SPE 62825

Matrix Acidizing of Water Injectors in a Sandstone Field in Saudi Arabia: A Case Study
H.A. Al-Anazi, SPE, H.A. Nasr-El-Din, SPE, M.K. Hashem, SPE, and J.A. Hopkins, SPE,
Saudi Arabian Oil Company (Saudi Aramco)

Copyright 2000, Society of Petroleum Engineers Inc.

This paper was prepared for presentation at the 2000 SPE/AAPG Western Regional Meeting
held in Long Beach, California, 1923 June 2000.
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Abstract
The aims of this study were to design a cost-effective
stimulation treatment to remove formation damage from water
injectors in a recently developed sandstone field in Saudi
Arabia and enhance well injectivity, while maintaining
formation integrity. This paper examines the design of the
treatment, field monitoring, and analysis of acid returns. Core
flow experiments were performed to screen various acid
formulations, and evaluate acid additives.
The designed treatment was applied on several water
injectors. Acid returns were analyzed to evaluate the
effectiveness of each treatment. It was found that a preflush of
5wt% NH4Cl solution was effective in displacing potassium
and sodium ions from feldspars and clay minerals compared to
a preflush that contained hydrochloric acid only. A multi-stage
treatment was designed to remove formation damage
encountered in several water injectors in this field. The
treatment significantly improved the injectivity index of the
treated wells.
Introduction
A newly developed field produces oil from sandstone
formations in the Central Saudi Arabia. Water injection is
used to maintain reservoir pressure and sweep oil. The first
water injection wells completion was started in March of
1997. The injection water was supplied from an aquifer that has
variable water quality and sulfate-reducing bacteria (SRB)
related problems. These bacteria produce biomass and iron
sulfide which cause significant loss of the injectivity1,2.
Based on our experience in a nearby sandstone field, water
injection wells in this new field may be damaged due to SRB
activities or invasion of drilling and completion fluids. Also,

low water injection rates can be encountered in some wells

which have low permeability. Various acid formulas are
available for acidizing purposes and each formula can be used
under a certain range of reservoir conditions. Therefore, the
objectives of this study were to: (1) design a cost effective
stimulation treatment to remove formation damage, and (2)
enhance the injectivity into low permeability zones.
Experimental Studies
Coreflood experiments were conducted using reservoir rocks and
conditions. Core plugs were selected from three wells in this
field. The injection water was synthesized in the lab according to
the chemical composition given in Table 1. Various acids were
used including: three formulas of HCl acid (Acid-I, Acid-II, and
modified Acid-II), and a retarded HF acid based on aluminum
chloride. The formulas of these acids are given in Table 2.
In each coreflood experiment, the core was first loaded
into a Hassler sleeve core holder at an overburden pressure of
2,500 psig and a temperature of 188F (reservoir temperature).
The core was subjected to vacuum for an hour. Then, it was
saturated with injection water until the brine permeability
became constant (10%). The acid was injected into the core
and followed with injection water as a postflush, until the core
permeability stabilized. Then, the brine injection was changed
to the reverse direction to simulate the injection well when it is
put on backflow cycle. The injection rate was tested at 2 and 4
ml/min. The injection mode was changed to the forward
direction to assess the potential of permeability loss due to
acid treatment. A new core plug was used in each experiment.
The concentrations of key ions in the core effluent were
measured. Calcium, magnesium, sodium, potassium,
aluminum, silicon, and total iron ions were analyzed by
Induced Coupled Plasma Emission Spectrometry (ICP).
Sulfate ion in the aqueous phase was measured
turbidimetrically following precipitation with a barium
chloride solution (0.1N). The detection limit is nearly 20 ppm
and precision is 5%. The concentration of hydrochloric acid
was measured (5%) by acid/base titration using 0.1 N NaOH
solution. X-Ray Powder Diffraction (XRD) and was used to
identify the crystalline material of the particulate solids
collected in the core effluent during coreflood experiments
and in acid returns. XRD analysis was also used to identify the
bulk mineralogy of field cores.

H.A. AL-ANAZI, H.A. NASR-EL-DIN, M.K. HASHEM, J.A. HOPKINS

Results and Discussion

Mineralogy of Reservoir Cores
Table 3 lists the bulk mineralogy of reservoir cores as
determined by XRD analysis. Quartz represents average values
of 84 and 83wt% in Well-A and B, respectively. The examined
cores contain large amounts of K-feldspar (5-18wt% for Well-A
and 6-12wt% for Well-B). These feldspars react with HF and
may cause precipitation of potassium fluosilicate. The presence
of potassium feldspar at high concentrations is of a major
concern if a retarded HF acid based on fluoboric acid is used.
This is because of potential precipitation of potassium fluoborate
which may damage the formation.
Clay minerals in the bulk sample ranged from 1-6wt% for
Well-A and 1-5wt% for Well-B. The clay fraction was
separated from the bulk sample and analyzed by XRD. Clay
minerals were reported as chlorite, kaolinite, and
illite/montmorillonite mixed layer. Illite and montmorillonite
(smectite) are the dominant clay minerals present in the core
samples. These minerals were detected as ordered mixed
layers. Sample#199 of Well-A had the highest concentration
(5.86wt%) of illite/montmorillonite ordered mixed layers
(97.7wt% of the total clays). Illite and smectite swell upon
contact with fresh water or polar liquids3,4. Illite may cause
severe damage by pore throat bridging because it is a fibrous
clay that can be detached or transported by high flow rates5.
Smectite may also damage the formation by clogging pore
throats by dispersed clays. Clay migration can be controlled
by proper design of the injected fluid and using suitable clay
stabilizers6-8.
Chlorite is an iron-rich clay which is partially soluble in
hydrochloric acid. During acidizing, iron is extracted from
chlorite leaving amorphous silica to precipitate9. Chlorite may
also cause pore lining where clays attach to the pore wall thereby
causing permeability to decline. Chlorite was found only in
Sample#199 (Well-A) and Sample#133 (Well-B): 0.07wt% and
0.03wt%, respectively. The presence of this type of clay in
reservoir cores requires the use of iron control agents during well
stimulation to minimize precipitation of iron compounds which
can cause formation damage10. Kaolinite is classified as a nonswelling clay. However, it is dispersed easily and behaves as
migrating fines through rock pores. Kaolinite migration can be
controlled by using clay stabilizers in the postflush after HF
stimulation5. Kaolinite content varied in the examined cores:
Sample#106 of Well-B had the highest amount (1.44wt%) of
kaolinite which represented 51.4wt% of the total clay minerals.
Hydrofluoric acid reacts with clay minerals at different
rates and disturbs the equilibrium of their structures. Some of
clay particles detach from the pore surface and move freely
through the pore spaces. This movement or fines migration
can cause accumulation of fines in the pore throats and
damage the formation. Accordingly, a clay stabilization
technique should be employed directly after HF acidization to
prevent fines migration in the studied field.
Evaluation of Acid-II Formula
Acid-I formula was successfully used to remove biomass and
iron sulfide. Two reducing agents were added to this acid to

