SPE 144007

Acidizing Induced-Damage in Sandstone Injector Wells: Lab Testing and a

Case History
A.M. Al-Mohammad, SPE; M.H. Al-Khaldi, SPE; S.H. Al-Mutairi, SPE; and A.A. Al-Zahrani, SPE, Saudi Aramco
Copyright 2011, Society of Petroleum Engineers

This paper was prepared for presentation at the SPE European Formation Damage Conference held in Noordwijk, The Netherlands, 710 J une 2011.

This paper was selected for presentation by an SPE program committee following review of information contained in an abstract submitted by the author(s). Contents of the paper have not been reviewed
by the Society of Petroleum Engineers and are subject to correction by the author(s). The material does not necessarily reflect any position of the Society of Petroleum Engineers, its officers, or
members. Electronic reproduction, distribution, or storage of any part of this paper without the written consent of the Society of Petroleum Engineers is prohibited. Permission to reproduce in print is
restricted to an abstract of not more than 300 words; illustrations may not be copied. The abstract must contain conspicuous acknowledgment of SPE copyright.


Abstract
Throughout well lifetime, formation damage can occur during the activities of drilling, completion, injection, or well stimulation
treatments. Typically, remedial treatments to restore the well performance involve injection of reactive fluids capable of removing
such damage. Therefore, understanding damage mechanism and type is critical for fluid selection and effective treatment design.
Without this knowledge, the conducted stimulation treatment could cause a more severe form of formation damage.
This report discusses the improper use of mud acid at (9 wt% HCl/1 wt% HF) in restoring the injectivity of N-510. The subject
well was stimulated with two acid stimulation treatments as an attempt to improve the poor results of a previous clean-out job,
conducted to remove mud filter cake. These treatments were designed to remove the damage that has been limiting the well
injectivity. However, it was found that these acidizing treatments created a new formation damage which resulted in severe decline
in the well injectivity.
Integration of chemical analysis techniques of return fluids and core-flood experiments was used to assess the effectiveness of
all conducted treatments. This report demonstrates the techniques used to identify the source and type of formation damage
mechanism that occurred during each treatment. Based on these studies, it was found that the poor results of clean-out job were
due to precipitation of calcium sulfate. This precipitation was a result of the mixing between spent cleanout acid, having a high
amount of calcium, and the high-content sulfate water. Most of this precipitation occurred in the well-bore vicinity during the last
stages of the well flow-back.
Calcium sulfate precipitation had a negative impact on the performance of the conducted acid stimulation treatments. In the
presence of this precipitation, the two successive mud acid stimulation treatments created another form of damage, i.e. in-situ
fluoride-based scale. Initially, the fresh injected mud acid dissolved most of the calcium sulfate scale and as a result it contained
high amount of dissolved calcium ions. However, upon the spending of injected mud acid in the formation, calcium fluoride
precipitated as a result of the increase of solution pH value.
The interactions between different acid systems and the constituent of down-hole environment, resulting in the precipitation of
calcium sulfate and calcium fluoride, are discussed. In addition, this report provides recommended modifications to future
stimulation treatments, conducted under similar conditions so as to prevent the formation of these scales.

Introduction
Field N is a sandstone reservoir, which consists of two bodies: Unayzah-A (top layer) and Unayzah-B (bottom layer), separated
by a siltstone section. Unayzah-A is a wet eolian depositional system having average porosity and permeability values of 19% and
65 mD, respectively, while Unayzah-B is a fluvial depositional system with an average porosity and permeability values of 16%
and 600 mD, respectively. The reservoir has a static bottom-hole temperature of 186F. Static bottom-hole pressure is
approximately 3,800 psi at 6750 ft. This reservoir pressure is maintained by injecting J ilah water, obtained from a shallow aquifer.
Table 1 gives the chemical analysis of the injected water.
The N field water injection system consists of eighteen wells. Most of these injectors were drilled as horizontal wells, and
completed as an open hole. Few of these injection wells were drilled recently into Unayzah-A formation, using water-based mud,
Table 2. The average open hole length is 3,000 ft, completed with 4 sand screen. Following drilling operations, wash acid
treatments, using HCl or HCl/formic mixture, were conducted to remove drilling mud damage. Typically, wash acid of 7.5 wt% or
2 SPE 144007
5 wt% HCl +5 wt% formic was used to remove filter-cake built on the face of drilled formation and near wellbore plugging
caused by mud filtrate or particulates invasion.
Pressure response of several wells, following clean-out treatments, indicated that the acid system was effective in removing the
filter cake around the wellbore. Injectivity tests performed in few wells showed that typical injection rate is nearly 15 MBD at 900
psi, which meets the expected rate. However, the results of clean-out treatment, conducted in N-510, were below expectation,
Figure 1. Therefore, this treatment was followed with two acid stimulation treatments to restore the well injectivity. However,
these treatments not only were unsuccessful, but they even resulted in additional decrease in the well injectivity.
It is clear that application of clean-out treatment in N-510 was not completely successful in restoring the well injectivity since
the two mud acid stimulation treatments created severe formation damage. However, the interaction between different acid
systems, wash/mud acids, and the constituents of down-hole environment were not fully known. Therefore, the objectives of this
study are: 1) integrate flow-back returns analysis with lab testing to assess different treatments conducted in N-510, 2) use this
integration to identify the damage type and mechanism that restricted the well injectivity, and 3) to recommend modifications to
current clean-out treatments so as to minimize potential formation damage due to these jobs.

Well description and history
N-510 is one of several power water injectors (PWI) drilled to provide pressure support for Unayzah-A reservoir in N field. It
was drilled with WBM DIF (KCl/CaCO
3
/XC-Polymer mud) and completed as an open-hole horizontal well in Unayzah-A
formation, with a total depth of nearly 13,332 ft. The well completion includes 9-5/8 casing and a 7 liner at 5,110 ft and 11,490
ft, respectively. The formation is poorly consolidated; therefore, 4-1/2 wire wrapped screens were used in the lateral open-hole
for sand control.
X-Ray Powder Diffraction (XRD) analysis of different field core plugs showed that the major minerals in this sandstone
formation are quartz, clay minerals (illite, chlorite & kaolinite), feldspar (potassium feldspar), and trace amounts of calcite are also
present. The well has static bottom hole temperature of 186F and static bottom hole pressure of 3,860 at 9,058 ft. Latest analysis
of the injected water showed that it contained high concentration of sulfate ion (approximately 4,000 ppm). This high sulfate
concentration had a great impact on the nature of the damage noticed in N-510, as will be explained later.
After drilling and completion operations, an acid wash/clean-out treatment to remove the drilling fluids filter cake was applied
in N-510. This treatment included injection of 5 wt% HCl and 5 wt% formic acid (15 gal/ft). The post-clean-out job injectivity
test showed that a maximum injection rate (IR) of 20 MBWD at 1,500 psi, as against expected IR of 30 MBWD at the same
pressure. Compared to IR of nearby/offset wells such as N-503, the injectivity results of N-510 were below expectation.
Following this limited success of the clean-out job, a matrix acid stimulation treatment was conducted in N-510. It involved
injection of mud acid (HCl/HF) at 9 wt% and 1 wt%, respectively. This treatment was conducted to remove any damage limiting
the well injectivity. However, instead of removing the existing damage, it created a severe formation damage, Figure 1. This is
evident from the well injectivity which decreased from 15 to 5 MBWD at 1,000 psi, following the acid stimulation treatment.
Another acid stimulation treatment using mud acid (9 wt% HCl/1 wt% HF) was applied in a second attempt to restore the well
injectivty. However, this treatment was also not effective and the well injectivity remained at 5 MBD at 1,000 psi.

