SPE 87454

A Single-Stage Acid Treatment to Remove and Mi tigate Calcium

Carbonate Scale in Sandstone and Carbonate Reservoirs
H.A. Nasr-El-Din, H.A. Al-Saiari, H.H. Al-Hajji, Saudi Aramco, M. Samy, M. Garcia, W. Frenier, M. Samuel,
Schlumberger
Copyright 2004, Society of Petroleum Engineers Inc.
th

This paper was prepared for presentation at the 6 International Symposium on Oilfield Scale
held in Aberdeen, UK, 26-27 May 2004.
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Abstract
Combining scale inhibition with matrix stimulation in a single
treatment has always been a challenge due to potential
formation damage. This concern has been historically
prominent in carbonate reservoirs, due to the accelerated
precipitation of the scale inhibitor at very low pH values.
Earlier experience in combining acid stimulation with scale
inhibition in carbonate reservoirs has been reported with
limited success.
This paper presents recent development in combining acid
stimulation and scale inhibition treatments in sandstone and
carbonate reservoirs. The combined treatment utilizes a newly
developed scale inhibitor (a polymer-based inhibitor) that
offers full compatibility with a wide range of the
commercially available acidizing systems, including
hydrochloric acid, mud acids and chelating agents.
This treatment minimizes the number of well interventions,
significantly reduces well maintenance cost and improves the
work-over efficiency. At least one scale inhibitor squeeze
treatment is eliminated with every acid stimulation treatment.
In addition, there are other inherent advantages including:
effective inhibitor placement and better coverage of the target
zone.
Results
A new acid-compatible scale inhibitor (polymer-based) was
developed. This new inhibitor is compatible with most acid
additives and can tolerate high levels of calcium and ferric
iron. Coreflood tests, utilizing reservoir cores, indicated that
the new acid system can be injected into sandstone or

carbonate cores. The combined acid system did not cause any
damage to reservoir cores tested. Analysis of core effluent
indicated that the scale inhibitor did not affect the acid
reaction with reservoir rocks. The inhibitor adsorbed on the
rock surface and desorbed during the injection of synthetic
brine (KCl brines).
Application
The new treatment can be applied in sandstone or carbonate
reservoirs. Previous work highlighted the need to flow the
well following acid descaling treatments.1 The new acid
system eliminates the need to flow back the well following
acid stimulation and/or descaling treatments and reduces the
volume of aqueous phase injected into the formation, which is
a major concern in tight formations.2 Finally, this treatment
significantly reduces well maintenance and workover costs. In
addition, it improves placement and performance of scale
inhibitor treatments.
Introduction
Calcium carbonate scale deposition is common in oil and gas
wells and can severely impact production. This type of scale
forms in three oil fields in Saudi Arabia: two carbonate
reservoirs, and a sandstone reservoir. Calcium carbonate scale
forms in the top 1,000 ft of the two carbonate reservoirs (B
and G),2-4 while forming downhole in the sandstone reservoir
(H).5-7 CaCO3 scale formation in the producing wells can be
represented by Equation 1.
Ca2+ + 2HCO3- CaCO3 + H2O + CO2 .. (1)
This type of scale forms in the carbonate reservoirs due to the
release of carbon dioxide, CO2, which occurs when the
pressure in the tubing decreases below the bubble point. It
occurs in the sandstone reservoir due to pressure changes that
occur in the electric submersible pumps (ESPs). The scale in
the three fields causes loss of well performance, and is usually
removed by an acid treatment. The procedure and field cases
of descaling producing wells in the sandstone reservoir were
given by Nasr-El-Din et al.8
Calcium carbonate scale problems in the three fields are
addressed by descaling followed by squeezing the wells with a
phosphonate-based inhibitor. These two steps are usually

