SPE 73706
Lessons Learned from Acid Pickle Treatments of Deep/Sour Gas Wells
H.A. Nasr-El-Din, SPE, S.H. Al-Mutairi, S.M. Al-Driweesh, SPE, Saudi Aramco
Copyright 2002, Society of Petroleum Engineers Inc.
This paper was prepared for presentation at the SPE International Symposium and Exhibition
on Formation Damage Control held in Lafayette, Louisiana, 20–21 February 2002.
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Abstract
Pickle treatments are commonly conducted to remove various
contaminants from the wellbore prior to performing chemical
treatments in various wells. Introduction of these contaminants
into the formation during the treatment can cause loss of well
performance, especially in tight formations. These treatments
should be designed to remove various contaminants from well
tubulars in an efficient and cost effective way.
A pickle treatment was designed to clean well tubulars in
several wells prior to performing acid fracturing in the
carbonate formation. The pickle treatment consisted of
several fluids such that each fluid removed one type of
contaminants. This paper examines the effects of fluid
composition, volume, and placement (bullheading versus
coiled tubing) on the efficiency of pickling treatments. More
than twenty pickle treatments performed on deep, sour, hot gas
wells were examined.
To assess pickle treatments in the field, spent acid was
analyzed and the concentrations of key ions were measured.
Sufficient measurements were made to obtain concentration
profiles of chemical species in the spent pickle acid. These
profiles were numerically integrated and the data were used to
assess the outcome of each pickle treatment. In addition,
particulate solids present in the spent acid were separated and
analyzed using XRD and XRF techniques.
Pickle treatments were conducted on more than twenty
gas wells. Some of these wells were perforated, while others
were not perforated. Un-perforated wells were pickled using
1.75” high-pressure coiled tubing. On the other hand,
perforated wells were pickled using bullheading. The pickle
treatments consisted of slugs of surfactants, organic solvents,
hydrochloric acid and gelled fluids. Samples of all pumped
fluids were collected and analyzed. In addition, well flow back
samples were collected every two minutes and were also
analyzed to determine their composition.
Analysis of spent acids indicated that the major tubular
contaminants are mill scale and pipe dope. Spent acid samples
collected from deep sour gas wells contained up to nearly
105,500 mg/L of total iron. The efficiency of removing pipe
dope was followed by tracing the concentration of zinc, the
main acid-soluble constituent in the pipe dope, in the spent
acid. The concentrations of acid and iron were used to
determine acid reaction with the corrosion products present in
the tubing. The concentration of the chloride ions was used to
determine the dispersion and mixing behaviour of the acid
slug.
This paper presents the results obtained from analyzing
more than 2000 samples obtained from twenty treatments. The
results of this work have been used to enhance the efficiency
of the pickle treatments and to significantly reduce the
treatment cost.
Introduction
Formation damage occurs during acidizing or chemical
treatments due to the presence of contaminants in the tubing.
Several researchers investigated the type and concentration of
these contaminants.1-4 The main contaminants present in a typical
well tubing are mill scale, iron sulfides, pipe dope, sand, and
other fine particles that were picked up during storage and
transportation of the tubing string. Oil or condensate may also be
present in old producers.
One of the contaminants in the wellbore is pipe dope. Pipe
dope is used to seal tubing joints, minimize thread erosion and
enhance the galling resistance of the threads.5,6 Many authors
recommended not to use excessive amounts of pipe dope, which
may end in the target zone and cause severe formation damage.1-
4
Another main source of wellbore contaminants is iron scale.
New low-carbon steel pipes (J-55, C-95 and L-80) are always
covered with mill scale (magnetite, Fe3O4).7-10 Iron oxides
dissolve in HCl and release ferric and ferrous ions into the acid.
Ferric ions will precipitate once the acid enters the formation and
the pH rises above a value of 1-2.10-13 Precipitation of iron
compounds will cause severe formation damage and, as a result,
the efficiency of the acid treatment will diminish. In old wells
and depending on the type of the treated well, iron scale can be
covered by oil, condensate, or biomass. In addition, if the well is
sour, then iron sulfide species will be present too.13,17 Some of
2 H.A. NASH-EL-DIN, S.H. AL-MUTAIRI, S.M. AL-DRIWEESH
the iron sulfide species react with HCl and produce hydrogen
sulfide, which can react with iron and precipitate iron sulfide at
pH values greater than 1.9.12,18 Hydrogen sulfide can also react
with ferric ions and precipitate elemental sulfur.
Contaminants present in the tubing will cause severe
formation damage if they invade the target zone. Therefore,
every effort should be made to remove these contaminants
before applying any chemical treatments. Tube pickling is
recommended to remove wellbore contaminants before acid
treatments.8,19-21
Recently, Saudi Aramco embarked on an extensive
campaign to develop its gas fields. Acid fracturing has been
used to enhance the performance of gas wells in a tight carbonate
gas reservoir. To ensure good results from acid frac treatments,
a thorough tube cleaning treatment was performed before
conducting the main acid treatment. The objectives of this work
were to: (1) investigate the nature of various contaminants that
may be present in the tubing, (2) design pickle treatments for
perforated and unperforated deep, sour gas wells, (3) assess
the treatment in the field, and (4) optimize the treatment based
on lab and field results.
Reservoir Description
One of the main non-associated gas reservoirs in Saudi Arabia
is the Khuff formation (carbonate). The Khuff formation is
located in the eastern province of Saudi Arabia. This
formation belongs to the late Permian age and is encountered
at an average depth of 11,500 ft.22 The Khuff formation is
subdivided into four main zones, denoted A, B, C, and D.
Zones B and C are the two main intervals producing non-
associated gas. Lithological studies show that the reservoir is
composed of dolomite intermingled with limestone and
intermittent anhydrite stringer within the tighter section of the
reservoir. The two reservoirs have varying pay thickness, on
average, from 120 ft in the Khuff B to 200 ft in the Khuff C.
