, K. that the 25 DTPA% solution at 80 °C and 12 hours
Wang et al., unpublished data, Putnis et al. 2008). dissolution time was the most efficient condition,
as noted in the evaluation of the dissolved mass
BaSO4( s ) + DTPA(5aq− ) → BaDTPA(3aq− ) + SO42(−aq ) percentage.
(2)
log K st = 8.78
DYNAMIC TESTS
2+
Thus, the difference between the total Ba
Mono-phase flow test
and free Ba2+ ions corresponds with the complexed
Ba 2+ ions, since the dissolver solutions had The mono-phase flow test results showed the
adequate amounts of DTPA molecules to react variation of absolute permeability. Figure 4, through
with. Therefore, it was observed that the total Ba2+ application of Darcy’s Law, shows the reduction of
concentration was bigger than the free Ba2+ in all korig (~119 md) after damage to kdam (~68 md), and
tests, indicating that the largest amount of Ba2+ ions the kfinal (~118 md) after removal of the damage.
was complexed with DTPA. The calculations applied the corrected value of
After contact between DTPA and barite crystal, viscosity equal to 0.6 10-3 Pa.s at 50 °C. These three
the barite crystal wears out in surface area and gets permeability values, represented by the curves,
corrosion points due to detachment of the barium showed that it was possible to reduce the original
ion from barium sulfate. Hence, the formed ion- permeability value due to the mixture of the FW
remover complex is responsible for the disruption and SW waters and the consequent precipitation
of the bonds that hold the fouling core intact and of BaSO4 into the pores of the rock, obstructing
thus with presence of the scale dissolver, the deposit the flow, which is, considerably reducing the rock
is gradually removed, and so one portion of barium original permeability. However, after treatment
ion is complexed and another is free. of the core material with DTPA dissolver, the
The barite dissolution can also be observed permeability increased (final permeability value)
on images of SEM, which show the pits on barite because the BaSO4 was dissolved and there was an
surface and testify the chemical attack caused by original permeability recovery. Nevertheless, the
DTPA. These pits have become more profound high permeability recovery value (almost 100%)
as the dissolution conditions were more severe could come from some rock stimulation, caused
(higher contact time, higher temperatures and by a chemical reaction between dissolver and rock
higher remover concentrations). The Figure S1a minerals, and thus contributing to a considerable
(Supplementary Material) shows a barite image increase in the rock’s original permeability, which
before the test (without remover solution) with a was also observed in some works in the literature
resolution of 40x. It is possible to observe that the (Todd and Yuan 1992, Ali et al. 2008).

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Figure 4 - Measurement of original (korig), damaged (kdam), and final permeabilities (kfinal) from
the Darcy law for the mono-phase flow test (15% DTPA/24h).

In addition to the permeability values obtained TABLE III

Concentration (mg L-1) of Ba2+ and SO42- obtained by IC
through Darcy’s Law, the effluent samples from
from mono-phase flow test.
mono-phase flow test were analyzed with IC
Scaling waters/ Concentration (mg L-1)
and Table III shows the concentrations of Ba2+ effluents Ba2+ SO42-
and SO42- in the effluents during the damaging SW a
- 2836.25
stage and removal stage. During damaging stage FW b
226.12 -
(simultaneous injection of FW and SW waters) c
ED 1 9.42 1182.25
there was significant reduction in concentration of ED2 12.70 1243.50
Ba2+ in the effluent due to the chemical reaction ED3 11.15 1308.25
between this ion and SO 42-, leading to BaSO 4 ED4 9.40 1367.50
scale formation in the rock pore, which caused a ERd1 203.27 281.50
significant permeability loss, a reduction of 42% ER2 110.95 149.25
from the original permeability. On the other hand, ER3 79.17 110.25
there was an increase in the concentration of Ba2+ in ER4 63.90 138.00
a
the effluent from removal due to dissolution process sea water.
b
formation water.
which breaks the scale structure. The IC was c
ED1 to ED4 = samples of effluents collected during formation
capable of detecting the ion Ba2+, even in samples damage stage.
with high concentrations of other typical ions in d
ER1 to ER4 = samples of effluents collected during removal
salt water, such as sodium (Na+) and potassium of damage stage.