SPE 62825

improve its efficiency to control iron precipitation. The new acid

formula is known as Acid-II. Similar to Acid-I, a hydrogen
sulfide scavenger was included in Acid-II formula. Because this
acid was never tested before, the first objective of the present
study was to evaluate its injectivity and propagation in reservoir
rocks. A core sample (Sample#68 @ 8,877.4 ft) from Well-B
was used to evaluate this acid. Fig. 1 shows the pressure drop
across the core as a function of the cumulative core effluent. The
pressure drop sharply increased to 472 psia after acid injection
due to acid propagation into the core. After injecting 8.12 PV of
the postflush, the pressure drop gradually decreased until it
stabilized at 410 psia. This increase in the pressure drop
indicated a loss of core permeability. To assess the effect of
Acid-II formula on core permeability, the core initial and final
brine permeabilities were determined using Darcys equation.
The return permeability ratio was defined as the ratio of the
injected fluid permeability to the initial brine permeability. The
core permeability decreased by 20% after the injection of AcidII. The final brine permeability was 93% of the initial one after
the postflush by the brine.
Another coreflood experiment was performed on a
different core (Sample#243 @ 8907.0 ft) from Well-A. Fig. 2
shows the pressure drop across the core as a function of the
cumulative core effluent. After injecting 1 PV of Acid-II, the
pressure drop increased from 92 to 136 psia. During the acid
displacement by the brine, the pressure drop decreased and
stabilized at 104 psia. When the brine injection was changed
to the reverse mode, the pressure sharply dropped and
stabilized at 88 psia. Because of filter cake formation and
subsequent decline in core permeability, it was thought to
increase the injection flow rate to reduce the formation of filter
cake. Therefore, a third coreflood experiment was conducted on
a core (Sample#52 @ 8861.3 ft) from Well-B at a higher flow
rate (4 ml/min). The pressure drop across the core is given in
Fig. 3 as a function of the cumulative core effluent. During the
brine saturation stage, the pressure drop across the core was
stable at 226 psia. After the injection of 1 PV of Acid-II, the
pressure drop sharply increased to 670 psia. When the brine
(postflush) injection was changed to the reverse direction, the
pressure drop abruptly decreased to 100 psia and finally
stabilized at 410 psia. The sharp decline in the pressure indicates
a face plugging which is in agreement with the previous results
(Figs. 1 and 2). To simulate the injection cycle, the brine was
injected into the forward direction and the core permeability was
measured. The final core permeability decreased by 27% after
the injection of Acid-II. This reduction in the pressure drop
observed in these experiments indicated that the Acid-II formula
formed a filter cake (face plugging) which reduced the core
permeability. This result indicates that this acid can reduce well
injectivity and, as a result, it is not recommended for field
application.
HCl concentration and pH in the core effluent are shown in
Fig. 4. The spent acid concentration reached a maximum of
2.2wt%/v% in the core effluent. The HCl acid reacts with
carbonate minerals and alumino-silicates which are present in
the core. This excess HCl in the core effluent helps to
maintain iron compounds dissolved in solution as will be

SPE 62825

MATRIX ACIDIZING OF WATER INJECTORS IN A SANDSTONE FIELD IN SAUDI ARABIA: A CASE STUDY

discussed later. After acid injection, the pH dropped from 7.4 to

less than 1 due to the arrival of the spent acid. After 18 PV of the
brine (postflush), the pH reached a value of 7.4 which is close to
the pH of the injected brine (Table 1). As a result, the spent acid
needs to be displaced by a large volume of the brine as a
postflush. It is recommended to flowback the well for a longer
period of time, until the pH of the return becomes greater than a
value of 4 to 5.
Fig. 5 illustrates the aluminum and total iron
concentrations in the core effluent. The aluminum
concentration sharply increased to 2,474 mg/l after the acid
injection, then, it reached a value less than 10 mg/l after the
core was post-flushed by 20 PV of the brine. This increase in
the aluminum ion concentration corresponded to the increase
in the HCl acid concentration (Fig. 4). Aluminum is present in
feldspars, and clay minerals. Bryant and Buller (Ref. 11)
found that the HCl extracted aluminum from alumino-silicates
in sandstone cores. They also found that the removal of
aluminum from alumino-silicate minerals lattices weakens the
structure of the clay particles and may induce fines migration.
Simon and Anderson (Ref. 12) found that chlorite is more
susceptible to HCl acid attack than illite, kaolinite, and
feldspars minerals. Because the examined reservoir cores
contained high amounts of alumino-silicate minerals (Table
3), the increase in the aluminum concentration in the core
effluent was most likely due to acid reactions with these
minerals. The total iron concentration profile behaved similar to
that of aluminum. However, the total iron concentration
increased to a maximum level at 5,225 mg/l, then dropped to less
than 1 mg/l during the postflush. The increase in the total iron
concentration occurred when the pH was low (<2). The HCl acid
leached iron from chlorite which was present in reservoir cores
(Table 3). This high level of iron was kept dissolved in the spent
acid due to the presence of the iron control agent and the excess
HCl acid which provided low pH (Fig. 4) environment13. The
amount of the iron control agent added to Acid-II formula was
enough to keep iron compounds in solution.
Fig. 6 shows the calcium, magnesium, silicon, and sulfate
ions concentrations in the core effluent. The calcium
concentration in the injected brine was 797 mg/l (Table 1).
Therefore, any increase in the calcium content above this
value results from acid/rock reactions. The calcium
concentration increased sharply from 800 to 4,845 mg/l then
decreased to reach an average value of 800 mg/l which is close
to the original calcium concentration present in the used brine.
The increase in the calcium concentration was due to the
dissolution of calcium containing materials by HCl acid. This
dissolution reaction explains the drop in the HCl acid
concentration (Fig. 4) in the core effluent. As a result, a
preflush of HCl is needed to dissolve calcium carbonate
materials before acidizing by HF to avoid a precipitation of
calcium fluoride which causes severe formation damage13-15.
After the acid had been injected, magnesium concentration
increased from 450 to 1,772 mg/l, then it decreased to a
constant value of 451 mg/l which is equivalent to the
magnesium content in the injected brine (Table 1). The
increase in the magnesium concentration was due to the