Calcium sulfate precipitation
Precipitation of insoluble reaction products during acid treatments of injection wells has long been known. The formation of
different precipitations such as iron hydroxide and calcium sulfate affects the treatment outcome and can decrease the well
injectivity. This decrease is mainly due to the non-permeable nature of these precipitations (Delorey and McMaster 1996, Crowe
1985, Allaga et al. 1992, Crowe 1986, Smith et al. 1968, Raju et al. 2005, Leal et al. 2007, Nasr-El-Din et al. 2006, Raju and
Nasr-El-Din 2004, Moghadasi 2003).
Considering the chemical composition of the injected water, and the nature of acids used to stimulate N-510, it is important to
discuss the process of calcium sulfate precipitation before the analysis of lab and field results. This scale forms when its solubility
limit is reached, therefore, understanding the factors that affect its solubility will help in predicting its precipitation.
There are three crystal forms of calcium sulfate: gypsum, hemi-hydrate, and anhydrite. Hemi-hydrate calcium sulfate is an
unstable solid form which changes to anhydrite at high temperature values, above 98C. At lower temperature values, (i.e. T <
98C), hemi-hydrate changes to gypsum. Generally, calcium sulfate has two stable solid forms: gypsum (CaSO
4
.2H
2
O) and
anhydrite (CaSO
4
) with a transition temperature of 98C (Ramsdell and Partridge 1929). The reservoir temperature in N-510 is
nearly 85C (186F); therefore any precipitation of calcium sulfate will be in the form of gypsum.
Calcium sulfate, gypsum, has relatively low solubility limits in water. At 25C, the solubility value of calcium sulfate is almost
2.36 kg in 1 m
3
of water. At higher temperatures, calcium sulfate becomes more in-soluble in water as low as 1.69 kg in 1 m
3
of
water at 90C. Besides temperature, pH value also has a great impact on calcium sulfate solubility. In general, calcium sulfate is
more soluble in low pH solutions where its solubility in 1 m
3
of 5 wt% HCl is 16.9 kg compared to only 2.36 kg in 1 m
3
of water
(Silcock 1979, Delorey and McMaster 1996, Carlberg and Matthews 1973).
SPE 144007 3

Experimental Procedure
Filter-cake removal
To assess the effectiveness of N-510 clean-out treatment, solubility experiments were conducted to remove the drill-in fluids (DIF)
filter cake using acid blend of 5 wt% HCl +5 wt% formic. These experiments were performed using high pressure-high
temperature filter press cell with the following procedure. Approximately 200 ml representative sample of water-based DIF, used
during N-510 drilling operations, Table 2, was introduced into the fluid loss cell. Using 5 m ceramic disk as a medium, filtration
process was initiated by applying a differential pressure of 300 psi. This filtration process was continued at 186F until the fluid
loss reached a constant rate, indicating that the mud filter cake was built on top of the used ceramic disk. The weight of the
formed mudcake was measured before and after it was soaked in clean-out acid, at 186F and 300 psi differential pressure. The
recorded values were used to calculate the loss percent in the cake weight due to its interaction with acid wash fluid.
In another set of solubility experiments, the efficiency of mudcake removal with wash acid was examined in the presence of
the formation rock cuttings. Different weight percents of rock cuttings at 2, 8, and 25 wt% were mixed with various mudcakes
formed at 186F and 300 psi differential pressure. At these temperature and differential pressure values, each generated mudcake-
rock cuttings mixture was left to react with fresh wash acid sample. Loss percent in mudcake weight was calculated from its initial
and final weight values before and after acid reaction, respectively.

Acid compatibility tests
Acid compatibility testing was determined with J ilah water. Representative field samples of J ilah water were obtained and used in
all lab experiments, Table 1. Wash acid sample was neutralized with calcium carbonate powder while stirring until the reaction
solution pH value reached approximately 3-4. This procedure represents the reaction of clean-out acid with mud filter cake,
mainly composed of calcium carbonate. The partially spent acid was then mixed at 1:1 weight ratio with J ilah water. Mixed spent
acid-J ilah water was heated up to almost 80C. Any solid precipitation in the mixture solution was collected using 1.2 m filter
paper for Environmental Scanning Electron Microscopy (ESEM) analysis.

Core-flood experiments
Core-flood testing was conducted to investigate the effect of various acid systems, wash acid and stimulation acid, on the
permeability of reservoir cores. These experiments were carried out in a linear mode at a temperature value of 186F and a back-
pressure of 1,500 psi using representative reservoir core plugs, Table 3.
In each conducted core-flood experiment, the core plug was first saturated with J ilah water while monitoring the pressure drop
across the core plug. Initial core permeability to J ilah water was determined before the injection of acid. After acid introduction at
1 cm
3
/min, J ilah water was injected again in forward or reverse direction to measure the retained permeability after acid interaction
with the core plug. At the end of any core-flood experiment that indicated a negative acid interaction, the treated core plug was
extracted and cut into two equal halves, along acid flow path, and then analyzed with ESEM.
In one of core-flood experiments involving injection of wash acid; the core plug was first saturated with NH
4
Cl brine to
prevent any induced damage as a result of clays instability during the experiment. This step was important in order to: 1) assess
the effect of mixing wash acid with J ilah water on the core permeability with no other potential damaging mechanisms and 2)
compare the effect of wash acid-J ilah water mixture on the core permeability to that of wash acid-NH
4
Cl mixture.

Results and discussion
Treatments and chemicals for returns analyses
A stimulation program was initiated to restore the injectivity of N-510. It consisted of two main treatments. The first one was a
wash acid job, which included injection of HCl/formic mixture to remove mud filter cake built on the face of the formation after
drilling operations. Following this treatment, an injectivity test showed that the well injection rate was below expectation.
Therefore, it was decided to proceed with the second treatment where the well was stimulated with HCl/HF blend to remove any
present formation damage limiting the well injection rate. Tables 4 and 5 show the main stages of the wash acid and the
acidization treatments, respectively.
Water of low salinity and sulfate concentration, Manjor water, was used for fluid preparation of pre-flush, acid, post flush, and
displacement stages of both wash acid and acid stimulation treatments. The chemical composition of this water along with those
of other injected fluids are shown in Table 1. It is worth noting that the injection water, J ilah water, contained relatively high
sulfate content, 4,100 ppm. This high sulfate concentration played a key role in the injectivity decline experienced by N-510, as
will be discussed later.