(K+), as also reported in the literature (Atwood and

Wallwey 1996). S2a shows EDS spectrum and 2Sb SEM image.
To confirm the presented methodology and Figure S2b shows a SEM image of a rock sample
illustrate the BaSO4 precipitation as a result of with BaSO4, obtained from extra tests performed
the mixture between FW and SW waters, Figure using only scaling waters injection and without

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3194 GEIZILA A.P. ABIB, GEORGIANA F. DA CRUZ and ALEXANDRE S.L. VAZ JUNIOR

the removal step. The identification and chemical observe relative permeability and saturation
elements quantification with EDS was made for variations throughout the experiment, during
the demarcated section. This area was chosen after stage 1 (before formation damage), stage 2 (after
scanning all surface rocks and only at this point formation damage) and stage 3 (damage removal)
identifying the presence of barium, sulfate and according to Figure 5. The kro, krw and Swi (stage
oxygen. Others crystalline materials were found, but 1) decreased after damage formation, while the Sor
they contained sodium and chloride. In this section, increased (stage 2). After the damage removal, kro,
the dispersive X-ray energy spectrum for chemical krw and Swi increased and the Sor decreased (stage
elements quantification was made, as shown in 3). These final values are acceptable because a
Figure S2a. It was possible to observe, besides the higher Swi indicates a water-wet rock by it and thus
common elements in sandstone rocks, the presence a smaller water volume tends to be produced. On
the other hand, a low value of Sor means that the
of sulfur (S) and barium (Ba) elements, along with
rock is less wettable to the oil and, thus, the fluid
oxygen (O) element, which are part of the chemical
has low adherence in the rock wall and can be
composition of the referred mineral scale.
easily produced. Due to the high values found in
Therefore, Figure 2S showed that the
stage 3, we raise the hypothesis that the DTPA may
methodology can represent the real damage caused
have improved the original permeability because it
by scaling waters injection.
reacted with the scale and it may also have reacted
Two-phase flow test with the rock, since a high concentration of this
product was used. However, it is necessary to repeat
One two-phase flow test was performed to exemplify this test to confirm this hypothesis. In the literature,
the methodology proposal. It was possible to some studies were carried out in which dissolvers

Figure 5 - Variation of relative permeability (kr) versus water saturation (Sw) for the three
moments of two-phase flow test: stage 1 - before damage formation (blue), stage 2 - after
damage formation (red) and stage 3 - after removal of damage (black).

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based on DTPA and EDTA dissolved sandstones IC - ion chromatography

(Todd and Yuan 1992, Ali et al. 2008). SEM - scanning electron microscopy
EDS - energy dispersive X-ray spectroscopy
CONCLUSIONS korig - original permeability
kdam - damaged permeability
In general, through the proposed experimental
kfinal - final permeability
procedures, it was possible to study the dissolution
kro - oil relative permeability
of BaSO 4 and the parameters (temperature,
krw - water relative permeability
dissolution time and DTPA concentration) involved.
Sor - residual oil saturation
Static tests have enabled prior knowledge on the
Swi - irreducible water saturation
BaSO4 dissolution study and showed that increasing
the temperature and dissolution time were positive ACKNOWLEDGMENTS
factors to achieve disintegration and enhanced scale
dissolution. Moreover, this study showed that a The authors would like to thank CENPES/Petrobras
high DTPA concentration under low temperatures, for supplying the barite and the other components
below 40 °C, is not efficient for BaSO4 dissolution. to prepare the DTPA solutions, and thank PRH20
Thus, DTPA solutions with a high concentration and Agência Nacional do Petróleo, Gás Natural e
must be used at higher temperatures and longer Biocombustíveis (ANP) for the financial support.
dissolution time, in order to avoid the shielding We are also grateful to Mrs. Francisca F. do Rosário
effect. With the dynamic tests (mono-phase and for allowing us to use the SEM and to Raquel M.
two-phase) it was possible to simulate the damage Fedrizzi for preparing the SEM/EDS images, and
formation (BaSO4 scale) in rock pores through Petroleum Engineer Sofia Forestieri da Gama
incompatible waters injection, by monitoring the Rodrigues for revising this text.
pressure rise, with a decrease in permeability. And
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