reaction of HCl acid with dolomite and/or ankerite which are

present in the core. The mass ratio of calcium to magnesium
in dolomite [CaMg(CO3)2] is 1.65. By comparing the results in
Fig. 6, the ratio of calcium to magnesium ion concentration
was 3.1 which is higher than that in dolomite. This result
means that the HCl acid reacted with dolomite besides other
carbonate contained materials. Because the XRD analysis
(Table 3) did not show any of carbonate materials in the core
plugs examined, it appears that the mineralogy in the studied
field varies with depth and location in the field. The silicon ion
concentration reached 1,331 mg/l after acid injection, then it
dropped to 52 mg/l at the end of the postflush. The initial
increase in the silicon concentration was due to the acid reactions
with feldspars and clay minerals which produced dissolved
silicon ions. A similar trend was noted by Ref. 11. After the
injection of 1 PV of Acid-II, the sulfate concentration dropped
to 1,776 mg/l. Then, the sulfate concentration reached 3,517
mg/l after displacing the injected acid by 6 PV of the brine as
a postflush. The drop in the sulfate concentration occurred
simultaneously with the increase in the acid concentration in
the core effluent (Fig. 4). The decline in the sulfate
concentration was due to dilution with the low sulfate content
acid. However, the dilution factor of the sulfate concentration
was 48% which is higher than that observed with the sodium
ion (41%). This result means that a part of the anhydrite
present in the core (Table 3) dissolved in the injected acid.
The dissolved sulfate ion will precipitate once the pH
increases and can further decrease the core permeability.
Therefore, it is very important to prepare the acid in a lowsulfate content water to minimize calcium sulfate
precipitation. During acid preparation, it was noted that a brown
layer separated at the top of the Acid-II. This layer disappeared
with mixing, but it formed when mixing was ceased. Thus, the
acid should be injected while mixing to avoid phase separation.
It was also observed that some solids precipitated in 3 tubes of
the core effluent after acid injection. The XRD analysis indicated
that the dominant mineral present in the solids is halite [NaCl],
and the secondary mineral is calcite [CaCO3]. There are also
trace amounts of quartz [SiO2], anhydrite [CaSO4], and gypsum
[CaSO4.2H2O].
Evaluation of Acid-I Formula
Acid-I formula was used successfully to stimulate water injectors
in a currently producing sandstone field, but it was not tested in
the new field. A core from Well-C (Sample#92 @ 8905.2 ft) was
subjected to 18 PV of the brine at a flow rate of 2 ml/min. Then,
1 PV of Acid-I was injected at the same flow rate. The initial
brine permeability of the core was 43.1 md. Then, the pressure
drop across the core decreased to less than 1 psia after acid
injection. The core permeability improved by a factor of 4. To
further confirm the results obtained with the Acid-I, another
coreflood experiment was conducted on a different core
(Sample#93 @ 8906.2 ft) from Well-C. During the displacement
of the acid with the brine, the pressure drop gradually decreased.
This trend was also observed in the first experiment. In other
words, Acid-I formula did not form a filter cake similar to that