4 SPE 144007
Well flow-back analysis (wash acid treatment)
The main objective of wash acid treatment was to remove mud filter cake built on the face of the drilled formation. The cleanout
fluids were pumped down using coil tubing and the well was shut-in and then flowed back for nearly 25 h. Samples collected after
flow-back were analyzed for pH and key ions.
Figure 2 shows the pH value of flow-back samples as a function of time. The pH remained nearly constant at 4 for almost 2 h
after the start of flow-back. This pH value indicated that these collected samples were pre-acid returns. The arrival of acid returns
was clearly indicated by the sharp drop in pH to the lowest value of 0.7. The pH remained at this level for the consecutive 4 h
after 2 h of the start of flow-back. In subsequent samples the pH increased again to 2.5 over the next two hours. It is interesting
to note that the rise again in the pH of flow-back samples was slower than its sharp decrease rate, which means that the late returns
of spent acid had more mixing degree than its early returns. This is also evident from the analysis of the excess acid in collected
samples.
Figure 3 depicts the excess acid in flow-back samples as a function of time. The excess acid was not present in the samples
collected before 2 h of flow-back. After the start of spent acid arrival, the excess acid value, with a sharp increase, reached an
average maximum value of 3 wt% in returns collected at 2-6 h. However, in subsequent samples, it gradually decreased to zero at
10 h. The difference between the concentrations of excess acid in flow-back samples and fresh injected acid is mainly due to two
factors namely: dilution effect and acid reaction. To assess the degree of dilution and the amount of acid consumed, chloride
content in produced fluids was used since spent acid, if present in the collected return, would still be detectable as a chloride salt.
Figure 4 shows the profile of chloride concentration in flow-back samples as a function of time. From the variation of chloride
concentration with time, three main observations can be stated. First, the samples before and after acid returns were mixtures of
J ilah water, pre-flush or post-flush samples, since chloride concentration of 16,700 ppm falls between those of J ilah water and
NH4Cl brine, Table 1. Second, similar to excess acid content, chloride concentration increased to a maximum of 48,500 ppm at 5
h and then, gradually decreased to the level of pre-acid samples after 18 hours. It is interesting to note that the maximum chloride
concentration obtained was nearly 100% of the injected acid chloride concentration. This result highlighted the fact that there was
no dilution or dispersion of acid between 5-7 h. The third observation from Figure 4 is that the decrease rate in chloride content
was slower than its sharp increase rate. This behavior re-states the fact that the later stages of the acid returns had higher degree of
mixing than its early stages.
Using the chloride ion as a tracer, the dilution factor, spent acid vol% in produced samples, was calculated, Figure 5. These
dilution factors were determined from measured chloride content in flowed back samples and chloride concentration of different
injected fluids. For example, the dilution factor of flow-back sample produced at 14 h with chloride content of 24,000 ppm can be
calculated as follows:
spcnt ociJ :ol roction (Jilution octor) + non - ociJ :ol roction = 1
lct
`
1
1
1
1
x = ociJ :ol roction (Jilution octor)
y = non -ociJ :ol roction = 1 - x
C = mcosurcJ cbloriJc contcnt in lowbock somplc ot 14 b = 24,uuu ppm
C
1
= CbloriJc contcnt in in]cctcJ ociJ (S wt% ECl + S wt% ormic) = 48,6Su ppm
C
2
= CbloriJc contcnt in non - ociJ somplc = 16,7uu ppm


tbcn _
xC
1
+ y C
2
= 24,uuu
x(48,6Su) + (1 -x)(16,7uu) = 24,uuu
x = u.2S


hese dilution factors provided new insights into the analysis of excess acid results. From Figure 5, it is clear that 5-7 h
flo

T
wback samples had dilution factors of nearly unity, indicating that they were un-diluted acid returns. Excess acid results of
these samples, Figure 3, highlighted the fact that 70% of injected acid was consumed in down-hole reactions, where excess acid
value is 30% of original acid concentration. The excess acid was a result of either using an acid amount more than needed for this
clean-out treatment or the acid did not have sufficient soaking time. The latter possibility was found to be the case, after analyzing
later acid returns. Flowed back sample at 10 h had nearly zero excess acid. This absence of excess acid could be due to dilution
effect or complete acid reaction. From, Figure 5, this sample had an acid vol% of 0.4. If the acid amount used was more than
required for this clean-out job or excess acid amount was diluted with brine, then an acid excess value of (3 wt% *0.4 =1.5 wt%)
would have been still detected in this sample. This result indicated that early acid returns did not have sufficient soaking time and
were flowed back with relativity high excess acid values. Most of this excess acid was in the form of formic acid. This is evident
from Figures 2 and 6, where at pH values from 0 to nearly 1, only very low percent of formic acid dissociates into hydrogen and
SPE 144007 5
formate ions. This indicated that only low amount of formic acid in early acid returns, having relatively short soaking time, was
consumed. Formic acid has retarded reaction time and requires long soaking time to be completely consumed.
At 20 h after flow back, the spent acid disappeared from flow-back samples, as indicated by dilution factors of nearly zero,
Fig
function of time. Similar to the chloride profile with time, aluminum
lev
that the spike in the content of both calcium and magnesium ions started at 2 h of flowback to reach a
ma
al sulfate ion concentration, in flow-
bac
rom the analysis of the wash acid returns, the following items can be concluded:
based on chloride as a tracer.
th calcium carbonate particles and rock cuttings present in
sulfate precipitated during the cleanout treatment. Most of this precipitation occurred in late stages of the
La testing results (filter cake removal)
used during mudcake removal treatment applied in N-510, the solubility of different
it is clear that the
HC
ure 5. This clearly indicated that the flow back was enough to produce all the spent acid. This also evident from the calcium,
magnesium, and aluminum contents in flow back samples.
Figure 7 shows the concentration of aluminum ion as a
el with time started increasing after the start of spent acid production at 2 h till it reached a maximum of 1,000 ppm and then,
decreased to nearly zero at 18 h. The most likely source of aluminum is the clay minerals present in the rock cuttings mixed with
the mud filter cake.
Figure 8 shows
ximum of 9,000 and 4,000 ppm, respectively, before dropping back to pre-acid levels. The source of magnesium ion is most
likely the ankerite and/or dolomite traces present in rock cuttings mixed with mudcake. The significant difference between the
calcium and magnesium levels is due to the additional reaction of acid with calcium carbonate particles present in the mudcake.
The un-diluted acid returns showed that nearly 7 wt% of the injected acid was consumed due to acid reaction. Considering only
the reaction of HCl with mudcake, a calcium concentration of approximately 26,000 ppm results from the complete reaction of 5
wt% HCl with limestone. However, there is a significant difference between the maximum measured calcium concentration of
9,000 ppm and the theoretical value of 26,000 ppm. This difference was initially attributed to only the partial acid reaction with
both the clay minerals and corrosion products in casing or screens to produce aluminum and iron, respectively, Figure 9.
However, this believe was ruled out after the analysis of sulfate ion in produced samples.
Figure 10 shows the variation of sulfate ion concentration with time. The profile of actu
k samples, can be divided into four main parts: (1) constant portion at 3,600 ppm, (2) sharp decrease to a minimum of 1,260
ppm, (3) sharp increase to 2,500 ppm, and (4) nearly constant portion at 2,500 ppm. The first constant portion of the sulfate ion
profile with time represents the sulfate concentration in pre-acid samples. It is worth noting that the sulfate content in these
samples is less than that in J ilah water; 4,100 ppm. This reduction in sulfate concentration was due to dilution with low-sulfate
post-flush. The mixing of injection water with acid returns also explains the sharp decrease in sulfate concentration at nearly 3.3 h
after flow-back, where the dilution factor increased from nearly 0.2 to unity. Similarly, it was noted that the sulfate concentration
in post-acid samples is lower than 4,100. At first, this reduction was expected to be also due to dilution effect. However, from
Figure 10, it is clear that the extent of this reduction in sulfate ion concentration was significantly more than that observed with
calculated sulfate concentrations based on dilution factors. This result indicated that the reduction in sulfate ion concentration was
partially due to dilution with acid returns. The additional reduction in sulfate concentration highlighted the presence of calcium
sulfate precipitation, which explains the difference noticed between the measured calcium concentration and its theoretical value.
Calcium sulfate occurred in the late stages of acid returns due to two main reasons. First, the mixing degree of spent acid with
high sulfate water is high towards the end of flow-back. Second, calcium sulfate is more soluble in low pH solutions than in
neutral pH solutions (Li and Demopoulos 2005, Vetter and Phillips 1970). It is expected that most of calcium sulfate
precipitated in the vicinity of the wellbore where most of the mixing between spent acid and J ilah water occurred.