separated by a period of time, where the well is allowed to

flow for several days. The objective of this period is to make
sure that there is no significant amount of iron in the critical
near wellbore area.1 It is well known that phosphonate-based
inhibitors precipitate in the presence of iron and can cause
formation damage. Moreover, these steps are costly, and there
is potential cost saving if the two treatments are combined into
a single treatment.
Precipitation and adsorption squeeze treatments are the two
major types of squeeze applications and, each has a different
dominant retention/release mechanism. These are matrix
operations where the fluid is pumped at rates that are lower
than the rate necessary to fracture the formation. In
precipitation squeeze treatments, the injected threshold scale
inhibitors react with divalent cations in the formation water to
generate scale inhibitor precipitates. These scale inhibitor
precipitates are slowly dissolved back into the produced fluids
where to prevent scale formation. Calcium-scale inhibitor
precipitates occur easily due to high calcium ion concentration
in the formation water; however other divalent cations, such as
magnesium, may also form precipitates with scale inhibitors.9
If a precipitating cation is not present, the inhibitor will adsorb
onto the native rock and clay surfaces. Inhibitor models
attempt to predict the squeeze life based on the major
mechanism, adsorption isotherm and inhibitor concentration in
the treatment fluid. The literature reviewed discusses major
mechanistic studies conducted to date.
A few studies examined adding a scale inhibitor during
acid descaling treatments. Vetter et al. tested several scale
inhibitors and concluded that none of the inhibitors tested
functioned in low pH environments.10 Smith et al.11,12
proposed a multifunctional fluid that included scale removal
and a scale inhibitor.
The objectives of the present study are to: (1) screen
various inhibitors that can be used during acid descaling
treatments, (2) determine if the scale inhibitor is compatible
with acid additives, (3) examine potential injectivity problems
and formation damage during matrix stimulation with acid
solutions that contain a scale inhibitor, and (4) study acid-rock
interactions in the presence of the scale inhibitor.
Experimental Studies
Materials
Six commercial acid-compatible scale inhibitors were
compared in this study. Table 1 shows the characteristics of
these inhibitors. Scale inhibitor (SI-3) is the only polymerbased inhibitor, which explains its low phosphorous content
compared to the other inhibitors examined.
Hydrochloric acid (ACS reagent grade) and deionized
water were used to prepare the acid solutions. Acid
concentration was determined by titration using 1M sodium
hydroxide solution, and was found to vary from 35.5 to 37
wt%. Acid solutions with additives were prepared such that
the final acid concentration was 15 wt% HCl.
Calcium carbonate (ACS grade) was used to neutralize the
live acid. Ferric chloride hexahydrate (a source of Fe (III)) and
two corrosion inhibitors that are commonly used with mineral

SPE 87454

acids (CI-A and CI-B), were tested.

Kinetic Tests
Rotating disk tests were conducted using marble disks (2.5 cm
in diameter). Tests with and without addition of scale
inhibitors were conducted at two temperatures to determine
the effect on the rate of dissolution of calcite. Details of the
test procedure were given by Frenier et al.13
Coreflood Tests
Coreflood experiments were conducted to determine if the
scale inhibitor can cause injectivity problems, and/or
formation damage. Another objective was to determine the
propagation of this inhibitor in reservoir cores. These tests
were conducted in a linear mode. The first set of tests was
performed using Berea sandstone cores. The second set of
experiments was done using core plugs obtained from
sandstone and carbonate reservoirs in Saudi Arabia. The
mineralogy of the sandstone cores is given in Table 2. The
core plugs were 1.5-inch in diameter and nearly 2-inch in
length. The tests were conducted at a constant injection rate of
2 cm3/min and a temperature of 150F, reservoir temperature.
The core was subjected to overburden pressure of 2,000 psi
and a back pressure of 1,000 psi. The coreflood experiments
started by the injection of 5 wt% KCl (to minimize fines
migration). Then 5 pore volume of the combined acid (15 wt%
HCl + 5 or 10 vol% SI-3 + 0.3 vol% CI-A) were injected into
the core. The pressure drop across the core was monitored
throughout the experiment. Finally, a post flush of 5 wt% KCl
was injected into the core. Samples of the coreflood effluent
were collected and the concentrations of key ions: Al, Si, Ca,
Mg, Na, K, total iron, and P were measured using ICP. The
concentration of chloride was determined by titration using
0.1N silver nitrate solution.
Screening Various Inhibitors
The main goal of the study was to select a scale inhibitor that
exhibits an optimum compatibility with various acid systems.
The selected scale inhibitor had to provide protection from
scale deposition, while maintaining the performance of the
acid treatment.
The following key performance criteria were considered
when selecting the optimum scale inhibitor:
(1) No change in the appearance or the rheology of the acid
system,
(2) Minimal precipitation upon mixing with the acid or
materials present in the wellbore, typically ferric iron or
calcite scale,
(3) No effect on the reaction kinetics or corrosivity of the acid
solutions, and
(4) Minimal loss in the performance of the inhibitor itself
when mixed in the acid.
Observations and results are summarized as follows:
In the initial screening, the inhibitors were mixed in a 7.5
wt% HCl system that contained a corrosion inhibitor, an
iron reducing agent and a chelating agent. None of the
inhibitors caused any noticeable change in the acid
appearance or viscosity either at room temperature or

SPE 87454

when heated to 150F.