H.A. AL-ANAZI, H.A. NASR-EL-DIN, M.K. HASHEM, J.A. HOPKINS

noted with Acid-II. The final core permeability increased by a

factor of 1.3.
The effect of Acid-I volume (1 to 4 PV) was also
investigated using different core plugs. Fig. 7 shows the final
permeability ratio as a function of injected acid (Acid-I)
volume. The final core permeability ratio increased as the
injected acid volume was increased. The increase in the core
permeability was due to the dissolution of carbonate minerals
and other acid soluble minerals by the acid. The results shown
in Fig. 7 indicate that increasing the acid volume improves the
efficiency of the stimulation job. However, it will take long
periods of time to lift this acid from the formation. Incomplete
lifting of the acid may cause severe corrosion to the well casing.
To determine the lifting requirements, the postflush volume
required to raise the pH of the core effluent to a value greater
than 4 as a function of injected Acid-I volume is also shown in
Fig. 7. The volume of the postflush required to displace the spent
acid is directly proportional to the injected acid volume. For
instance, when 4 PV of Acid-I were injected, more than 20 PV
of the postflush were needed to raise the pH of the core effluent
up to 4. Accordingly, it is very important to realize that the time
required to lift the acid will increase as the volume of the
injected acid increases.
Evaluation of Modified Acid-II Formula
The results obtained regarding Acid-II formula were
confirmed by the service company. To eliminate the filter cake
observed with this acid, the reducing agent was removed from
the acid formula. It should be noted that this chemical is used
to increase the reduction rate of iron reducing agent in HCl
acid. The results obtained using the modified Acid-II formula
(Table 2) are shown in Fig. 8. Similar to the results obtained
with Acid-I no decline in injectivity was noted with the
modified formula of Acid-II. Based on these studies, Acid-I and
modified Acid-II formulas did not cause sanding and/or
injectivity problems. Therefore, either Acid-I or modified AcidII can be used in stimulation of water injection wells in this field.
Evaluation of RHF
Retarded hydrofluoric acid (RHF) is used to generate HF acid at
slower rate which leads to deep penetration of live HF16,17. The
retarded HF system (Table 4) examined in the present study is
based on aluminum chloride. Ammonium bifluoride reacts with
the HCl acid and generates HF acid. When AlCl3 is added to HF
acid, the aluminum ions form aluminum fluoride complexes
which retard the formation of HF acid. Gdanski (Ref. 17)
discussed the retardation chemistry of this system in detail.
Because the formation has a high content of feldspars (Table 3),
lower HF concentration should be used to avoid undesirable
precipitation2,18. Table 5 gives the chemical composition of the
RHF formula. The concentration of HF acid in the RHF formula
is 1.2wt%/v%, while the total acidity in terms of HCl acid is
16.9wt%/v%. Acetic acid at a concentration of 3vol.% was
added to the RHF to provide a low pH environment which
prevents precipitation of aluminum fluoride complexes once the
HF acid is spent19.

SPE 62825

The first coreflood experiment was performed on a core

(Sample#245 @ 8903.5 ft) from Well-A at a flow rate of 2
ml/min. The core was subjected to the following fluids in
sequence: brine, 2 PV 15wt% HCl + 0.2wt% corrosion
inhibitor, 1 PV RHF, 2 PV 5wt% NH4Cl + 2wt% clay
stabilizer, and brine. The solution contained the clay stabilizer
was filtered using a 0.2 m filter paper. All the fluids were
injected in the forward direction, except the final stage of the
postflush (brine) was injected in the reverse mode. The
pressure drop across the core was 24 psia during the first stage
of the brine injection. Then, the pressure drop across the core
increased up to 120 psia after injecting the acids (HCl and
RHF) and dropped to 96 psia in the postflush by the brine in
the reverse direction. Therefore, the permeability ratio was
0.25. This permeability ratio indicated that the core was
damaged due to the injected acids.
The concentrations of sodium and potassium ions in the
core effluent are given in Fig. 9. The sodium concentration
dropped from 5,700 to 2,136 mg/l which is close to the
concentration of sodium in the injected RHF (Table 5). Thus,
this initial drop in the sodium concentration was due to the
dilution by the spent acid and/or fluosilicate precipitation. The
concentration of sodium increased again to 4,729 mg/l as a
result of the RHF reaction with sodium feldspar which is
present in the core (Table 3). However, it sharply dropped to
less than 700 mg/l during the postflush and returned to 5,761
mg/l which is the same as the sodium concentration in the
injected brine. The decline in the sodium concentration was
accompanied by an increase in the pressure drop across the
core. This result indicates that the core might be damaged due
to precipitation of sodium fluosilicates (Na 2SiF6). The
concentration of potassium (Fig. 9) increased up to 2,230 mg/l
because of the RHF acid reaction with potassium feldspar (Table
3). The concentration of potassium ion in the core effluent was
similar to that noted with sodium ion. The drop in the potassium
concentration indicated precipitation of potassium fluosilicate
(K2SiF6). Precipitation of sodium or potassium fluosilicates in
the core is of a major concern because they can reduce the core
permeability and induce severe formation damage. Therefore, it
is very important to displace these ions before the injection of
any form of HF acid.
Fig. 10 combines the concentrations of aluminum and silicon in
the core effluent. After the injection of HCl and RHF acids, the
aluminum concentration fluctuated between 2,000 to 12,000
mg/l. It is important to note that the RHF acid contained 4,626
mg/l aluminum. Thus, any increase in the aluminum
concentration above this level is due to the reaction of the RHF
acid with clay minerals and feldspars. The aluminum
concentration dropped to less than 1,000 mg/l, which coincides
with the increase in the pressure drop across the core. It appears
from these results that increase in the pressure drop was due to
precipitation of aluminum complexes. The silicon concentration
increased to 207 mg/l as a result of the reaction of HF acid with
clay minerals and silica, then it dropped to a minimum of 71
mg/l, and finally it sharply increased to 376 mg/l. The silicon
concentration measurements were repeated two times, but gave