F
During flow-back, the injected acid was diluted. The dilution factor can be calculated
More soaking time is required for clean-out treatments utilizing formic acid or its mixtures.
The flow-back time was enough to produce the spent acid.
The injected acid was mainly consumed by the reaction wi
mud filter cake. In addition, the acid was partially consumed by the reaction with corrosion products present in the
casing.
Calcium
well flow-back when the spent acid, with high calcium ion, was mixed with high sulfate water in the wellbore vicinity.

b
To evaluate the performance of wash acid
mudcakes in 5 wt% HCl +5 wt% formic acid was measured, using HPHT filter pressure cell, at 186F and 300 psi differential
pressure. The solubility tests were used to determine the percent loss in mudcake weight due to acid interaction.
Figure 11 shows the solubility values of different mudcakes in clean-out acid solutions. From this figure,
l/formic mixture at 5/5 wt% was efficient to dissolve significant amount of the original mud filter cake, where the weight loss
percent, after acid/cake interaction, reached nearly 85%. This high weight loss value was expected since the main component of
the mud filter cake was calcium carbonate, which is very soluble in HCl solutions.
6 SPE 144007
In order to simulate down-hole drilling operations, different weight percents of formation rock cuttings were added to several
generated mudcakes. The presence of formation rock cuttings had negative impact on the effectiveness of the wash acid in
removing the mudcake, as shown in Figure 11. For example, increasing the formation cuttings weight percent to 2 wt% decreased
the mudcake solubility in wash acid from 85 to nearly 25%. Although rock cuttings were present in low amount, however, they
resulted in significant decrease in acid dissolving power. This behavior can be understood knowing that these cuttings are mainly
composed of quartz, which has low solubility in HCl. This characteristic enabled these cuttings to act as a barrier that prevented
the acid contact with the remaining un-dissolved mudcake, Photo 1.
The discussion stated above provides another possible explanation to the presence of high excess acid in flowed back samples
after N-510 wash acid treatment. It was stated earlier that this excess acid indicated that the acid did not have enough contact time
with the mudcake. However, the high excess acid in flow-back returns could also be due to the presence of rock cuttings in mud
filter cake, where these cuttings may have acted as a slow-soluble barrier between the clean-out acid and the mudcake. Hence, this
led to the partial acid spending which in turn led to the presence of high excess acid in flow-back returns.

Lab testing results (acid compatibility)
Samples of wash acid system were reacted with calcium carbonate powder while stirring until the pH value reached nearly 3-4.
This procedure represents the reaction of wash acid system with mud filter cake, which is mainly composed of calcium carbonate.
Samples of partial spent acid were mixed with J ilah water at 1:1 weight ratio.
No precipitation resulted from the mixing of spent wash acid samples with J ilah water at room temperature. However, onset of
precipitation started only after 15 minutes when spent wash acid-J ilah water mixtures were heated up to 80C. SEM analysis
conducted has shown that calcium sulfate, CaSO
4
, is the main component present in collected solids from this precipitation. These
results indicated that spent wash acid is not completely compatible with J ilah water. This interesting finding was supported by the
analysis of flow-back returns from N-510 wash treatment, which indicated that calcium sulfate precipitated during clean-out
treatment was due to the mixing of spent wash acid, having high calcium content, with J ilah water, having high sulfate ion content.
The calcium sulfate precipitation has high impact on formation permeability as will be discussed in the following section.