Upon spiking the samples with 2,000 ppm of ferric iron
and heating the samples up to 150F, all the samples
showed precipitation. The precipitation in all samples was
less than 5 g/100 cm3, the level at which loss of injectivity
in subsequent core flow tests is commonly experienced.
Therefore, all inhibitors passed this screening test, Fig. 1.
Upon spending the samples with calcium carbonate, still
spiked with ferric iron, the samples that contained
inhibitors SI-2 and SI-4 showed precipitation in excess of
5 g/100 cm3, Fig. 2. Inhibitors SI-2 and SI-4 were then
eliminated from the comparison.
Samples of the remaining inhibitors mixed in the acid
system, only spiked with ferric iron with no calcium
carbonate added, were analyzed for the amount of iron
that remained in solution, versus the iron that precipitated
as a result of adding the scale inhibitor. All samples were
compared to a blank acid sample spiked with the same
amount of ferric iron without a scale inhibitor. The
sample containing SI-6 retained less than 35% of the
ferric iron compared to the blank acid. This indicated a
low tolerance to ferric iron contamination by SI-6 and
therefore SI-6 was eliminated. The rest of the samples
retained more than 80%, with SI-3 showing the highest
tolerance to ferric iron, Fig. 3.
The remaining three samples where then spent with
calcium carbonate and analyzed again for the retained
ferric iron. The sample containing SI-5 showed less
tolerance to iron in the spent acid system (65% retained),
but was not considered enough to eliminate SI-5. SI-3
showed the highest tolerance to ferric iron in the spent
acid, Fig. 4.
The retained phosphorous (of the original added
respective to each inhibitors phosphorous content) in
each sample of mixed inhibitor in acid, spiked with 2,000
ppm of ferric iron in all cases, before and after spending
with calcium carbonate, was analyzed. The % P retained
was used as an indication of the retained active inhibitor
in the sample. No excessive loss of active inhibitor was
noted in any of the samples, Fig. 5.
The effect of the scale inhibitors on the acids calcium
carbonate dissolving capacity, with samples spiked with
2,000 ppm of ferric iron in all cases, was also measured.
The capacities of all samples were compared to that of a
blank acid sample. Although SI-3 showed the highest
tolerance to calcium (the sample had exactly the same
dissolving capacity as that of the blank acid), the two
other samples showed a small effect on the acid capacity
to dissolve calcium, Fig. 6.
Continuing to evaluate the compatibility with other acid
systems, much of the same procedure was repeated using
a 9:1 mud acid system containing the same additive as the
previous HCl system. Figure 7 shows that the
precipitation levels when samples of the three inhibitors,
SI-1, SI-3 & SI-5, were mixed in the 9:1 mud acid system
spiked with 2,000 ppm ferric iron. None of the three
inhibitors showed excessive precipitation.

Again, much of the same procedure was repeated with a

chelating-agent based system, containing a corrosion
inhibitor. Figure 8 compares the effect of the three
inhibitors mixed in the chelant system on the systems
reaction kinetics measured by the rate of dissolution of
calcium carbonate. The performances of all samples are
compared to that of a blank sample of the chelating agent
system. Comparable dissolution rates where noted by the
three samples at 150F, while SI-3 actually enhanced the
dissolution rate of calcium carbonate by the chelating
agent at the lower temperature.