SPE 62825

MATRIX ACIDIZING OF WATER INJECTORS IN A SANDSTONE FIELD IN SAUDI ARABIA: A CASE STUDY

the same values ( 2%). Although HF acid can dissolve more

silicate materials compared to HCl acid, the concentration of
silicon in the core effluent was below expectations. According to
the results shown in Fig. 6, HCl acid at a concentration of
7.5wt% dissolved silicon ion up to 1,331 mg/l. The
concentration of silicon in the core effluent was relatively low in
the case of RHF acid. This indicates that most of the silicate
materials dissolved by the RHF precipitated inside the core in the
form of hydrated silica which damaged the core. The silicon
concentration decreased with a corresponding increase in the
aluminum content. Therefore, some of the silicon which was
dissolved by the HF acid precipitated in the core because the
aluminum has a greater affinity for fluorides than silicon21,22.
To enhance the overall efficiency of the stimulation job,
the concentrations of sodium and potassium ions should be
reduced. One way to achieve this goal is to use a preflush of
ammonium chloride. A stage of 2 PV NH4Cl solution at
concentration of 5wt% was added as a preflush to the previous
stages on a new core (Sample#125 @ 8944.0 ft, Well-C). The
new added stage helped to improve the core permeability by a
factor of 1.2. Fig. 11 depicts the silicon and aluminum
concentrations in the core effluent. Both the silicon and
aluminum concentrations increased and reached a maximum of
1,116 and 6,386 mg/l, respectively. This increase in the
concentrations of the silicon and aluminum ions was due to the
dissolution of clays and siliceous materials by HCl and RHF
acids. It can be noticed that the concentrations of silicon and
aluminum ions increased smoothly without the decrease which
was observed in Fig. 10. Therefore, the new stage of 5wt%
NH4Cl solution preflush minimized precipitation of hydrated
silica, fluosilicates, and/or aluminum fluorides. Sodium and
potassium ion concentrations are plotted in Fig. 12. The sodium
ion concentration decreased by 66% compared to that in the
injected brine due to the dilution with acids which were prepared
in a low-sodium content water (Table 5). Also, the decrease in
the sodium concentration was prolonged for 3 PV compared to 6
PV in Fig. 9. Accordingly, the amount of sodium fluosilicate
precipitate, if present, is less than that formed in the previous
experiment without using NH4Cl solution as a preflush. The
same trend was observed for the potassium ion concentration
which increased due to the reaction of acids with feldspars. For
this purpose, the benefit of the preflush of NH4Cl solution is to
displace the cations (Na+ and K+) from the core, to minimize the
contact between the HF-silicates reaction products and these
cations, and to avoid undesirable precipitation21.
Stimulation Program
The recommended procedure to stimulate power water injectors
in the new field was as follows:
Preflush Stage. The objective of this stage is to remove calcium
and other divalent ions away from the wellbore area.
Ammonium chloride solution at a concentration of 5 wt% should
be used. The volume of the treatment is 100 gal/ft of
perforations.
First Acid Treatment. This stage consists of 15 wt% HCl with
several additives. The objective of this stage is to remove

damage due to iron sulfide and biomass. This acid will also
remove calcium and magnesium away from the wellbore area.
The recommended acid volume is 120 gals/ft of perforations. A
soaking time of 45 minutes is recommended. This time period
should be enough to remove the damage, while maintaining the
integrity of the formation.
Nitrogen Lift. Nitrogen lift is important to lift particulate solids
from the wellbore. It is recommended to add a foaming
surfactant during the nitrogen lift. Using a viscofier, a watersoluble polymer, is also recommended to increase the efficiency
of removing sand particles, if present, from the wellbore. Adding
a biocide at 2,000 ppm to the polymer slug is recommended to
protect the polymer (biopolymer) from bacteria.
Injectivity Test. After the removal of solid particles from the
wellbore, an injectivity test should be conducted. It is strongly
believed that the first acid treatment will remove all plugging
material (iron sulfide and biomass) and a good injectivity should
be obtained. Filtered ammonium chloride solution at 5 wt%
should be used during the injectivity test. If a good injectivity is
obtained at this stage, then there is no need to proceed with the
injection of the RHF acid, and injection of water should be
resumed.
RHF Acid Treatment. Failure to obtain good injectivity at this
stage means that the either damage is deep in the formation or
the formation has a tight permeability range. In this case, a half
strength retarded HF acid can be used to enhance well injectivity.
Decreasing the volume proposed for this treatment to 50-75
gals/ft of perforations is recommended (the higher limit applies
for tight zones). The soaking time should not exceed 30 minutes.
Postflush. After the second acid treatment, a postflush of 5wt%
HCl + 5 wt% ammonium chloride should be injected. Increasing
the volume of the postflush to 100 gals/ft of perforations is
strongly recommended. It is extremely important to inject large
volumes of ammonium chloride to remove the reaction products
away from the wellbore area. Another injectivity test can be
done during the injection of ammonium chloride solution into
the formation. The addition of HCl is needed to maintain a low
pH environment which will prevent secondary or tertiary
precipitation.
Clay Stabilizer. A clay treatment is recommended when an HFbased acid is used. A suitable clay stabilizer at a concentration of
2wt% is recommended. The clay stabilizer solution should be
prepared in 5wt% ammonium chloride and should be filtered
using a 10-micron filter.
Field Application
Based on an extensive lab work, a stimulation program was
recommended to acidize Well-D. This well was completed on
March 1997. The treatment was performed June 1997. The well
injectivity increased after performing the first acid treatment
(15wt% HCl). Table 6 lists the treatment stages used in
stimulation of Well-D. Due to the treatment, the well injectivity
index has increased by 10-fold. During the backflow period, 58
samples were collected over the period of four days (06/2907/02/1997). It was observed that all the collected samples
contained particulate solids. The solids were separated using