Lab testing results (core-flood)
Four core-flood experiments were carried out with (5 wt% HCl/5 wt% formic) acid, or mud acid (9 wt% HCl/1 wt% HF) and core
plugs, selected from N field, at reservoir temperature of 186F. These experiments were conducted to investigate the effect of
different injected fluids and their mixtures on the permeability of reservoir cores.
The first core-flood test was performed using N-704 core plug #101. The experiment was carried out such that it simulated the
clean-out and stimulation treatments conducted on N-510. The first step commenced with injection of J ilah water (10 PV) in the
forward direction. This step was done to saturate the core plug with J ilah water and to measure its initial permeability. Once the
pressure drop across the core stabilized, the experiment was stopped to extract the core plug and build a mudcake on its inlet face.
This cake was generated at reservoir temperature and pressure using HPHT filter press and a mud sample similar to the one used
during N-510 drilling operations. After that, the core plug was charged again into the core holder and the experiment was resumed
by injecting nearly 2 PV of clean-out acid (5 wt% HCl/5 wt% formic) in the forward direction at 1 cm
3
/min. After the acid
injection, the core was again retrieved and the residual materials of mud filter cake after its reaction with wash acid were removed
mechanically from the core inlet face. Then, the saturated core with spent wash acid was partially flushed out by injecting 0.5 PV
of J ilah water at 1 cm
3
/min in the reverse direction. The remaining acid in the core (0.5 PV) was mixed with J ilah water, where 2
PV of J ilah water were introduced into the core plug in the forward direction. This sequence of clean-out acid and J ilah water
injection simulated the mixing that occurred between wash acid and J ilah water during the well flow-back and well injectivity
stages, following clean-out treatment. The final steps of the core-flood experiment included the injection of 1 PV of mud acid (9
wt% HCl/1wt% HF) at 1 cm
3
/min in the forward direction, 3 PV and 4 PV of J ilah water in the forward and reverse directions at 1
cm
3
/min, respectively. These three stages of injection simulated the first stimulation treatment conducted on N-510.
Figure 12 shows the pressure drop across the N-704 core plug #101 as a function of cumulative pore volume of injected
fluids. The pressure drop increased upon the injection of wash acid into the core, at 1 cm
3
/min, from nearly zero to 1,000 psi.
Since the injection was at constant flow rate (1 cm
3
/min) and the wash acid viscosity value is comparable to that of J ilah water, the
pressure increase across the plug was considered to be as a result of two causes: 1) presence of partially-removed mudcake on the
inlet face of core plug; 2) incompatibility between partially spent wash acid with J ilah water. Mechanical removal of the
remaining residual materials of mudcake from the plug inlet face resulted in a decrease in the pressure drop from 1,000 to almost
10 psi. This indicated that most of the observed initial increase in the pressure drop was due to the un-complete removal of the
filter cake. In addition, it highlighted that the mixing of partially spent wash acid with J ilah water had negative impact on the core
permeability, where the retained permeability after acid injection, with no presence of any mudcake residual materials, was only
8% (defined as the final J ellh water permeability divided by the initial J ellh water permeability). This suggests that mixing of
spent wash acid with J ilah water can significantly reduce the formation permeability, and hence, injectivity. This incompatible
SPE 144007 7
mixing resulted in calcium sulfate precipitation as observed in compatibility lab testing. It was considered that the precipitation of
calcium sulfate could have caused this additional 10 psi of pressure drop. This precipitation can be partially removed with fresh
mud acid since the retained permeability increased from 8 to 57% upon the injection of 1 PV of 9 wt% HCl/1 wt% HF at 1
cm
3
/min.
Damage due to the mixing of partially spent acid with J ilah water was also observed in a second core-flood using N-704 core
plug #87. This experiment was designed such that the extent of calcium sulfate precipitation effect on core permeability can be
investigated with no other induced damage. Therefore, injected wash acid was first partially reacted with calcium carbonate
powder prior to its injection into the core plug. This step simulated the wash acid reaction with mud filter cake, mainly composed
of calcium carbonate, and eliminated the need to cover the inlet face of the core plug with a mudcake. Another important step is
that the core was saturated with NH
4
Cl brine to ensure that no any potential damage due to clays instability during the experiment.
Finally, the core plug was analyzed before and after the experiment using CT scan.
Figure 13 shows the pressure drop across the core #87 as a function of cumulative pore volume of injected fluids. It is clear
from this figure that partially-spent wash acid had some stimulation effect on the core when it was injected after the NH
4
Cl
saturation step. The core permeability to NH
4
Cl brine increased from 47 to nearly 50 mD after injection of 1 PV of 5 wt% HCl/5
wt% formic acid at 1 cm
3
/min. After this stage, the core was saturated with J ilah water by injecting nearly 4 PV of J ilah water at 1
cm
3
/min in the forward direction. This was followed by injection of 1 PV of partially-spent acid and 2 PV of J ilah water at 1
cm
3
/min in the forward and reverse direction, respectively. The final core permeability to J ilah water was measured by injecting
nearly 3 PV of J ilah water in the forward direction and it was found to be 44 mD. This value is nearly 88% of core permeability to
NH
4
Cl brine prior to mixing J ilah water and spent wash acid in the core. This difference between the two permeability values
attributed to the difference between the J ilah water viscosity to that of NH
4
Cl brine or due to calcium sulfate precipitation. To
investigate the presence of calcium sulfate precipitation, the treated core plug was first analyzed using CT scan and then cut into
two halves along the flow path and both pieces were analyzed using SEM. Figure 14 shows the CT scans of the core plug before
and after its interaction with injected fluids. Basically, these scans showed that a lower density material, indicated by low CT scan
numbers (1,600-1,700), precipitated in the core and significant amount of this material was present near the inlet face of the core.
SEM analysis identified the precipitated material as calcium sulfate, Figure 15. These results indicated that calcium sulfate
precipitated during the mixing of J ilah water with partially-spent acid. However, the effect of this precipitation on the core
permeability was not significant, possibly due to the stimulation effect of wash acid.
The effect of calcium sulfate on core permeability was more pronounced in a core-flood experiment using N-704 core plug #
125, Figure 16. The core was first saturated with J ilah water with initial permeability to J ilah water of 200 mD. Unlike other
core-flood experiments, the J ilah water was not completely displaced out of the core with wash acid. Only 0.75 PV of wash acid
was injected at 1 cm
3
/min in the forward direction and soaked for 1 h. Then, J ilah water was injected in the reverse direction at 1
cm3/min, simulating flow-back stage in the field. Finally J ilah water was injected at 1 cm
3
/min in the forward direction, thereby
simulating the injectivity test in the field. The retained core permeability to J ilah water was nearly 72% of initial permeability.
This result combined with other core-flood results, clearly indicated the negative impact of the mixing of J ilah water with partially-
spent wash acid on the permeability of reservoir cores.
The effect of the mud acid injection on reservoir cores permeability was completely investigated in a core-flood experiment. In
Figure 17, 3 PV of mud acid were injected at 1 cm
3
/min into N-704 core plug #71, following the plug saturation with J ilah water.
The pressure drop across the plug decreased from 1.4 psi to almost 0.5 psi upon the injection of mud acid. The core permeability
to J ilah water increased after the injection of mud acid from 63 to 195 mD, a permeability enhancement of 68% (defined as
difference between initial and final permeability values to J ilah water divided by initial J ilah water permeability). This core-flood
experiment clearly showed that mud acid was able to stimulate M sandstone core plugs, with no observed negative impact. The
mud acid interaction with core plugs and with calcium sulfate precipitation was studied with fresh acid samples. The effect of
spending of mud acid on its interaction with both calcium sulfate and sandstone formation will be discussed later.

Well flow-back analysis (acid stimulation treatment)
N-510 well was stimulated with 9 wt% HCl-1 wt% HF to improve its injection rate. The treatment included the injection of pre-
flush (4 wt% NH
4
Cl brine), acid pre-flush (5 wt% HCl/5 wt% formic), mud acid (9 wt% HCl/1 wt% HF), acid over-flush (5 wt%
HCl), and post-flush (4 wt% NH
4
Cl brine). These fluids were pumped down and the well was shut-in and then flowed back for
nearly 18 h. Samples collected after flow-back were analyzed for pH, acid concentration and key ions.
The pH values of the flowed back fluids are shown in Figure 18. The high pH values (~7) measured at 2 and 3 h after the start
of flow-back are due to the use of post-flush and displacement NH
4
Cl brines at the end of treatment. However, earlier fluid returns
had relatively lower pH values (2-4), which indicated that low amounts of spent acid returned with these flow-back samples.
Further production of partially spent acid returns decreased the pH values of produced fluids to reach a minimum of 0.7 at nearly 5
h after the start of flow-back. The pH remained at this value for the 7 consecutive hours before it increased again to 1.9 at 18 h
8 SPE 144007
after flow-back. This low pH value at the end of flow-back stage suggested that the spent acid was not completely recovered.
This is also evident from chloride contents in produced samples.
Figure 19 depicts the profile of chloride content in flow-back samples as a function of time. The chloride content was initially
around 10,000 ppm, but it increased to a maximum of 70,000 ppm in 4 hours. It remained at this value for the 5 consecutive hours
before it decreased to 45,000 ppm at the end of flow-back. The highest value of chloride content in returns represented nearly 78%
of maximum injected chloride content during mud acid stage (9 wt% HCl-1 wt% HF). Dilution of mud acid returns with acid pre-
flush served as a major cause of this difference between injected chloride content and that measured in flow-back samples. This
extent of mixing or dilution factor can be calculated using the measured chloride content in returns, the injected chloride content
during mud acid (90,000 ppm), and acid pre-flush (50,000 ppm), as shown earlier. For example, at 8 h after flow-back, the
measured chloride content of 70,000 ppm indicated that the dilution factor of the mud acid returns was nearly 0.7. In other words,
70 vol% of the flow-back sample at 8 h was spent mud acid.
Based on these calculated dilution factors, the maximum fluoride content of 7,000 ppm is expected to be in flow-back samples
at 8 h to 12 h after flow-back, where the minimum dilution extent of spent mud acid occurred. However, the most striking feature
of Figure 19, showing fluoride content in returns, is the low concentration of fluoride ion, as low as 200 ppm. In general, the
reduction in fluoride concentration in returns is due to two main causes: dilution and precipitation. Given the measured fluoride is
drastically lower than expected diluted values, this significant additional reduction in fluoride content is due to precipitation.
Fluoride loss can be a result of its interaction with different dissolved ions produced from reaction of mud acid with different
minerals. Among the common fluoride precipitates are aluminum fluoride and sodium, potassium fluosilicates:
3 F
-
+Al
3+
AlF
3