The average initial reservoir pressure is 7,000 psi and the
average bottom hole static temperature is 275°F.23 The
reservoir has a permeability of 0.1 to 5 mD and tends to have
significant porosity.24 Hydrogen sulfide content depends on
well location and depth. Wells in the northern part of the
reservoir produce gas with up to 10 mol% H2S, whereas those
in the south produce gas at nearly zero H2S content.25 The
produced gas contains up to 4 mol% carbon dioxide. There are
approximately 40 bbls of condensate and 1.5 bbls of water
produced per 1 MMSCF of gas.16
Stimulation efforts in the Khuff reservoirs are needed to
remove drilling mud filter cake and enhance reservoir
permeability. Both matrix and fracturing acidizing treatments
were conducted in this field. Regular, emulsified and gelled
acids at 28 wt% HCl have been used to stimulate gas wells in
this formation.22 A thorough tubing pickling was conducted
before each treatment. Some of these treatments were done
before well perforation, while others were pickled following
perforating these wells.
SPE 73706
Well Completion
More than twenty vertical, cased (unperforated and perforated)
wells were examined. These wells were completed with 4.5,
5.5” tubing or combinations of both. C-95 grade tubing with
new Vam connecters are used in these wells. L-80 grade
connections or crossovers are also used in some cases. Table 1
gives the elemental composition of C-95, L-80 and the high-
pressure coiled tubing that was used to pickle the tubing of
some wells. All wells are completed with 7” or 7x4.5”
cemented liners. The perforation density is 6 shot per foot at
60° phasing. The perforation diameter is 0.32” and the length
of the perforation tunnel is 22”. A typical cross section of gas
wells in this field is shown in Fig. 1. Solares gave more
details on well completion and the mechanical strength
requirements for well tubulars for the frac treatments.23 Rahim
and Al-Qahtani discussed the criterion used for selecting the
perforation intervals.22
Experimental Studies
A thorough experimental program was conducted to optimize
tube pickling procedures. The study is divided into several
parts. In the first part, the composition of pipe dope and its
characteristics were determined. Two types of pipe dope were
noted: one is used for the joints of well casing and production
tubing, whereas the second one is used for the joints of drilling
pipe. Photos 1 and 2 show the two types of pipe dope.
Samples of pipe dope were obtained from a local supplier and
they typical to those used in the field.
To determine the composition of pipe dope, the samples
were first soaked in xylene (typically 100 g of pipe dope in
1000 cm3 of xylene) to dissolve the organic portion (heavy
hydrocarbons). The hydrocarbon content of the pipe dope was
then determined using gravimetric techniques. Acid solubility
tests were conducted on xylene-insoluble material.
Hydrochloric acid at 20 wt% was used in these tests. The acid
to solids weight ratio was 10:1 and the soaking time was two
hours. Chemical analysis of the supernatant was conducted to
determine the concentrations of key ions. The composition of
the acid in-soluble portion was determined using XRD and
XRF techniques. The density and particle size distribution of
the xylene-insoluble portion were also determined.
Pickle treatments were conducted on perforated and
unperforated wells. For unperforated wells, the acid was
pumped down the tubing then lifted from the wellbore using
coiled tubing (CT). For perforated wells, the acid was
bullheaded and the reservoir pressure was used to lift the spent
acid from the wellbore. Every effort was made to avoid
pumping the spent acid into the formation. Therefore, the acid
was placed up to 50 ft above the upper set of perforations.
Samples of well flow back were collected every two minutes.
This short interval was needed to follow acid reactions with
wellbore contaminants.
The well flow back samples typically contained diesel
(unperforated wells) or condensate (perforated wells), aqueous
phase, mainly the spent acid, and solids. Each phase was
separated and analyzed. Several analyses were conducted on
the aqueous phase including measuring sulfide, pH, Cl, Na,
SPE 73706 LESSONS LEARNED FROM ACID PICKLE TREATMENTS OF DEEP/SOUR GAS WELLS
Ca, Mg, Zn, Pb, Mn, and total iron. Sulfide content and pH
were determined on site. In addition, ferrous ion concentration
was measured in the field using the method of Taylor et al.26
The concentrations of various cations were determined by
Inductively Coupled Plasma Emission Spectroscopy (ICP).
The sulfate ion concentration in the aqueous phase was
measured turbidimetrically following precipitation with a 0.1N
barium chloride solution. The chloride ion was measured by
titration using a 0.1N silver nitrate solution. The concentration
of hydrochloric acid was measured by acid/base titration using
a 0.1N NaOH solution.
The solids were filtered out, dried then analyzed using
SEM, XRD, and XRF techniques.
Governing Equations
Reaction of Acid with Magnetite (Fe3O4)
Magnetite is the most likely iron scale present on the tubulars
of new and old wells where there is no hydrogen sulfide
present in the system. Dissolution of magnetite in HCl acid
can be described by the following equation:27
Fe3O4 + Fe + 8H+ = 4 Fe2+ + 4 H2O
Tanaka and Tamamushi examined the reaction rate of HCl
with magnetite.28 The fraction coQYHUVLRQ RI VFDOH  c) as a
function of time, t, can be expressed as:
− ln (1 - α c ) = β sinh kt
LVDFRQVWDQWWKDWHTXDOVIRU+&O-magnetite system. The
approximate reaction rate of the acid, k, is:27
k = k i (a H ) 0.5 (a Fe ) 0.5 (a Fe ) -0.5 (a An ) u
+ 2+ 3+ y-
where aj is the activity coefficient for a species j and u is a
constant that depends on the type of acid used. For HCl, the
value of u is approximately 0.7.