H.A. AL-ANAZI, H.A. NASR-EL-DIN, M.K. HASHEM, J.A. HOPKINS

0.45 m filter papers and analyzed by XRD. Aqueous phases

were analyzed for key ions. Table 7 gives the chemical analyses
of HCl samples collected from the top and bottom of the filter.
The acids collected from the top and bottom of the filter
contained 111 and 89 mg/l of total iron, respectively.
Fig. 13 shows the HCl concentration and pH values in the
acid returns of Well-D. The HCl acid concentration increased
after 42 hours (at 22:45, 07/01/97) from the backflow and
reached a maximum concentration of 4.9wt%/v% at 24:15.
The presence of the HCl in the acid returns lasted for 4.25
hours. The presence of HCl in the fluid returns indicates the
arrival of the spent acid. Not all the injected acid was
consumed during the treatment. However, the remaining acid
is needed to minimize precipitation of iron compounds which
might cause further formation damage. The pH ranged from 6 to
8 during the first 42 hours of the backflow. Then, it dropped to
less than 1 for a period of three hours. This decrease in the pH
occurred simultaneously with the increase in the HCl
concentration. This signifies the arrival of the spent acid. At the
end of the backflow, the pH reached a value of 3. Therefore,
measuring the pH of the return fluids during the backflow gives
an indication about lifting the spent acid from the formation.
The total iron and aluminum concentrations in the acid returns
are shown in Fig. 14 as a function of time. The total iron
concentration increased and reached a maximum of 14,374
mg/l after 44 hours from the backflow and gradually decreased
to less than 100 mg/l. The concentration of total iron in the
fluid returns was extremely high. Iron compounds remained in
solution because the pH of the acid returns was less than 1.
Also, the addition of iron control agent to the injected acid did
help in keeping the iron in solution. High iron concentrations
were also observed in core flood experiments. The source of
this iron is the iron containing minerals that are present in the
formation. The aluminum concentration in the fluid returns
behaved in a similar way as that noted with the total iron. The
aluminum was leached from the clays by the acid. The
presence of high values of total iron and aluminum in the acid
returns indicates that the formation is rich in iron/aluminum
contained minerals. Therefore, a large amount of HCl preflush
is needed to dissolve carbonate minerals and reduce aluminum
concentration near the wellbore area. This will reduce the
consumption of HF with these minerals and, as a result, HF
will react with clays and feldspars.
It is interesting to note that the potassium concentration
was high (>33,000 mg/l) in the samples collected during the
first 5 hours from the backflow (Fig. 15). It then decreased to
less than 2,000 mg/l in the rest of the acid returns. The main
sources of potassium ion are drilling and workover fluids
which contain KCl. Potassium chloride was added to these
fluids as a temporary clay stabilizer. The sodium concentration
(Fig. 15) increased from 1,300 mg/l to more than 3,000 mg/l
because of the arrival of the injected water (Table 1), the
dissolution of feldspars22, and ion exchange with the ammonium
ion8. As a result, ammonium chloride solution displaced
potassium and sodium ions from clays and feldspars and
prevented precipitation of fluosilicates when HF acid was used.

SPE 62825

The solids collected from the acid returns were divided

into four groups based on the date of the backflow period.
Table 8 gives the minerals identified by XRD analysis. Group
1 consisted of sylvite [KCl], magnetite [Fe3O4], and quartz
[SiO2]. The most likely source of sylvite is the workover
fluids. The source of magnetite is corrosion product or the
formation. The second group collected on 06/30/97, consisted
of quartz, magnetite, and halite. Calcite [CaCO3] was detected
as a major compound in Group 3. The sources of quartz and
goethite [FeOOH] present in Group 4 are the formation and
iron compounds, respectively. The second acid treatment was
performed on Well-E. The treatment was successfully applied
where by it enhanced the injection rate of the well. The change in
the ion concentrations in the acid returns of Well-E is very
similar to those obtained from the stimulation of Well-D.
Conclusions
1. The examined cores contained a large amount of Kfeldspar (5-18wt% for Well-A and 6-12wt% for Well-B).
Therefore, it is not recommended to use RHF acid based on
fluoboric acid to stimulate water injector in this field.
2. Clay minerals present in the bulk sample ranged from 16wt% for Well-A and 2-5wt% for Well-B. Clay minerals were
reported as chlorite, kaolinite, and illite/montmorillonite
mixed layer.
3. Reservoir cores contained high contents of iron and low
concentrations of carbonate materials. Therefore, there is a
need to add an iron control agent to the injected acids.
4. Acid-II formula caused a filter cake formation and
injectivity problems. Therefore, this acid is not recommended
for field application.
5. Acid-I and modified Acid-II formulas did not cause
injectivity problems in coreflood experiments. Thus, either
one can be used in stimulation of water injection wells in the
studied field.
6. A preflush of 5wt% ammonium chloride solution was
effective in enhancing the final permeability after RHF
stimulation. It appears that this preflush displaced sodium and
potassium from the core and minimized precipitation of
fluosilicates.
7. Increasing the volume of HCl (15wt%) acid improved
the efficiency of the RHF acid in improving the permeability
of reservoir cores.
8. A multi-stage stimulation treatment was designed to
remove formation damage to enhance wells injectivity in the
new developed field. The recommended treatment was
successfully applied in Well-D and Well-E.
Acknowledgments
The authors would like to thank the Ministry of Petroleum and
Mineral Resources and Saudi Aramco for permission to
publish this paper. We acknowledge the Chemistry Unit for
performing chemical analyses of the core effluent and the acid
returns, and the Advanced Instruments Unit for conducting
bulk and clay XRD analyses. The efforts of O.A. Al-Harthi,
M.S. Al-Jawfi, and T.A. Al-Shafai are highly appreciated for

SPE 62825

MATRIX ACIDIZING OF WATER INJECTORS IN A SANDSTONE FIELD IN SAUDI ARABIA: A CASE STUDY

conducting lab experiments. We want to thank fields

personnel for collecting samples from the studies wells.

19. Shuchart, C.E., and Ali, S.A., Identification of Aluminum Scale

With the Aid of Synthetically Produced Basic Aluminum Fluoride
Complexes, SPE 23812 presented at the 1992 SPE International
Symposium on Formation Damage Control held in Lafayette, LA,
Feb. 26-27.
20. Labrid, J.C., Thermodynamic and Kinetic Aspects of Argillaceous
Sandstone Acidizing, SPEJ (Apr. 1975) 117-28.
21. Schechter, R.S., Oil Well Stimulation, Prentice-Hall, Inc., A Simon
& Schuster Co., Englewood Cliffs, New Jersey, 1992.
22. Bertaux, J., Treatment Fluid Selection for Sandstone Acidizing:
Permeability Impairment in Potassic Mineral Sandstones, SPE
15884 presented at the 1986 SPE European Petroleum Conference
held in London, UK, Oct. 20-22.