H
2
SiF
6
+2 Na
+
Na
2
SiF
6
+2H
+

H
2
SiF
6
+2 K
+
K
2
SiF
6
+2H
+

Aluminum fluoride precipitates when F/Al ratio is 3 or above. The F/Al is dependent on the pH value of the mud acid reaction
solution where it reaches 3 at pH values of 2.5 and above (Shuchart and Gdanski 1996). From Figure 18, it is clear that the
maximum pH in spent mud acid returns was around 2, indicating that aluminum fluoride did not precipitate during N-510
stimulation treatment. This is also clear from the profile of aluminum concentration, in returned samples, with time, Figure 20.
The aluminum content increased upon the start of production of spent mud acid returns until it reached a maximum of 7,000 at 10
h after flow-back. No reduction was observed in aluminum content, in subsequent samples, except for the one expected due to
dilution effect near the end of flow-back. Similarly, the potassium content showed similar profile to that of aluminum, Figure 21.
It increased to a maximum of 3,000 ppm, suggesting that low amounts of illite and feldspars minerals were dissolved. At the end
of flowback stage, potassium ion concentration decreased due to mixing of spent mud acid with acid pre-flush returns. Sodium
content in return samples as function of time showed different profile, Figure 22. The Na content was initially around 7,000 ppm,
but decreased throughout the returns to as low as 2,300 ppm in spent acid returns. The major source of sodium is the pre-acid
samples which contained around 7,000 ppm. Based on calculated dilution factor of 0.7, the expected sodium content in this
mixture of acid returns with pre-acid samples is approximately 2,100, which is equal to the measured value. Therefore, the
observed reduction in sodium content in spent acid returns is mainly due to mixing effect.
Contacting HF with calcium ions will produce calcium fluoride, a white precipitate that can cause formation damage.
2 HF +Ca
++
CaF
2
+2H
+

Figure 23 depicts the calcium ion content in fluid returns as a function of time. The spike in calcium concentration started upon
the production of spent acid returns to reach a maximum of around 8,500 ppm. It remained constant at this level before it
decreased at 15 h after flow-back. Based on calcium concentration trend with time, no calcium precipitation was expected.
However, striking features of this trend were noted when it was compared with that of both sulfate and magnesium. Figure 24
shows the concentration of magnesium ion in flow-back samples. Unlike the calcium concentration, the magnesium content had a
continuous increase before it decreased at 15 h after flow-back. The source of magnesium is the reaction of acid with ankerite
and/or dolomite which are present in the formation, Table 3. Therefore, if magnesium content increased, then calcium content
would increase as well. However, from Figures 23 and 24, the magnesium content increased from 3,500 to 4,100 ppm at 10 and
12 h, respectively, while calcium content decreased from 8,700 to 7,900 ppm. This suggested that calcium-based precipitation
occurred. This precipitation is expected to be calcium fluoride since it resulted in the reduction of both calcium and fluoride
content at the same time. This precipitation of calcium fluoride occurred in-situ due to spending of mud acid. At low pH values,
mud acid was first compatible with dissolved calcium because the fluoride is associated with hydrogen ion, with no free fluoride
ions. In other words, calcium fluoride is very soluble in low pH mud acid solutions, (Pan and Darvell 2007). However, as the
mud acid reacted with aluminum-silicates or calcite in the formation, acid concentration decreased and more free fluoride ions
SPE 144007 9
produced in the reaction solution, Figure 25, and as a result calcium fluoride precipitated. In addition to calcium fluoride scale,
calcium sulfate precipitation also occurred during N-510 stimulation treatment.
Figure 26 shows the sulfate ion content as a function of time. It increased to a maximum of 9,000 at 7 h after flow-back, and
then decreased to a minimum of 3,000 ppm and remained constant until the end of flow-back. The source of this high sulfate ions
content in the returns was the calcium sulfate scale that precipitated during the wash acid treatment, as stated earlier. Calcium
sulfate has high solubility in HF solutions compared to that of HCl and brine solutions. Therefore, the peak in sulfate
concentration was expected to occur in spent mud acid returns. However, the maximum sulfate concentration was measured in
acid post-flush returns. This suggested that high amounts of initially dissolved calcium sulfate during mud acid stage precipitated
upon the spending of the acid in the formation.
During mud acid stimulation treatments, acid pre-flush stage is pumped ahead of the mud acid stage in order to dissolve the
calcium/magnesium materials and prevent the mud acid contact with calcium/magnesium ions, which results in
calcium/magnesium fluoride precipitations at high pH values. In N-510, the acid pre-flush did not prevent the contacting of mud
acid with calcium ions because they were present as calcium sulfate solids, which have relatively low solubility in HCl solutions.
As a result, the injected mud acid initially dissolved most of calcium sulfate scale and then calcium re-precipitated as calcium
fluoride upon the acid spending in the formation.

Conclusions and Recommendations:
Formic is a weak acid and its reaction rate is relatively slow. Therefore, long soaking time is required for HCl/formic
clean-out jobs.
Mixing between spent acid, high in calcium content, and high sulfate water will result in calcium sulfate precipitation.
Live mud acid can dissolve calcium sulfate scale. However, upon acid spending, both calcium sulfate and calcium
fluoride will precipitate due to the increase in acid solution pH value.
Large volume of acid pre-flush, during clean-out jobs, should be injected to prevent the mixing between spent acid
and high sulfate water during the well flow-back. This will prevent the precipitation of calcium sulfate.
Calcium sulfate scale inhibitor should be added to the acid stage during mudcake clean-out treatments. This is
required to prevent calcium sulfate precipitation when the spent acid is mixed with high-content sulfate water.

Acknowledgments
The authors wish to acknowledge the Saudi Arabian Oil Company (Saudi Aramco) for granting permission to present and publish
this paper. Special thanks go to the Chemistry and Advanced Instruments Units of the R&D Center for their analysis of different
solutions and solids

References
Allaga, D.A., Wu, G., Sharma, M.M., and Lake, L.W., 1992. Barium and calcium sulfate precipitation and migration inside sand-packs. SPE
Formation Evaluation, (March), 7986.