Criteria Used to Select Scale Inhibitor

The following factors were considered in order of priority:
1) The amount of precipitation: the three inhibitors, SI-1, SI3 and SI-5 produced precipitates less than 5 g/100 cm3;
therefore, the three inhibitors were acceptable.
2) Tolerance to calcium and ferric ions: Although the
difference was not significant, SI-3, the polymer-based
scale inhibitor, outperformed SI-1 and SI-5 in tolerance to
these two ions. Therefore, SI-3 was favored compared to
the other two inhibitors.
3) Wider applicability range: The improvement in the
calcium dissolution rate, by the chelating agent system at
the lower temperature, upon adding SI-3, was taken to be
a positive indication of the applicability of SI-3 in a wider
range of stimulation fluid systems. Therefore, SI-3 was
again favored compared to other two.
SI-3, the polymer-based scale inhibitor, was selected as the
optimum acid-compatible scale inhibitor out of the six
inhibitors examined in this study. This inhibitor contains
phosphorus, which can be used to measure the inhibitor
concentration in coreflood or field samples. This inhibitor
was subjected to extensive testing before conducting coreflood
tests.
Extensive lab tests were conducted to examine
compatibility of SI-3 with corrosion inhibitors. Combined
acid solutions that contained 15 wt% HCl acid, 0.3 vol% CI-B
and various concentrations of SI-3 were prepared. A black
precipitate was noted on the bottom and sides of the container,
Photo 1. It is clear from this experiment that the inhibitor
may interfere with the corrosion inhibitor at these conditions.
The same experiment was repeated with CI-A. No detectable
precipitate was observed for the first 24 hours. However, a
small amount of precipitate was observed after 24 hours. As a
result, it was decided to use CI-A in the coreflood
experiments. And the scale inhibitor was added to the acid
just before use.
Compatibility of SI-3 to calcium and Fe(III) ions in live
acid was examined over a wide range of concentrations. A
combined acid system was prepared such that acid
concentration was 15 wt%, and the concentration of calcium
was varied from 0 to 60,000 mg/L.
Another set of
experiments were done, but Fe(III) was used. In both sets, no
precipitate was noted until the concentration of Ca or Fe(III)
exceeded 50,000 mg/L. A small amount of precipitate was

noted at high concentrations of Ca and Fe(III) ions, Photos 2

and 3. These observations were noted at room temperature
and 150F. These results clearly indicate that SI-3 is tolerant
to very high levels of Ca and ferric iron.
The viscosity and density of combined acid solutions that
contained 15 wt% HCl and various SI-3 concentrations were
measured at ambient conditions, Table 3. The viscosity and
density of the acid solutions did not significantly change due
to the presence of the scale inhibitor, SI-3.
Results and Discussion
Inhibitor Adsorption/Desorption Berea Sandstone
A number of core flow tests were run to verify that the
inhibitor retention on mineral surfaces is not adversely
affected by the acidic conditions. In addition, it was necessary
to verify that the fluid system can be injected into sandstone
and carbonate cores across an acceptable permeability range
without causing formation damage. The inhibitor return
profile must remain at or above that seen for standard squeeze
treatments under equivalent conditions.
Figure 9 compares the inhibitor return profiles after two
coreflood tests, one mixing the inhibitor in an HCl acid system
(simulating the combined treatment) and the other mixing the
inhibitor in 2 wt% KCl brine (simulating an inhibitor squeeze
treatment). SI-3 was mixed in both the acid and the brine at a
concentration of 7.5 vol%. Berea sandstone cores were used in
these tests, with an average of 10-15 wt% feldspar, 5 wt%
clays, nearly 1 wt% calcite and the balance is quartz. The shutin time for inhibitor adsorption was 4 hours after flooding the
cores with the acid or the brine system containing the
inhibitor. Flowback was done at a rate of 5 cm3/min and the
tests were run at 150F. The inhibitor adsorption efficiency in
the sandstone core improved when it was mixed in acid,
evident by a consistently higher inhibitor return concentration
over the same volume of flow back fluid in both tests. The
scale inhibitor SI-3 is adsorbed on the rock surface via
hydrogen boning. As a result, its retention in the core will be
enhanced in the presence of the acid.
Coreflood Studies Using Sandstone Cores
Another set of experiments were conducted using sandstone
cores from reservoir H. Table 2 gives the mineralogy of the
cores used. The cores contained iron-containing minerals;
hematite and ankerite. The presence of the former mineral
gives the cores (core # 327) a reddish color as can be seen in
Photo 4a. Only data obtained from this core plug will be
discussed in the present paper.
Since the core contained clay minerals, 5 wt% KCl was
used in the pre and post flushes. Petrophysical properties of
this core include a porosity of 20.7 vol% and an air
permeability of 1,202 mD. The core plug was 1.5 inch in
diameter and 1.5 inch in length. Coreflood procedure included
injection of 5 wt% KCl at various flow rates. The KCl brine
was filtered to 0.2 m. Then 5 pore volumes of the combined
acid were injected followed by 5 wt% KCl. All fluids were
injected continuously, without allowing these fluids to soak in
the core. The pressure drop across the core during the