Reaction of Acid with Iron Sulfide (FeS)
The type of iron scale present on well tubulars depends on the
composition of the produced gas, especially its hydrogen
sulfide content. Iron sulfide scale is present in perforated
wells. This is especially true for the northern area wells where
hydrogen sulfide content can reach 10 mol%. Iron sulfide
scale is present in several chemical species, which differ in
acid solubility. Iron sulfide species with iron to sulfur molar
ratios close to unity are soluble in minerals acids. However,
iron sulfide species with sulfur to iron a molar ratio of two
have very low solubility in HCl acid.17,29
Hydrochloric acid reacts with iron sulfide (FeS) as
follows:
FeS + 2H+ → H2S(g) + Fe2+
3
The rate of this reaction was given by Lawson et al.,30
Equation 5:
Rate = kf [H+]– kb [Fe2+]0.5 (PH2S)0.5 (5).
Where kf and kb are the rates of the forward and backward
reactions, respectively. Several important points can be
inferred from Equation 5. The rate of dissolution of iron
sulfide can be increased by using concentrated acids. This
finding was confirmed by Lawson et al.30 using sulfuric acid
and by Nasr-El-Din et al.31 using hydrochloric acid.
Accumulation of hydrogen sulfide in the system will reduce
the rate of acid reaction with the scale. Therefore, it is very
important to scavenge hydrogen sulfide so as to dissolve iron
sulfide scale. It may be also useful to use an iron chelating
agent to maintain the forward (dissolution) reaction.
Based on the experimental work performed by Nasr-El-
Din et al.,31 HCl at 20 wt% was recommended for pickling
treatments that were conducted in the field. Higher acid
concentrations were not recommended because the acid
becomes very corrosive at high concentrations, especially at
(1) high temperatures. Concentrated acids will require large
amounts of corrosion inhibitors, which many adversely affect
the ability of the acid to dissolve iron scale.31
Based on Equation 5, and the nature of iron sulfide scale,
the acid should contain several additives. First, the acid
should contain a corrosion inhibitor to protect the base metal.
(2) Secondly, a water-wetting surfactant should be added to the
acid to remove condensate and other hydrocarbons from the
surface of iron sulfide scale. The surfactant will enhance acid-
scale contact. Thirdly, the acid should contain a suitable
hydrogen sulfide scavenger. Nasr-El-Din and coworkers have
examined the performances of hydrogen sulfide scavengers
(3) that are used during well acidizing.31-33
Mass Transfer during Acid Pickling
To perform an efficient acid pickling treatment, the injected
acid and other cleaning chemicals should come in contact with
mill scale or the material they suppose to dissolve and remove.
Mill scale and other scales, in general, will be always covered
with hydrocarbons and other contaminants. These
contaminants are insoluble in acid and, as a result, they will
act as a diffusion barrier that will prevent the acid from
contacting iron scale. Therefore, there is a need to remove
these materials so that the surface of the scale becomes water-
wet and there will be good chance that the acid will dissolve
the iron scale. To overcome this problem in the field, various
surfactants were added to the preflush and to the acid. In
addition, slugs of organic solvents were employed to remove
pipe dope. Once these contaminants are removed, the acid
will diffuse into the surface and reacts with the iron scale.
This mass transfer process includes acid diffusion to the
surface, then acid reaction with the scale, a heterogeneous
(4). reaction, and finally diffusion of the reaction products from
the tubing surface into the main stream.
4 H.A. NASH-EL-DIN, S.H. AL-MUTAIRI, S.M. AL-DRIWEESH SPE 73706

Mass transfer of a reactive species to the surface of a tube unperforated wells where a CT was used, e.g., well WHD-
was examined by Levich35 and Loewen et al.8 According to X10, Re for fluid flow in the tubing was nearly 12,813 and
Levich, the local mass transfer rate of the acid depends on the 11,400 for fluid flow in the line (liner has a larger diameter
type of flow in the tubing: laminar or turbulent flow. than the tubing). For perforated wells, e.g., WHW-X14, Re
For laminar flow, the local mass transfer rate, JL, is: numbers are 33,085 and 18,741 for fluid flow in the tubing
1 and liner, respectively. Based on these values, the flow of the
 U b  3
acid slug was turbulent in all cases studied. Therefore,
J L = 0 . 67 C b D m
  (6)
Equation 7 can be used to predict the local mass transfer rate
 D m Rx  during pickling treatments.
All symbols are defined in the nomenclature. For turbulent Results and Discussion
flow, the local mass transfer rate, JT, is: Characteristics of Pipe Dope
Samples of the pipe dope (Photos 1 and 2) used during
k f U o Cb placing well casing and the drill pipe were examined. Table 2
JT = (7) summarizes the results obtained with the two types of pipe
2 α Pr 3 4 dope. The pipe dope that was used for the casing contained
nearly 26 wt% of organic material, whereas that was used in
where is a constant (equals unity) and Pr is Prandtl number, drill pipe had 39 wt% organic materials.
given by: In order to characterize the inorganic portion of the pipe
dope, the hydrocarbon portion was first dissolved using
Pr = (8) xylene. Several tests were conducted on the xylene insoluble
Dm material. XRD analysis indicated that the casing and tubing
Kf is the friction coefficient and its value depends on Reynolds pipe dope (brown) contained mainly lead. Zinc, copper, talc,
number as follows: Mg3Si4O10(OH)2, muscovite KAl3Si3O10(OH)2 and graphite
were present at lower concentrations. On the other hand, zinc
0.32 was the main constituent of the drill pipe dope (gray), whereas
Kf = 1
Re ”6 (9) talc, graphite, and zincite, ZnO, were present in minor
4
Re amounts.
The concentrations of various cations in the inorganic
0.221 portion of pipe dope were determined using XRF techniques,
K f = 0.0032 + Re > 106 (10) and the results are given in Table 3. The drill pipe dope
0.237Re contained mainly zinc and almost no lead. This is in
agreement with the XRD analysis. The casing pipe dope
Reynolds number can be calculated for the tubing as follows: contained lead and zinc. Both types of pipe dope contained
other elements, but in smaller concentrations including Si, Ca,
UbD Mg, and Al.