Crowe, C.W., 1985. Evaluation of agents for preventing precipitation of ferric hydroxide from spent treating acid. J. Pet. Technol. 37(4), 691.

Crowe, C.W., 1986. Prevention of Undesirable Precipitates from Acid Treating Fluids. Paper SPE 14090 presented at the SPE 19
th
International
Meeting on Petroleum Engineering held in Beijing, China, March 17-30.

Smith et al., 1967. Removal and Inhibition of Calcium Sulfate Scale in Waterflood Projects. Paper SPE 1957
presented at the SPE 42
nd
Annual Fall Meeting held in Houston, USA, October 1-4.
Carlberg, B.L., and Matthews, R.R., 1973. Solubility of calcium sulfate in brine. Paper SPE 4353 presented at SPE Oilfield Chemistry Symp.,
held in Denver, CO, USA, May 24-25.

Nasr-El-Din, H.A., Zabihi, M., Al-Dossary, K., Djelliout, M.A., and Kelkar, S.K., 2006. Restoring Injectivity of Wells Drilled in Sour Carbonate
Formations. Paper SPE 102860 presented at the SPE Annual Technical Conference and Exhibition, San Antonio, Texas, USA, September
24-27.

Delorey, J .R., Allen, S., and McMaster, L.,. 1996. Precipitation of Calcium Sulphate During Carbonate Acidizing: Minimizing the Risk. Paper
SPE 96-84 presented at the 47
th
Annual Technical Meeting of The Petroleum Society in Calgary, Alberta, Canada, J une 10 -12.

Leal, J . et al., 2007. A Systematic Approach to Remove Iron Sulphide Scale: A Case History. Paper SPE 105607 presented at the SPE Middle
East Oil and Gas Show and Conference, Kingdom of Bahrain, March 11-14.

10 SPE 144007
Moghadasi, J . et al., 2003. Scale Formation in Iranian Oil Reservoir and Production Equipment During Water Injection. Paper SPE 80406
presented at the International Symposium on Oilfield Scale, Aberdeen, UK, J anuary 29-30.

Raju, K.U., Nasr-El-Din, H.A., Hilab, V.V., Siddiqui, S., and Mehta, S., 2005. Injection of Aquifer Water and GOSP Disposal Water into Tight
Carbonate Reservoirs. SPEJ, 10, 374-384.

Raju, K.U., and Nasr-El-Din, H.A., 2004. Calcium Sulfate Scale: Field Tests and Model Predictions. Paper 04397 presented at the NACE
International, CORROSION, New Orleans, La, March 28 - April 1.

Ramsdell, L.S., and Partridge, E.P., 1929. The crystal forms of calcium sulphate. J. American Mineralogist, 14, 59-74.

Li, Z., and Demopoulos, G., 2005. Solubility of CaSO
4
Phases in Aqueous HCl +CaCl
2
Solutions from 283 K to 353 K. J. Chem. Eng. Data,
50, 1971-1982.

Pan, H., and Darvell, B., 2007. Solubility of calcium fluoride and fluorapatite by solid titration. Archives of Oral biology, 52, 861868.

Shuchart, C., and Gdanski, R., 1996. Improved Success in Acid Stimulations with a New Organic-HF System. Paper SPE 36907 presented at
European Petroleum Conference held in Milan, Italy, October 22-24.

Silcock, H.L. Solubilities of Inorganic and Organic Compounds vol. 3. Pergamon, New York, USA, pp. 754755.

Vetter, O., and Phillips, R., 1970. Prediction of Deposition of Calcium Sulfate Under Down-Hole Conditions. J. Petroleum Technology,
October, 1299-1308.



































SPE 144007 11
Table 1: Chemical composition of injected fluids.
Variable
Manjor
water
Jilah
water
Pre-flush
Post-flush
Displacement
Acid
(HCl/formic)
Acid
(HCl/HF)
Chloride, mg/L 542 7,800 39,542 48,542 86,842
Fluoride, mg/L 0 0 0 0 9,500
Aluminum, mg/L 0 0 0 0 0
Calcium, mg/L 202 672 202 202 202
Magnesium, mg/L 72 409 72 72 72
Sulfate, mg/L 1,500 4,100 1,500 1,500 1,500
pH 7-8 7-8 4-5 <0 <0




Table 2: Formulation of 1.0 bbl of water-based mud formulation used during M-5 drilling operations.
Variable Value
XC-Polymer, gal 0.5-1.0
Pac-L, lb 3.0-4.0
KCl, lb 22.0
KOH, lb 0.15-0.50
CaCO
3
(fine), lb 9.0
CaCO
3
(medium), lb 15.0
Lubricant, vol% 1-3
Distilled water, bbl 0.95
pH 9-10





Table 3: Average mineralogical composition of core used in core-flood experiments
Mineral Concentration, wt%
Quartz (SiO
2
) 68 - 97
Feldspar (KAlSi
3
O
8
- NaAlSi
3
O
8
- CaAl
2
Si
2
O
8
) 0 - 19
Illite/smectite KAl
4
(Si
8
,Al)O
20
(OH)
4
/(Ca,Na)(Al,Mg,Fe)
4
(Si,Al)
8
O
20
(OH)
4
0 - 13
Kaolinite (Al
2
Si
2
O
5
(OH)
4
) 0 - 8
Ankerite ((Ca,Fe, Mg)(CO
3
)
2
) 0 - 7
Anhydrite (CaSO
4
) 0 - 4
Chlorite (Fe
5
Al)(AlSi
3
)O
10
(OH)
8
0 - 2
Calcite (CaCO
3
) 0 - 1










12 SPE 144007
Table 4: Main stages of wash acid treatment
Treatment stage Main fluid & additives Volume, gal
Pre-flush
4 wt% NH
4
Cl
Surfactant, mutual solvent
4,550
Acid
5 wt% HCl +5 wt% Formic
Corrosion inhibitor, iron control agent, surfactant
13,650
Post-flush
4 wt% NH
4
Cl
Surfactant, mutual solvent
2,730
Displacement
4 wt% NH
4
Cl
Surfactant, mutual solvent
5,887








Table 5: Main stages of acid stimulation treatment
Treatment stage Main fluid & additives Volume, gal
Pre-flush
4 wt% NH
4
Cl
Surfactant, mutual solvent
4,550
Acid pre-flush
5 wt% HCl +5 wt% Formic
Corrosion inhibitor, iron control agent, surfactant
13,650
Main acid
9 wt% HCl +1 wt% HF
Corrosion inhibitor, iron control agent, surfactant
18,200
Post-flush
4 wt% NH
4
Cl
Surfactant, mutual solvent
4,550
Displacement
4 wt% NH
4
Cl
Surfactant, mutual solvent
5,887


SPE 144007 13
0
500
1000
1500
2000
2500
0 10,000 20,000 30,000 40,000
W
e
l
l

h
e
a
d

p
r
e
s
s
u
r
e
,

p
s
i
Injection rate, BWD
N510afterMudAcid N510afterAcidwash
N511 N503

Figure 1: Injection rates results after stimulation treatments in different N wells.