SPE 87454

injection of these fluids was closely monitored, Fig. 10. All

fluids were injected without indication of core damage.
Examination of the inlet face of the core after the treatment,
Photo 4b, did not indicate any filter cake or polymer retained
at the core face. These observations indicated that the
combined acid system is compatible with reservoir cores, and
is not expected to cause any damage in reservoir cores.
Figures 11 to 16 show the concentrations of acid and key
ions in the core effluent. Acid concentration reached the
injection levels (nearly 15 wt%) then rapidly decreased during
the injection of the postflush, Fig. 11. The pH decreased and
reached nearly zero during the injection of the acid, then
slowly increased and reached 3.5.
The chloride concentration was nearly 23,800 mg/L during
the injection of the 5 wt% KCl, Fig. 12. It increased to nearly
150,000 mg/L during the injection of the 15 wt% HCl
combined acid, then gradually decreased to its level in the
postflush, which is similar in this case as the preflush.
Figure 13 shows the concentration of phosphorus in the
core effluent. SI-3 contains phosphorus, as shown in Table 1,
and the presence of phosphorus during acid injection is a clear
indication of the propagation of the inhibitor in the core.
Figure 14 shows the concentration of potassium and
sodium in the core effluent. The concentration of potassium
was equivalent to that present in 5 wt% KCl. Potassium
concentration decreased during acid injection. The
concentration of sodium ion increased during acid injection.
The most likely source of sodium is the scale inhibitor.
Reservoir cores contained clays and carbonate minerals,
Table 2. It is of interest to examine the concentration of Ca,
Mg and total iron in the core effluent. The concentrations of
these cations will give an indication of acid reactions with
carbonate minerals present in the core: calcite, dolomite and
ankerite. Figure 15 shows that the concentration of the three
cations peaked during the acid injection. The concentration of
total iron was higher than that of Ca or Mg. The main sources
of iron are ankerite and hematite minerals present in the core.
Calcium ion was the second highest, followed by Mg. The
concentrations of the three cations decreased and reached
almost zero during the injection of the postflush.
Figure 16 shows the concentrations of aluminum and
silicon in the core effluent. The concentration of both cations
peaked during acid injection. The source of these two cations
is the clay minerals present in the core. It is well known that
HCl acid can extract aluminum from clay particles leaving
non-crystalline material.14-16 It is interesting to note that this
process did not cause damage to core at the test temperature.
The concentration of silicon is within its solubility limit in
hydrochloric acid.17
Coreflood Studies Using Carbonate Cores
Coreflood tests were also conducted using carbonate cores,
reservoir G. Only one case will be discussed in this paper.
The core is mainly calcite, with a porosity of 16.8 vol% and an
air permeability of 4.2 mD. This core is much tighter than the
sandstone core, Fig. 10. The length of the core plug was 1.7

SPE 87454

inches, whereas its diameter was 1.5 inches. Similar to the

coreflood conducted on sandstone cores, filtered 5 wt% KCl
brine was used in the pre and postflushes. Five pore volumes
of the combined acid were injected into the carbonate core.
The acid created deep wormholes, as shown in Photos 5a and
5b. Similar to the sandstone core, there was no evidence of
polymer retained on the face of the core.
Figure 17 shows the pressure drop across the core as a
function of the cumulative core effluent. The pressure drop
decreased once the acid reacted with the carbonate core. It
significantly decreased once the acid exited from the core,
through the wormholes. These results and those obtained
with sandstone core indicate that SI-3 can be injected into both
types of cores (sandstone and carbonate) without causing loss
of injectivity. There is no evidence that the inhibitor adversely
affected acid reactions with the minerals present in both cores.
Conclusions
The results obtained from this study indicated that the scale
inhibitor, SI-3, is compatible with most acid additives and can
tolerate high levels of calcium and iron (III) ions. Coreflood
tests, utilizing reservoir cores and Berea sandstone, indicated
that the combined acid system did not damage sandstone or
carbonate cores. There no evidence that the scale inhibitor SI3 affected acid-rock interactions
The combined acid system will significantly reduce well
maintenance and workover costs. It will improve placement
and performance of scale inhibitor treatments. In addition, it
will reduce the volume of aqueous phase introduced to the
formation. This is a very important factor in tight formations,
where water blockage is a major concern.
Acknowledgments
The authors wish to acknowledge the Saudi Arabian Oil
Company (Saudi Aramco) and Schlumberger, LTD for
granting permission to present and publish this paper. The
Elemental Analysis and Chemical Analysis Units of the Saudi
Aramco R&D Center were helpful in measuring the
concentrations of various ions and XRD/XRF analyses.
References
1. Lynn, J.D., Nasr-El-Din, H.A., and Hashem, M.K.:
Iron Phosphonate Stabilized Emulsions: Formation
Damage during an Adsorption Squeeze Treatment for
Scale Mitigation, paper SPE 73718 presented at the
2002 SPE Int. Symposium on Formation Damage
Control, Lafayette, LA, 20-21 February.
2. Al-Qahtani, A.M., Nasr-El-Din, H.A., Raju, K.:
Scale Inhibitor Squeeze Treatment in a Tight
Carbonate Reservoir Problems and Solutions,
paper SPE 80389 presented at the 2003 SPE Oilfield
Scale, Aberdeen, Scotland, 29-30 January.
3. Lewis, D.R., Zainalabedin, K.A., Al-Habib, N.S., AlBeaiji, T.M., Al-Qahtani, A.M., Nasr-El-Din, H.A.:
Scale Mitigation Enhances Safety and Production,
SPE 81569 presented at the 2003 SPE Middle East
Oil Show & Conference held in Bahrain, 9-12 June.