Re = (11) Particle size distribution of the xylene insoluble material
was determined using sieve analysis. The results indicated
that the mean particle size for the drill pipe type (gray) was
For annular flow, the hydraulic diameter, DH, should be used 0.25 mm, whereas that of the casing type (brown) was nearly
instead of D. The hydraulic diameter can be calculated as per 0.08 mm.
Equation 12: The density of the inorganic portion in the pipe dope that
is used for the casing is slightly higher than that of the pipe
4 × volume of liquid dope used in the drill pipe. The casing pipe dope contained
DH = = ( D2 − D1 ) (12)
lead (density = 11.34 g/cm3 at 20ºC), and copper (density =
Surface wetted by liquid
8.95 g/cm3 at 20ºC). The pipe dope used in the drill pipe has
zinc (density = 7.14 g/cm3 at 20ºC) as a major component.
where D2 is the outer diameter of the CT and D1 is the inner
The difference in the density of various elements resulted in
diameter of tubing or liner.
the apparent difference noted in the density of the inorganic
Equations 6 and 7 suggest that to increase the local rate of
portion of the two types of pipe dope examined.
mass transfer, the acid should be used at high concentration
Composition of the inorganic portion and surface area also
and should be pumped at the highest possible rate. Pickling
affect acid solubility (Table 2). The drill pipe dope has a
treatments were designed to take these two points into
solubility of 75 wt%, whereas that of the casing dope has only
consideration.
25 wt%. The former pipe dope contains zinc at high
It is important to note that the acid (20 wt% HCl) used in
concentration. As a result, its acid solubility was high. On the
the pickling treatment had a density of 1.1 g/cm3 and a
other hand, the casing pipe dope contained lead and copper
viscosity 2 mPa.s, both at ambient conditions. Reynolds
and much less zinc. Lead has a low solubility in HCl. It forms
number will vary during a typical pickling treatment. For
SPE 73706 LESSONS LEARNED FROM ACID PICKLE TREATMENTS OF DEEP/SOUR GAS WELLS
PbCl2, which has low solubility in water at ambient
conditions. Copper does not dissolve in HCl under the test
conditions. Other elements that dissolve in acid include
calcium, magnesium and iron. However, these elements are
present in both types of pipe dope. Therefore, they cannot be
used to explain the difference noted in acid solubility of the
two types of pipe dope.
XRD analysis was also conducted on the acid-insoluble
solids. For the casing pipe dope, lead chloride, PbCl2, was the
main component followed by talc, muscovite, copper and lead.
Different results were obtained with the drill pipe dope. Talc
and graphite were the main components followed by
muscovite and quartz. It is evident from these results that
almost all zinc was dissolved in the acid.
Analysis of the supernatant following acid reaction is
shown in Table 4. The concentration of zinc was extremely
high in the supernatant of the drill pipe dope, reaching 71,774
mg/L. Because of the acid reaction with zinc, acid
concentration decreased from 19.4 to 9.2 wt%. Zinc was also
present in the supernatant of the casing pipe dope, but at a
much lower concentration. Lead was present in the casing pipe
dope. Calcium, iron and magnesium were also present in both
types of pipe dope, but at much lower concentrations.
It is evident from these data that zinc is the main acid
soluble component present in both types of pipe dope. In
addition, Zn is not present in the low-carbon steels that were
used to manufacture the CT, tubing or casing (Table 1).
Therefore, Zn can be used as a marker for the pipe dope. Its
concentration in the flow back samples can be used to
determine the effectiveness of clean-up procedures in the field.
Pickling of Unperforated Wells
Unperforated wells were pickled using 1.75” high pressure
coiled tubing. Before the pickling treatment, the wellbore had
a suspension fluid (87 lb/ft3 (pcf) calcium chloride brine) in
the liner and an inhibited diesel in the tubing. The CT was
placed in the wellbore few feet above the well total depth
(TD). Then the cleaning fluids were pumped through the CT at
a rate of nearly 2 bbls/min. The type and sequence of the
cleaning fluids are given in Table 5. It is very important to
follow this sequence because of the nature of each chemical
and the material it is supposed to remove. The cleaning
sequence started with a surfactant wash, an organic solvent,
and 20 wt% acid and finally the displacing water (field mixing
water). Each stage was sandwiched with gelled water stages.
The objective of the gelled slugs was to lift solids released
during wellbore cleaning. Samples of the flow back were
collected and analyzed as explained before.
Several unperforated wells were pickled by this procedure.
Well WHD-X10 is one of these wells. Table 6 gives the acid
formula used, whereas Table 7 gives a typical chemical
analysis of the field mixing water and pickling acid used in
these wells. WHD-X10 has a 5.5”, 20 lb/linear ft (ppf) tubing
(C-95) and 7”, 35 ppf liner (L-80). The surface areas of the
tubing, liner, and CT are given in Table 8. Figure 2 shows
the chloride concentration in the flow back samples. Chloride
5
ion is not a reactive species during the pickling process;
therefore, it can be used as a tracer. The chloride ion exhibits
two main peaks. The first peak occurred during the first 50
minutes and represents the suspension fluid (87 pcf calcium
chloride brine) that was placed in the liner. The second peak
lasted for a longer period of time and represents the acid slug
(5,000 gals of 20 wt% HCl). It is interesting to note that the
rising and falling portions of the peak are narrow. This is
because of the gelled fluids that were pumped before and after
the acid slug. The higher viscosity fluids reduced dispersion
of the acid slug in the wellbore.
Acid concentration and pH of the well flow back samples
are shown in Fig. 3. Acid concentration in the live acid was
measured on site using a titration method and found to be 23.1
wt%, Table 7. The aqueous phase present in the initial
samples had a pH values greater than 7. This is due to the
alkaline nature of the suspension fluid that was placed in the
liner. The pH values reached nearly zero once the acid arrived
at the wellhead. Low pH values lasted for a long period of
time, then gradually increased and reached a value of 2-3 by
the end of the pickling process. Acid concentration increased
gradually until it reached 19.6 wt% (i.e., 85% of the injected
value) then gradually decreased due to pumping of the
displacing water. These results indicated that a portion of the
acid was spent in the wellbore.