0
2
4
6
8
10
0 2 4 6 8 10 12 14 16 18 20 22 24 26 28
p
H
Time, h
Arrival of acid returns

Figure 2: Flow-back analysis (wash acid treatment): pH.

14 SPE 144007

Figure 3: Flow-back analysis (wash acid treatment): excess acid.
0
2
4
6
0 2 4 6 8 10 12 14 16 18 20 22 24 26 28
A
c
i
d

c
o
n
c
e
n
t
r
a
t
i
o
n
,

w
t
%
Time, h
Effectofdilution
Acidwithnodispersion




0
10000
20000
30000
40000
50000
60000
0 2 4 6 8 10 12 14 16 18 20 22 24 26 28
C
o
n
c
e
n
t
r
a
t
i
o
n
,

m
g
/
L
Time, h
Chloride inacidwashfluid=48,630ppm
Chloridecontent inpreandafteracidreturns =16,700ppm
Acidwithnodispersion
Figure 4: Flow-back analysis (wash acid treatment): chloride.

SPE 144007 15
0
0.2
0.4
0.6
0.8
1
1.2
0 5 10 15 20 25 30
D
i
l
u
t
i
o
n

f
a
c
t
o
r
Time, h
Dilutionfactorofacidsolution=
Acidvolume
Acidvolume+Injected watervolume
Dilutionfactor=0.4
(40% ofproducedsampleisacid)

Figure 5: Flow-back analysis (wash acid treatment): dilution factor.



Figure 6: Distribution of formic acid species as a function of pH.
0.00
0.20
0.40
0.60
0.80
1.00
0 2 4 6 8 10 12 14

pH
Formateion
Formic acid



16 SPE 144007

Figure 7: Flow-back analysis (wash acid treatment): aluminum.
0
200
400
600
800
1000
1200
0 5 10 15 20 25 30
A
l
u
m
i
n
u
m
,

m
g
/
L
Time, h



Figure 8: Flow-back analysis (wash acid treatment): calcium and magnesium.
0
2000
4000
6000
8000
10000
12000
0 5 10 15 20 25 30
C
o
n
c
e
n
t
r
a
t
i
o
n
,

m
g
/
L
Time, h
Magnesiumlevelinpreacidand
postacid samples=420ppm
Calciumlevelinpreacidandpostacid
samples=1,070ppm

SPE 144007 17

Figure 9: Flow-back analysis (wash acid treatment): iron.
0
1000
2000
3000
4000
5000
0 5 10 15 20 25 30
I
r
o
n
,

m
g
/
L
Time, h



Figure 10: Flow-back analysis (wash acid treatment): sulfate.
0
1000
2000
3000
4000
5000
0 5 10 15 20 25 30
C
o
n
c
e
n
t
r
a
t
i
o
n
,

m
g
/
L
Time, h
Sulfate concentration calculated
based on dilution factor, only
mixing occured
[SO
4
2
]
actual
<[SO
4
2
]
dilution
,indicatingthe
formationofsulfatebasedscale
[SO
4
2
]
actual=
[SO
4
2
]
dilution
,
nopreceipitation
Zoneofprecipitation
18 SPE 144007

0
20
40
60
80
100
0 2 8 25
W
e
i
g
h
t

l
o
s
s
,

%
Rock cuttings, wt%
Figure 11: Solubility of mud filter cake in 5 wt% HCl +5 wt% formic fluid at 186F as a function of rock cuttings wt%.


Figure 12: Pressure drop across the core during injection of clean-out and mud acids, core plug #101.
SPE 144007 19


Figure 13: Pressure drop across the core during injection of clean-out acid, core plug #87.






20 SPE 144007






Figure 14: CT scan analysis of core plug #87 before and after injection of spent clean-out acid and J ilah water at 186F.
SPE 144007 21


Figure 15: Calcium sulfate precipitation in core plug #87 after injection of spent clean-out acid and J ilah water at 186F.
Calcium sulfate
(CaSO
4
.H
2
O)
Quartz (SiO
2
)
22 SPE 144007

Figure 16: Pressure drop across the core during injection of clean-out acid, core plug #125, soaking time =1 h.

Figure 17: Pressure drop across the core after injection of mud acid (9 wt% HCl/1 wt% HF), core plug #71.
SPE 144007 23

Figure 18: Flow-back analysis (stimulation acid treatment): pH.
0
1
2
3
4
5
6
7
8
0 5 10 15 20
p
H
Time, h
Start of spent acid returns
pH
final flow-back sample
= 2
Spent acid was partially flowed back


Figure 19: Flow-back analysis (stimulation acid treatment): chloride and fluoride.
0
100
200
300
400
500
600
700
800
900
0
20000
40000
60000
80000
100000
0 2 4 6 8 10 12 14 16 18 20
C
o
n
c
e
n
t
r
a
t
i
o
n
,

m
g
/
L
Time, h
F
-
Cl
-
(9 wt%HCl/1 wt% HF)
returns with minmum
dispersion
F
-
Cl
-
C
o
n
c
e
n
t
r
a
t
i
o
n
,

m
g
/
L
24 SPE 144007

Figure 20: Flow-back analysis (stimulation acid treatment): aluminum.
0
1000
2000
3000
4000
5000
6000
7000
8000
0 5 10 15 20
A
l
u
m
i
n
u
m
,

m
g
/
L
Time, h


Figure 21: Flow-back analysis (stimulation acid treatment): potassium.
0
500
1000
1500
2000
2500
3000
3500
4000
0 5 10 15 20
P
o
t
a
s
s
i
u
m
,

m
g
/
L
Time, h
SPE 144007 25

Figure 22: Flow-back analysis (stimulation acid treatment): sodium.
0
1000
2000
3000
4000
5000
6000
7000
8000
0 5 10 15 20
S
o
d
i
u
m
,

m
g
/
L
Time, h


Figure 23: Flow-back analysis (stimulation acid treatment): calcium.
0
2000
4000
6000
8000
10000
0 5 10 15 20
C
a
l
c
i
u
m
,

m
g
/
L
Time, h
26 SPE 144007

Figure 24: Flow-back analysis (stimulation acid treatment): magnesium.
0
1000
2000
3000
4000
5000
0 5 10 15 20
M
a
g
n
e
s
i
u
m
,

m
g
/
L
Time, h




Figure 25: Distribution of HF acid species as a function of pH.
0.00
0.20
0.40
0.60
0.80
1.00
0.0 2.0 4.0 6.0 8.0 10.0 12.0 14.0

i
pH
F

HF

SPE 144007 27

Figure 26: Flow-back analysis (stimulation acid treatment): sulfate.
0
2000
4000
6000
8000
10000
0 5 10 15 20
S
u
l
f
a
t
e
,

m
g
/
L
Time, h





























28 SPE 144007


Fresh mudcake, no acid interaction



Mudcake residuals after acid reaction Mudcake residuals after acid reaction
Rock cuttings = 0 wt% Rock cuttings = 2 wt%


Mudcake residuals after acid reaction Mudcake residuals after acid reaction
Rock cuttings = 8 wt% Rock cuttings = 25 wt%