Reference
1. Rosnes, J.T., Graue, A., and Lien, T., Activity of SulfateReducing Bacteria Under Simulated Reservoir Conditions, SPE
19429 presented at the 1990 SPE Formation Damage Control
Symposium, Lafayette, LA, Feb. 22-23.
2. Nasr-El-Din, H.A., Al-Anazi, H.A., and Hopkins, J.A.,
Acid/Rock Interactions During Stimulation of Sour Water
Injectors in a Sandstone Reservoir, SPE 37215 presented at the
1997 International Symposium on Oilfield Chemistry held in
Houston, TX, Feb. 18-21.
3. Grim, R.E., Clay Mineralogy, 2nd ed., Manchester, McGraw-Hill,
1968.
4. Bennett, R.H., and Hulbert, M.H., Clay Microstructure,
International Human Resources Development Corp., Boston, 1986.
5. McLeod, H.O., Matrix Acidizing, JPT (Dec. 1984) 2055.
6. Peters, F.W., and Stout, C.M., Clay Stabilization During
Fracturing Treatments With Hydrolyzable Zirconium Salts, SPE
5687 presented at the 1975 SPE/AIME Eastern Regional Meeting
held in Charleston, Nov. 6-7.
7. Clementz, D.M., Clay Stabilization in Sandstones Through
Adsorption of Petroleum Heavy Ends, JPT (Sep. 1977) 1061-66.
8. Zaitoun, A., and Berton, N., Stabilization of Montmorillonite Clay
in Porous Media by High-Molecular-Weight Polymers, SPEPE
(May 1992) 160-66.
9. Simon, D.E., Kaul, F.W., and Culbertson, J.N., Anadarko Basin
Morrow-Springer Sandstone Stimulation Study, SPE 6757
presented at the 1981 SPE Annual Technical Conference and
Exhibition held in Denver, CO, Oct. 5-7.
10. Smith, C.F., Crowe, C.W., and Nolan III, T.J., Secondary
Deposition of Iron Compounds Following Acidizing Treatments,
JPT (Sep. 1969) 1121-28.
11. Bryant, L.S., and Buller, C.B., Formation Damage From Acid
Treatments, SPEPE (Nov. 1990) 455-460.
12. Simon, D.E., and Anderson, M.S., Stability of Clay Minerals in
Acid, SPE 19422 presented at the 1990 SPE Formation Damage
Control Symposium held in Lafayette, LA, Feb. 22-23.
13. Smith, S.F., and Hendrickson, A.R., Hydrofluoric Acid
Stimulation of Sandstone Reservoirs, JPT (Feb. 1965) 215-222.
14. Hill, A.D., Sepehrnoori, K., and Wu, P.Y., Design of the HCl
Preflush in Sandstone Acidizing, SPE 21720 presented at the
1991 Production Operations Symposium held in Oklahoma City,
OK, April 7-9.
15. Shuchart, C.E., and Ali, S.A., Identification of Aluminum Scale
With the Aid of Synthetically Produced Basic Aluminum Fluoride
Complexes, SPE 23812 presented at the 1992 SPE International
Symposium on Formation Damage Control held in Lafayette, LA,
Feb. 26-27.
16. McBride, J.R., Rathbone, M.J., and Thomas, R.L., Evaluation of
Fluoboric Acid Treatment in the Grand Isle Offshore Area Using
Multiple Rate Flow Test, SPE 8399 presented at the 1979 SPE
Annual Technical Conference and Exhibition, Las Vegas, Sept. 2326.
17. Gdanski, R., AlCl3 Retards HF Acid for More Effective
Stimulations, Oil & Gas J. (Oct. 28, 1985) 111-115.
18. Gdanski, R.D., and Peavy, M.A., Well Return Analysis Causes
Re-Evaluation of HCl Theories, SPE 14825 presented at the 1986
7th SPE Symposium on Formation Damage Control, Lafayette,
LA, Feb. 26-27.

Table 1: Geochemical analysis of injection watera.

Ion
Concentration, mg/l
Calcium
797
Chloride
8,254
Magnesium
459
Potassium
<10
Sodium
5,545
Sulfate
3,675
a
pH = 7.7.

Table 2: Formulas of examined acids per 1,000 gals of 7.5wt%

HCl acid.
Component
Acid-I
Acid-II
Modified Acid-II
Surfactant
5 gals
2 gals
2 gals
Corrosion Inhibitor
3 gals
4 gals
4 gals
Citric Acid
50 lbs
Mutual Solvent
20 gals
20 gals
Iron reducing Agent
4 gals
4 gals
Reducing Agent
0.5 lbs
H2S Scavenger
20 gals
20 gals
20 gals

Table 3: Bulk mineralogy of reservoir cores as determined by

XRD analysis.
Well-A
Well-A
Well-B
Well-B
Sample #
199
242
106
133
Depth, ft
8,875.1
8,903.5
8,960.5
8,988.4
Quartz, wt%
75.1
92.1
85.8
79.2
K-Feldspar, wt%
17.8
5.1
6.5
11.9
Na-Feldspar, wt%
2.8
2.0
Anhydrite, wt%
1.1
1.3
1.6
1.9
Sylvite, wt%
0.7
Trace
I/M Orda, wt%
5.86
1.29
1.36
4.47
Chlorite, wt%
0.07
0.03
Kaolinite, wt%
0.07
0.21
1.44
0.5
a

Illite/montmorillonite ordered mixed layer.

Table 4: Formula of RHF acid (half strength) based on AlCl 3.

Component
Quantity/1,000 gals
15 wt% HCl
868 gals
Corrosion Inhibitor
3 gals
Glacial Acetic Acid
30 gals
Surfactant
2 gals
AlCl3 Solution (32oBe)
77 gals
Ammonium Bifluoride
200 lbs

H.A. AL-ANAZI, H.A. NASR-EL-DIN, M.K. HASHEM, J.A. HOPKINS

Table 5: Chemical analysis of the RHF acid used in the coreflood

experiments.

Variable

Fig. 1: Pressure drop across the core at 2 ml/min.

Value

500

4,626
6,350
204
196,042
1.2
16.9
178
<10
2,102

Pressure Drop, psia

Aluminum, mg/l
Ammonia, mg/l
Calcium, mg/l
Chloride, mg/l
Fluoride, wt%/v%
Total Acidity (HCl), wt%/v%
Magnesium, mg/l
Potassium, mg/l
Sodium, mg/l

SPE 62825

450

400

350
0

10

20

30

40

Cumulative Core Effluent, PV

A. Brine (Forward)
B. 1PV Acid-II (Forward)
C. Brine (Forward)

Table 6: Treatment stages used in stimulation of Well-D.