One of important points to highlight is the role of the acid
in the pickling treatment. This is demonstrated in Figs. 4 to 7.
The reason for using an acid in the pickling process is to
remove iron scale and other acid-soluble contaminants from
the wellbore. Hydrochloric acid reacts with magnetite and
produces ferrous and ferric ions. Figure 4 shows the total iron
in the flow back samples. The concentration of ferrous ions
was measured on site in few samples and is also shown in Fig.
4. Iron was noted in all acidic samples and the total iron
concentration reached 26,799 mg/L after nearly 140 minutes.
Iron profile shows a long tailing, which lasted for more than
60 minutes.
Sources of the produced iron include: iron present in the
live acid, mill scale on the inner surface of the liner, tubing
and the external surface of the coiled tubing. Iron
concentration in the live acid was closely monitored and kept
under 100 mg/L. For well WHD-X10, the injected acid
(5,000 gals of 20 wt% HCl) contained 77 mg/L of total iron.
This means that a total of 1.46 kg of total iron was present in
the injected acid.
Figure 4 also shows concentration of Fe(II) in few flow
back samples. Fe(II) concentrations were lower than Fe(III).
Maximum Fe(II) measured was 3,175 mg/L. This means that
the Fe(III):Fe(II) ratio at the peak was 7.4:1. The sources of
Fe(II) are magnetite and the tubing. The amount of iron
produced during well flow back was obtained by integrating
the data shown in Fig. 4 and was found to be 56.6 kg. This
result means that 2.6 wt% of the total produced iron is due to
the iron originally present in the injected acid. The source of
the majority of produced iron is the tubing, liner and may the
6 H.A. NASH-EL-DIN, S.H. AL-MUTAIRI, S.M. AL-DRIWEESH
CT. In other words, the main source of produced iron is the
well tubulars.
The amount of produced iron is significant, which confirms
the importance of cleaning and pickling the tubing before
performing acid treatments. This iron would have invaded the
formation and caused formation damage, if the tubing and
liner were not pickled.
Acid will also dissolve some of the heavy metals present in
the pipe dope. Figure 5 depicts the concentration of Zn in the
flow back samples. Zinc appeared in the acidic samples only.
The main source of Zn is the pipe dope. The maximum Zn
concentration noted in the flow back was 194 mg/L. The
amount of Zn dissolved by the acid is 284 g, Table 8.
Pipe dope also contains lead. Figure 5 also shows that
lead peaked in the acidic samples and reached a maximum of
104 mg/L. The amount of lead produced in the flow back
samples was 256 g. The amount of Zn and Pb produced are
very small. However, their presence in the flow back samples
indicates that the organic solvent was able to dissolve the
greasy material of the pipe dope and exposed its heavy
elements to the acid. It is interesting to note that the amount
of Zn and Pb found the flow back samples is 388 g. This is a
small quantities if compared with the amount of iron produced
(56.6 kg). These results clearly indicate that iron scale is the
main material dissolved by the acid.
The results discussed thus far demonstrate the importance
of tube pickling process. However, acids are corrosive and can
attack the well tubulars. One way to determine down hole
corrosion during tube pickling treatments is to follow the
concentration of manganese. The tubing and liner are made of
low-carbon steels (C-95 and L-80). Both materials contain
manganese, Table 1. Moreover, the CT contains manganese,
however at nearly half the concentration in the tubing or liner.
If the acid attacks the tubing, then it will dissolve manganese.
Figure 6 shows that Mn peaked in the acidic samples and
reached a maximum of 266 mg/L. The total amount of
manganese is 143.4 g. It is important to note that Mn lagged
total iron peak, which indicates that the acid dissolved the mill
scale first, magnetite, then reacted with the tubing.
The presence of Mn confirms that the acid attacked the
tubing, liner and the CT. However, the total amount produced
was very small, 143.4 g (Table 8). The weight ratio of Fe:Mn
produced in the flow back samples is much higher than that
present in the low carbon steel tubing, Table 1. This indicates
that the acid dissolved the mill scale and did not significantly
attack the tubing. Considering the total amounts of iron and
manganese dissolved by the acid and the exposed area of the
tubing and liner, the amount of dissolved material is 0.0078
lb/ft2. If the amount of iron diss9olved from the tubing and
liner, then the corrosion rate is 0.001 lb/ft2. Both values are
much less than the industry accepted corrosion rate of 0.05
lb/ft2. In other words, the corrosion package (inhibitor and
intensifier) was able to protect well tubulars during the
pickling treatment.
Figure 7 shows the concentrations of calcium and sodium
in the flow back. Both cations peaked during the first 50
minutes. This is due to the suspension fluid that was placed in
SPE 73706
the liner. Calcium exhibits another peak in the acid samples.
The second peak resulted from the dissolution of calcium
carbonate particles using the suspension fluid by the acid.
Flow back samples collected from the wellhead contained
suspended solids. These solids were separated and analyzed
using XRD and XRF techniques and the results are presented
in Tables 8 and 9. Pre-acid samples contained barite, calcium
and magnesium carbonates. These materials are used in the
suspension fluid that was present in the liner before the pickle
treatment. The pickling process was effective in removing
these solids. The acidic fluids contained barite and magnetite.
Calcium carbonate and dolomite particles are soluble in HCl
acid. Therefore, they were not detected in the acidic samples.
It is interesting to note that solids contain heavy metals, e.g.,
lead, copper. The source of these elements is the pipe dope. It
is likely that the diesel that was present in the tubing or the
organic solvent that was used during the pickling treatment
dissolved the greasy material in the pipe dope and, as a result,
the heavy elements settled in the wellbore. Some of these
particles were suspended and carried with the cleaning fluids
to the surface.