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13.

Lynn, J.D.: Development of the Ghawar Scale

Squeeze Simulation Model: Using Core Analysis to
Evaluate Treatment Chemicals, paper SPE 25589
presented at the 1993 SPE Middle East Oil Technical
Conference and Exhibition held in Bahrain, 3-6
April.
Nasr-El-Din, H.A., Lynn, J.D., Hashem, M.K., Bitar,
G.: Field Application of a Novel Emulsified Scale
Inhibitor System to Mitigate Calcium Carbonate
Scale in a Low-Temperature, Low-Pressure
Sandstone reservoir in Saudi Arabia, paper SPE
77768 presented at the 2002 SPE Annual Meeting,
San Antonio, TX, 29 September 2 October.
Al-Saiari, H.A., Nasr-El-Din, H.A., Lynn, J.D.,
Hashem, M.K., Bitar, G.: Field Application of an
Emulsified Scale Inhibitor System to Mitigate
Calcium Carbonate Scale in a Sandstone Reservoir in
Saudi Arabia: Field Monitoring and the Impact of
Descaling Treatment, paper NACE # 04385 to be
presented at NACExpo 2004 that will be held in
Houston, TX, March 28- April 1.
Lynn, J.D. and Nasr-El-Din, H.A.: A Novel LowTemperature, Forced Precipitation Phosphonate
Squeeze for Water Sensitive, Non-Carbonate Bearing
Formations, paper SPE 84404 presented at the 2003
SPE Annual Conference and Exhibition, Denver, CO,
5 - 8 October.
Nasr-El-Din, H.A., Lynn, J.D., Hashem, M.K., Bitar,
G., and Al-Ali, A.: Lessons Learned from Descaling
Wells in a Sandstone Reservoir in Central Saudi
Arabia, paper SPE 74690 presented at the 2002 SPE
Symposium on Oilfield Scale held in Aberdeen,
Scotland, 30-31 January.
Browning, F.H., et al.: Precipitation and Dissolution
of Calcium Phosphonates for the Enhancement of
Squeeze Lifetimes, SPEPF (1995) p. 144-150.
Vetter, O.J., Lankford, S., Nilssen, T., Shelton, M.:
Well Stimulation and Scale Inhibitors, paper SPE
17284 presented at the 1988 SPE Permian Basin Oil
and Gas Recovery Conference, Midland, TX, 10-11
March.
Smith, P.S., Clement, C.C., JR, and Rojas, A.M.:
Combined Scale Removal and Scale Inhibition
Treatments, paper SPE 60222 presented at the 2000
SPE Symposium on Oilfield Scale held in Aberdeen,
UK, 26-27 January.
Smith, P.S., Cowie, L.G., Bourne, H.M., Grainger,
M., and Heath, S.M.: Field Experiences with a
Combined Acid Stimulation and Scale Inhibition
Treatment, paper SPE 68312 presented at the 2001
SPE Symposium on Oilfield Scale held in Aberdeen,
UK, 30-31 January.
Frenier, W.W., et al.: Hydroxyaminocarboxylic
Acids Produce Superior Formulations for Matrix
Stimulation of Carbonates, paper SPE 68924
presented at the 2001 SPE European Formation
Damage Conference held in The Hague, The

SPE 87454

Netherlands, 21-22 May.