5 wt% NH4Cl Solution
15 wt% HCl Acid
Composition/1,000 gals:
2 gals Iron Reducing Agent
4 gals Corrosion Inhibitor
20 gals H2S Scavenger
15 gals Surfactant
5 wt% NH4Cl Solution
a

Stage

Volumea, gals

Preflush
Main Acid

4,700
5,700
Fig. 2: Pressure drop across the core at 2 ml/min.
150

Postflush

4,700

Target zone = 47 ft

Table 7: Chemical analyses of HCl (field sample) collected in the

top and bottom of filter during stimulation of Well-D.
Variable
Filter Top
Filter Bottom
Calcium, mg/l
120
125
Total Iron, mg/l
111
89
Magnesium, mg/l
34
37
Potassium, mg/l
26
32
Sodium, mg/l
134
142
Sulfate, mg/l
1,286
929

Pressure Drop, psia

Fluid

100

50

0
0

20

40

60

80

Cumulative Core Effluent, PV

A. Brine (Forward)
C. Brine (Forward)

B. 1PV Acid-II (Forward)

D. Brine (Reverse)

Fig. 3: Pressure drop across the core at 4 ml/min.

700

600

Pressure Drop, psia

Table 8: Composition of solids collected from the acid returns of

Well-D as determined by the XRD analysis.
Group No.
1
2
3
4a
Date
06/29/97 06/30/97 07/01/97 07/02/97
Sylvite [KCl]
Major
Magnetite [Fe3O4]
Major
Major
Quartz [SiO2]
Major
Major
Minor
Major
Halite [NaCl]
Major
Calcite [CaCO3]
Major
Trace
Goethite [FeOOH]
Major
a
The spent acid was detected in the acid returns of Group 4.

500
400
300
200
100
0
0

20

40

60

80

100

120

Cumulative Core Effluent, PV

A. Brine (Forward)
C. Brine (Forward)

B. 1PV Acid-II (Forward)

D. Brine (Reverse) E. Brine (Forward)

140

SPE 62825

MATRIX ACIDIZING OF WATER INJECTORS IN A SANDSTONE FIELD IN SAUDI ARABIA: A CASE STUDY

5000

2
6
pH

HCl Conc., wt%/v%

pH

10

Fig. 5: Aluminum and total iron concentrations in the

core effluent.
6000

4
1
2

Concentration, mg/l

Fig. 4: HCl concentration and pH in the core effluent.

4000
3000
2000

0
0

10

20

30

Al
Fe

1000

HCl
0

40

10

Cumulative Core Effluent, PV

Fig. 6: Calcium, magnesium, silicon and sulfate

concentrations in the core effluent.

15
20
25
30
Cumulative Core Effluent, PV

35

40

Fig. 7: Return permeability ratio and postflush volume

required to raise the pH of the core effluent to greater
than 4 as a function of injected Acid-I volume.

5000

40

30

20

10

Mg
Ca
Si
SO4--

2000

1000

10

15
20
25
30
Cumulative Core Effluent, PV

35

40

Fig. 8: Pressure drop across the core at 2 ml/min using

modified Acid-II formula..

2
3
Injected Acid Volume, PV

Fig. 9: Sodium and potassium concentrations in the core

effluent.

20

7000

2500

Na
6000

18
16
14
12

5000
1500

4000

1000

3000
2000

500
10

1000

K
35

40

45

50

55

Cumulative Core Effluent, PV

A. Brine (Forward)
C. Brine (Forward)

B. 1PV modified Acid-II (Forward)

D. Brine (Reverse) E. Brine (Forward)

60

0
20

25

30

35

40

Cumulative Core Effluent, PV

45

Na Conc., mg/l

2000

K Conc., mg/l

Pressure Drop, psia

Postflush Vol., PV

3000

Return
Permeability Ratio

Concentration, mg/l

4000

H.A. AL-ANAZI, H.A. NASR-EL-DIN, M.K. HASHEM, J.A. HOPKINS

Fig. 10: Silicon and aluminum concentrations in the core

effluent.
400

12000

1200

10000

1000

8000

Si
6000
4000

100

25

30

35

40

5000

800

4000

600

3000

400

2000

200

1000

0
20

0
130

45

135

Cumulative Core Effluent, PV

1000

800

4000
600
3000
400

2000

10

pH
8

4
6

pH

Na Conc., mg/l

5000

1200

HCl Conc., wt%/v%

Na

3
4
2
2

200

HCl

0
130

135

140

0
150

145

0
0

10

20

16000

4000

Fe

2500

8000

2000

Al

1500

4000

1000

2000

500

0
30

Time, hrs

40

50

K Conc., mg/l

10000

20

6000
5000

40000

Al Conc., mg/l

Total Fe Conc., mg/l

3000

10

50

50000

3500

12000

6000

40

Fig. 15: Potassium and sodium concentrations in the acid

returns of Well-D.

Fig. 14: Total iron and aluminium concentrations in the

acid returns of Well-D.
14000

30

Time, hrs

Cumulative Core Effluent, PV

0
150

145

Fig. 13: HCl concentration and pH in the acid returns of

Well-D.

K Conc., mg/l

7000

1000

140

Cumulative Core Effluent, PV

Fig. 12: Na and K concentrations in the core effluent

after adding a preflush stage of 5wt% NH4Cl .
6000

6000

Si

2000
0

7000

Al

4000

Na

30000

3000
20000
2000
10000

1000

0
0

10

20

30

Time, hrs

40

50

Na Conc., mg/l

200

Si Conc., mg/l

Al

1400

Al Conc., mg/l

Si Conc., mg/l

Fig. 11: Si and Al concentrations in the core effluent

after adding a preflush stage of 5wt% NH4Cl .

14000

300

SPE 62825

Al Conc., mg/l

10