Pickling of Perforated Wells
Pickling of perforated wells is different from that performed
on unperforated wells in several aspects. First, there is
communication between the wellbore and the formation
through the perforations. Spent acid, which is usually loaded
with iron, should not be allowed to invade the formation under
any circumstances. Secondly, the spent acid will be lifted by
the reservoir pressure, or simply by allowing the formation gas
to flow to the surface. In this case, there will be no need to use
a CT to lift the spent acid. Thirdly, the flow path of the spent
acid is different. Unlike unperforated wells, the spent acid
will flow back in the same tubing where it was pumped in the
first place. This means that the acid will contact the same
surface two times. Fourthly, the produced gas may contain
hydrogen sulfide and other acidic gases. These gases may
react with various chemical species present in the spent acid
and precipitate iron sulfide and iron carbonate. The nature of
iron scale present in the wellbore is different. Iron oxides are
present in the unperforated wells; whereas various iron sulfide
species will be present in perforated wells. Finally, flow of
gases through wellbore fluids will increase mixing and
dispersion of the acid slug. These differences will affect the
concentration profiles as will be discussed later in this paper.
Lifting spent pickle acid from the wellbore of perforated
wells is a major concern for sour wells. The well flow back
will contain significant amount of hydrogen sulfide, which is a
toxic gas. To address this problem, several modifications were
introduced to the sequence and additives used to pickle
perforated wells. First, a suitable hydrogen sulfide scavenger
was added to the acid slug. Secondly, the pH of the gelled
water was raised to 10. This is to ensure that all hydrogen
sulfide is captured before the spent acid reached the wellhead.
Several perforated wells were pickled by bullheading the
acid. The spent acid in this case was lifted by the reservoir
pressure. The pickling sequence for perforated wells is given
SPE 73706 LESSONS LEARNED FROM ACID PICKLE TREATMENTS OF DEEP/SOUR GAS WELLS
in Table 5. The results of well WHW-X14 will be discussed
in this paper. Table 8 gives the surface areas of the tubing,
and liner for this well. Chemical analysis of the pickling acid
and mixing water were similar to those given in Table 7. Total
iron concentration in the live acid was 17 mg/L.
Figure 8 shows the chloride ion concentration in the flow
back samples of well WHW-X14. Initial chloride
concentrations were very low. This is due to the low senility
water that was used to perforate this well. The chloride
concentration increased to almost 20,000 mg/L marking the
acid slug. Chloride concentration started to decrease after 60
minutes and showed a very long tail.
Acid concentration and pH values in the flow back samples
are depicted in Fig. 9. The two profiles were in general similar
to those noted in well WHD-X10. The only difference
between the two profiles is the tendency for tailing noted with
the perforated well.
Total iron concentration is shown in Fig. 11. Iron
concentration reached up to 105,488 mg/L and showed high
values for a long period of time. The total amount of iron was
1,027 kg, Table 8. Considering the surface areas given in
Table 8 and the fact that he acid contact the same surface two
time, the amount of iron dissolved per unit area is 0.075 lb/ft2.
This amount is almost an order of magnitude greater than that
noted in well WHD-X10.
Ferrous ion concentrations were not measured for this well.
However, they were measured in well WUT-X20, another
perforated well which produces gas with 10 mol% H2S.
Figure 10 illustrates the concentrations of total iron and
ferrous ions in the well flow back samples. The maximum
total iron obtained in this well was 75,215 mg/L and the
maximum Fe(II) was 24,000 mg/L. The ratio of Fe(III) to
Fe(II) at the peak was nearly 2.1. This value is much smaller
than that note in well WHD-X10. During the flow back, there
was a strong reducing environment, which promoted the
formation of the Fe(II).
The acid did dissolve Zn and Pb, as shown in Fig. 12. Both
ions peaked simultaneously with the iron peak was noted. The
maximum concentration of Zn and Pb were 301 and 45 mg/L,
respectively. Integration of both peaked indicated that the total
amount produced from the two elements were 1.178 and 0.273
kg, respectively.
The concentrations of total iron and manganese are plotted
in Fig. 13. Maximum Mn concentration was 525 mg/L. The
total amount of Mn produced is 6.584 kg. The total amount of
iron that dissolved from the base metal is 59.05 kg. The
amount of metal dissolved by acid per unit area is 0.0098
lb/ft2. Similar to the results obtained with well WHD-X10, this
value is significantly less than the accepted value of 0.05
lb/ft2.
Low initial concentrations of calcium and sodium were
noted with well WHW-X14, Fig. 14. No major changes were
observed with the sodium during flow of acidic solution.
However, a small peak was noted for the calcium. The most
likely source of calcium is the residual of calcium carbonate
particles that were used during drilling and work-over
7
operations.
A Comparison of Pickling Treatment of Perforated and
Unperforated Tubing
The results discussed thus far show that there are some
differences between the tube pickling treatment conducted
before and after perforation. It is of interest to compare the
two cases. Pickling of unperforated tubing was conducted via
a CT. In this case, the acid flows through the CT, then
through the CT/tubing annulus. The acid will contact a given
surface of the tubing one time only. The leading edge of the
acid will arrive first to the wellhead. Also, the front edge has
to flow from the bottom of the well to the top.
In perforated wells, the situation is different. The acid is
bullheaded and placed nearly 50 ft above the upper set of
perforations. The spent acid is lifted by the reservoir pressure.
In this case, the acid will contact the surface of the tubing two
times. Also, the trailing edge of the acid slug will arrive to the
wellhead first. The time required for the trailing edge to reach
the wellhead is shorter. These differences will affect the
concentration profiles of key species in the flow back samples.
Figure 15 shows the total iron and acid profiles in the flow
back samples of well WHD-X10. The leading edge of the
acid produced first in unperforated wells. Note that the iron is
detected earlier than the acid. This indicates that a portion of
the acid was spent due to iron scale dissolution. High iron
concentration can be seen close to the leading edge of the acid.