14. Simon, D.E. and Anderson, M.S.: Stability of Clay
Minerals in Acid, paper SPE 19422 presented at the
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Lafayette, LA, 22-23 February.
15. Nasr-El-Din, H.A., Hopkins, J.A., Shuchart, C.E. and
Wilkinson, T.: Aluminum Scaling and Formation
Damage due to Regular Mud Acid Treatment, paper
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Table 3: Viscosity and density of 15 wt% HCl + SI-3a

Concentration of SI-3, vol%

Density, g/cm3

Viscosity, cSt

1.078

1.370

10

1.086

1.284

a. Measured at ambient temperature

Photo 1: 15 wt% HCl + 0.3 vol% CI-B +

5 vol% SI-3

Surface
Table 1: Acid-compatible inhibitors examined. Phosphorus content is
based on the chemical as received
Inhibitor

Type

pH

P, wt%

SI-1

Phosphonate

6.7

3.5

SI-2

Phosphonate

3.8

18.5

SI-3

Phosphino-Polyacrylate

7.9

0.5

SI-4

Phosphonate

0.2

15.1

SI-5

Phosphonate

0.5

18.5

SI-6

Phosphonate

0.4

18.7

Photo 2: 15 wt% HCl + 5 vol% SI-3 +

6 wt% Ca

Table 2: Mineralogy of sandstone cores, reservoir H

Mineral
Quartz-SiO2

Sample
# 327
97

Sample
# 328
97

Sample
# 329
97

Kaolinite- Al2Si2O5(OH)4

Ankerite-Ca(MgFe)(CO3)2

Trace

Trace

Trace

Trace

Microcline-KAlSi3O8
Hematite-Fe2O3

Bottom

SPE 87454

Photo 3: 15 wt% HCl + 5 vol% SI-3 +

6 wt% Fe (III)

Photo 4: core # 327, Reservoir H

Before and after treatment
15 wt% HCl + 0.3 vol% CI-A + 5 vol% SI-3

Figure 1: Total weight of precipitate upon spiking the 7.5

wt% HCl acid system, containing different scale inhibitors,
with 2,000 ppm of ferric iron at 150F.

Figure 2. Total weight of precipitate upon spending the 7.5

wt% HCl acid system with calcium carbonate to a pH of 5,
containing the scale inhibitors and spiked with 2,000 ppm of
ferric iron at 150F.

Inlet before

Inlet after

Photo 5: core # 41, Reservoir G

Before and after treatment
15 wt% HCl + 0.3 vol.% CI-A+ 5 vol% SI-3

Inlet before

Inlet after

Figure 3: Percent iron that stayed in solution upon spiking the

scale inhibitor-acid blends with 2,000 ppm ferric iron. Percent
Fe is calculated based on the amount of iron that stayed in
solution in the straight acid without inhibitor.

Figure 4: Percent iron that stayed in solution upon spiking

different inhibitor-acid blends with 2,000 ppm ferric iron, then
spending the acid system with calcium carbonate to a pH of 5.
Percent Fe is calculated based on the amount of iron that
stayed in solution in the straight acid without inhibitor

Figure 5: Percent phosphorous that stayed in solution upon

spiking the different inhibitor-acid blends with 2,000 ppm
ferric iron, before and after spending with calcium carbonate
to a pH of 5. Percent P is calculated based on the amount of
phosphorous added with each inhibitor.

Figure 6: Effect of adding different inhibitors to the HCl acid

system on its dissolving capacity of calcium carbonate. The
test was up to the point at which Ca precipitation started.

SPE 87454

Figure 7: Total weight of precipitate upon spiking the 9:1

mud acid system, containing the scale inhibitors, with 2,000
ppm of ferric iron at 150F.

Figure 8: Effect of adding the scale inhibitors to chelatingagent based system on the rate of dissolution of calcium
carbonate, both at room temperature and at 150F.

Figure 9: A comparison between the scale inhibitor (SI-3)

return profile from Berea sandstone coreflood tests when
mixed once in 15 wt% HCl and once when mixed in 2 wt%
KCl brine. Tests were run at 150F.