An opposite trend can be seen in Fig. 16 for well WHW-
X14, a perforated well. In this case, the trailing edge of the
acid came first. Iron peak is close the leading edge of the acid
slug, which can be seen after nearly 60 minutes of flow back.
It is interesting to note that the acid profile started with high
concentration, which decreased with time. This is again
opposite to the trend noted with well WHD-X10.
The results shown in Figs. 15 and 16 highlight the need
to understand the flow path of the acid in a given system. This
understanding is essential in deciding sampling frequency and
timing.
The mode of acid pumping also affect mixing pattern
between the acid slug and other fluids present in the well bore
area. This point is demonstrated in Figs. 17 and 18. In these
figures, the normalized concentration of the chloride ion is
plotted as a function of flow back time. The normalized
concentration is defined as the chloride concentration at a
given time divided by the chloride concentration in the
injected acid). For well WHD-X10, there was minimum
mixing in the leading and trailing edges of the acid slug, Fig.
17. Figure 18 demonstrates a different trend for well WHW-
X14. In WHW-X14, the leading edge of the acid slug, which
appeared after 60 minutes of well flow back. There was strong
mixing of the acid slug with the preflush and, as a result, the
leading edge looked dispersed. The fact that the reservoir rock
has a low permeability before the acid fracture treatment, may
explain this effect.
8 H.A. NASH-EL-DIN, S.H. AL-MUTAIRI, S.M. AL-DRIWEESH SPE 73706

Conclusions Production Engineering Division and local service companies

are acknowledged for many useful discussions. Mr. A.A. Al-
1. Analysis of spent acids indicated that the major
Thawaiqib and Mr. J.A. Hopkins are greatly appreciated for
tubular contaminants are mill scale and pipe dope.
their support.
2. Spent acid samples collected from deep sour gas
wells contained up to nearly 105,500 mg/L of total
References
iron.
1. Maly, G.P.: “Close Attention to the Smallest Job Details
3. The concentration of zinc in spent acid was used to
Vital for Minimizing Formation damage,” paper SPE 5702
assess the efficiency of removing pipe dope.
presented at the 1976 SPE Symposium on Formation
4. The concentrations of acid and iron were used to
Damage Control, Lafayette, LA, 29-30 January.
determine acid reaction with the corrosion products
2. Holub, R.W., Maly, G.P., Noel, R.P., Weinbrandt, R.M.:
present in the tubing.
“Scanning Electron Microscope Pictures of Reservoir Rocks
5. The concentration of the chloride ions was used to
Reveal Ways to Increase Oil Production,” paper SPE 4787
determine the dispersion and mixing behavior of the
presented at 1974 SPE Symposium on Formation Damage
acid slug.
held in New Orleans, LA, 7-8 February.
This work presents the results obtained from analyzing
3. McLeod, H.O., Jr., Ledlow, L.B., and Till, M.V.: “The
more than 2000 samples obtained from twenty treatments. The
Planning, Execution and Evaluation of Acid Treatments in
results of this work have been used to enhance the efficiency
Sandstone Formations,” paper SPE 11931 presented at the
of the pickle treatments and to significantly reduce the
1983 Annual Technical Conference and Exhibition held in
treatment cost. This is extremely important in deep sour gas
San Francisco, CA, 5-8 October.
wells.
4. McLeod, H.O., Jr.: “Matrix Acidizing,” JPT (Dec. 1984)
2055.
Nomenclature
5. Ertas, A., Cuvalci, O., and Carper, H.J., Jr.: “Determination
aj activity coefficient of a species j -
of Friction Characteristics of J-55 OCTG Connections
Cb Bulk Concentration of H+ mole/m3
Lubricated with Environmentally Safe Thread Compounds,”
D Inner diameter of CT or tubing m
Tribology Transactions, 42 (1999) 881-887.
D1 Inner diameter of Tubing m
6. Prengaman, R.D.: “How Do they Work?” JPT (October
D2 Outer diameter of Coiled Tubing m
1981) 93-106.
DH Hydraulic diameter m
7. Smith, B.: “Proper Treatment of Tubulars Key to Iron
Dm Diffusion Coefficient of H+ m2/s
Control,” Southwestern Petroleum Short Course, 1990.
J Local Mass Transfer Rate mole/m2.s
8. Loewen, K., Chan, K.S., Fraser, M., and Leuty, B.: “A
k Reaction Rate Coefficient -
Well Stimulation Acid Tube Clean Methodology,” paper
Kf Friction Coefficient -
CIM/SPE 90-47 presented at the 1990 International
Q Pickle Acid Pump Rate m3/s
Technical Meeting of the CIM and SPE held in Calgary,
R Tubing Inner Radius m
AB, Canada, 10 - 13 June.
t Time s
9. Coulter, A.W., Jr. and Gougler, P.D.: “Field Tests
x Length of Contact m
Indicate Tubing is Main Source of Iron Precipitation in
Re Reynolds Number -
the Wellbore,” OGJ (Sept. 3, 1984) 87.
Pr Prandtl Number -
10. Hall, B.E. and Dill, W.R.: “Iron Control Additives for
Ub Bulk Velocity m/s
Limestone and Sandstone Acidizing of Sweet and Sour
Wells,” paper SPE 17157 presented at the 1988 SPE
Greek Symbols
Formation Damage Control Symposium held in
αc Fractional Conversion -
Bakersfield, CA, 8-9 February.
β Reaction Constant - 11. Smith, C.F., Crowe, C.W. and Nolan, T.J., III:
Fluid Viscosity mPa.s “Secondary Deposition of Iron Compounds Following
Fluid Density kg/m3 Acidizing Treatments,” JPT (Sept., 1969) 1121.
12. Crowe, C.W.: “Evaluation of Agents for Preventing
Kinematic Viscosity m2/s
Precipitation of Ferric Hydroxide from Spent Treating
Acid,” JPT (April 1985) 691.