HCl wt% & pH

12

0
1000
400

HCl

pH

1100
600

200

Reverse 5 wt% KCl at 2 cm /min

0
800

Cumulative Volume, cm3

1200
1000
1200

1300

Reverse 5 wt% KCl at 2 cm3/min

Forward 5 wt% KCl at 2

cm3/min

15 wt% HCl + 5 vol% SI-3 + 0.3

vol% CI-A at 1 cm3/min

Forward 5 wt%
KCl at 2 cm3/min

Reverse 5 wt% KCl at 3

cm3/min

Reverse 5 wt% KCl

at 2 cm3/min

Forward 5 wt% KCl at 3

cm3/min
Reverse 5 wt% KCl
at 1 cm3/min

15 wt% HCl + 5 vol% SI-3 + 0.3

3
vol% CI-A at 1 cm /min

2.5

Forward 5 wt%
KCl at 2

5
Forward 5 wt% KCl at
1 cm3/min

7.5

5 wt% KCl at 2 cm /min

Pressure Drop Across the

Core, psi

SPE 87454
9

Figure 10: Core # 327 Sandstone Reservoir "H"

(15 wt% HCl + 5 vol% SI-3 + 0.3 vol% CI-A)

10

1400
1600

Cumulative Volume, cm

Figure 11: Core # 327 Sandstone Reservoir "H"

(15 wt% HCl + 5 vol% SI-3 + 0.3 vol% CI-A)

16

1400

10

SPE 87454

Figure 12: Core # 327 Sandstone Reservoir "H"

(15 wt% HCl + 5 vol% SI-3 + 0.3 vol% CI-A)

100000

50000

0
1000

1100

Reverse 5 wt% KCl at 2

3
cm /min

5 wt% KCl at 2 cm /min

Chloride, mg/L

150000

15 wt% HCl + 5 vol% SI-3 + 0.3

3
vol% CI-A at 1 cm /min

200000

1200

Cumulative Volume, cm3

1300

1400

Figure 13: Core # 327 Sandstone Reservoir "H"

(15 wt% HCl + 5 vol% SI-3 + 0.3 vol% CI-A)

0
1000

1100

1200
Cumulative Volume, cm 3

Reverse 5 wt% KCl at 2 cm /min

15 wt% HCl + 5 vol% SI-3 + 0.3

3
vol% CI-A at 1 cm /min

100

5 wt% KCl at 2 cm /min

200

Phosphorus, mg/L

300

1300

1400

SPE 87454

11

Figure 14: Core # 327 Sandstone Reservoir "H"

(15 wt% HCl + 5 vol% SI-3 + 0.3 vol% CI-A)

10000
5000

Reverse 5 wt% KCl at 2 cm /min

15000

5 wt% KCl at 2 cm /min

K & Na, mg/L

20000

Na

vol% CI-A at 1 cm /min

K
25000

15 wt% HCl + 5 vol% SI-3 + 0.3

30000

0
1000

1100

1200

1300

Cumulative Volume, cm 3

1400

Figure 15: Core # 327 Sandstone Reservoir "H"

(15 wt% HCl + 5 vol% SI-3 + 0.3 vol% CI-A)

500
0
1000

1100

1200

Cumulative Volume, cm

1300
3

cm /min

Reverse 5 wt% KCl at 2

1000

vol% CI-A at 1 cm /min

1500

2000

Ca
Mg
Fe

15 wt% HCl + 5 vol% SI-3 + 0.3

Ca, Fe & Mg, mg/L

2500

5 wt% KCl at 2 cm /min

3000

1400

Pressure Drop Across the

Core, psi

10

Forward 5 wt%

200

400

600
3

Reverse 5 wt%

KCl at 2 cm /min

Forward 5 wt%

30

800

Cumulative Volume, cm 3

1000
3

Reverse 5 wt% KCl at 2 cm /min

cm /min

Forward 5 wt% KCl at 2

1200

vol% CI-A at 1 cm /min

Cumulative Volume, cm3

15 wt% HCl + 5 vol% SI-3 + 0.3

KCl at 3 cm /min

KCl at 2 cm /min

1100

Reverse 5 wt%

Reverse 5 wt% KCl at 2

3
cm /min

15 wt% HCl + 5 vol% SI-3 + 0.3

3
vol% CI-A at 1 cm /min

Si

Reverse 5 wt%

Al

KCl at 1 cm /min

0
1000

KCl at 3 cm /min

KCl at 2 cm /min

Forward 5 wt%

100

5 wt% KCl at 2 cm /min

200

300

20

Forward 5 wt%

400

KCl at 1 cm /min

Al & Si, mg/L

12
SPE 87454

Figure 16: Core # 327 Sandstone Reservoir "H"

(15 wt% HCl + 5 vol% SI-3 + 0.3 vol% CI-A)

500

1300
1400

Figure 17: Core # 41 Carbonate Reservoir "G"

(15 wt% HCl + 5 vol% SI-3 + 0.3 vol% CI-A)

1200