Acknowledgments
13. Taylor, K.C., Nasr-El-Din, H.A. and Al-Alawi, M.:
The authors wish to acknowledge the Saudi Arabian Oil
“Systematic Study of Iron Control Chemicals Used
Company (Saudi Aramco) for granting permission to present
During Well Stimulation,” SPEJ, 4 (1999) 19-24.
and publish this paper. Udhailiyah Lab Unit, SALD and the
14. Walker, M.L., Dill, W.R., Besler, M.R. and McFatridge,
Chemistry Unit and Advanced Instruments Unit of the R&D
D.G.: “Iron Control in West Texas Sour-Gas Wells
Center, Saudi Aramco were very helpful in their field
Provides Sustained Production Increases,” JPT (May,
monitoring and analysis of the spent acids, respectively.
1991) 603.
Members of the stimulation group, R&DC are acknowledged
for processing well flow back samples. All engineers in Gas
SPE 73706 LESSONS LEARNED FROM ACID PICKLE TREATMENTS OF DEEP/SOUR GAS WELLS
15. Walker, M.L., Dill, W.R., and Besler, M.R.: “Iron Control
Provides Increase in Wells Containing Sour Gas,” JCPT
(November 1990) 46.
16. Kasnick, M.A. and Engen, R.J.: “Iron Sulfide Scaling and
Associated Corrosion in Saudi Arabian Khuff Gas Wells,”
paper SPE 17933 presented at the 1989 SPE Middle East
Oil Technical Conference and Exhibition held in Manama,
Bahrain, 11-14 March.
17. Ford, W.G.F., Walker, M.L., Halterman, M.P., Parker,
D.L., Brawley, D.G., and Fulton, R.G.: “Removing a
Typical Iron Sulfide Scale: The Scientific Approach,”
paper SPE 24327 presented at the 1992 SPE Rocky
Mountain Regional Meeting held in Casper, WY, 18-21
May.
18. Brezinski, M.M.: “Chelating Agents in Sour Well
Acidizing: Methodology or Mythology,” paper SPE
54721 presented at the 1999 SPE European Formation
Damage Conference, The Hague, The Netherlands, May
31 – June 1.
19. Ashford, D.I.: “Effective Acid Pickling Increase
Production,” paper CIM # 13 presented at the 1987
Technical Meeting of the South Saskatchewan held in
Regina, SK, Canada, 6-8 October.
20. Smolarchuk, P., and Dill, W.: “Iron Control in Fracturing
and Acidizing Operations,” paper CIM 86-37-28
presented at the 1986 Annual Meeting of CIM held in
Calgary, AB, Canada, 8-11 June.
21. Gougler, P.D., Jr., Hendrick, J.E. and Coulter, A.W.:
“Field Investigation Identifies Source and Magnitude of
Iron Problems,” paper SPE 13812 presented at the 1985
SPE Production Operations Symposium, Oklahoma City,
OK, 10-12 March.
22. Rahim, Z. and Al-Qahtani, M.: “Selecting Perforation
Intervals and Stimulation Technique in the Khuff Reservoir
for Improved and Economic Gas Recovery,” paper SPE
68216 presented at the 2001 SPE Middle East Oil
Technical Conference and Exhibition held in Manama,
Bahrain, 17-20 March.
23. Solares, J.R.: “Efficient Technology Application to
Optimize Deep Gas Well Completions in the Khuff and
Jauf Formations Requiring Hydraulic Fracturing in Saudi
Arabia,” paper SPE 68206 presented at the 2001 SPE
Middle East Oil Technical Conference and Exhibition
held in Manama, Bahrain, 17-20 March.
24. Lynn, J.D. and Nasr-El-Din, H.A.: "Formation Damage
Associated with Water-Based Drilling Fluids and
Emulsified Acid Study,” paper SPE 54718 presented at
the European Formation Damage Conference, The Hague,
The Netherlands, May 31-June 1, 1999. Also appeared in
JPT (November 1999) 28-29.
25. Temeng, K.O., Al-Sadeg, M.J., and Al-Mulhim, W.A.:
“Compositional Grading in the Ghawar Khuff
Reservoirs,” paper SPE 49270 presented at the 1998
Annual Technical Conference and Exhibition held in New
Orleans, LA, 27-30 September.
26. Taylor, K.C., Nasr-El-Din, H.A. and Al-Alawi, M.: “Field
9
Test Measures Amount and Type of Iron in Spent Acids,”
paper SPE 50780 presented at the 1999 SPE Oilfield
Chemistry, Houston, TX, 16-19 February.
27. Frenier, W.W. and Growcock, F.B.: “Mechanism of Iron
Oxide Dissolution – A Review of Recent Literature,”
Corrosion, 40 (1984) 663.
28. Tanaka, N., Tamamushi, R.: “Kinetic Parameters of
Electrode Reactions,” Electrochimica Act., 9 (1964) 963.
29. Nasr-El-Din, H.A., Al-Humaidan, A., Mohamed, S.K.,
and Salman, A.: “Iron Sulfide Scale Formation in Water
Supply Wells with Gas Lift,” paper SPE 65017 presented
at the 2001 SPE Oilfield Chemistry, Houston, TX, 13-16
February.
30. Lawson, M.B., Martin, L.D. and Arnold, G.D.: “Chemical
Cleaning of FeS Scales,” paper NACE # 219,
Corrosion/80 held in Houston, TX, March.
31. Nasr-El-Din, H.A., Al-Humaidan, A., Fadel, B.A., and
Saleh, R.: “Effect of Acid Additives on the Efficiency of
Dissolving Iron Sulfide Scale,” paper NACE # 439
presented at the NACExpo X20, Orlando, FL, March 26-
31.
32. Nasr-El-Din, H.A., Al-Humaidan, A., Fadel, B., Frenier,
W.W., and Hill, D.G.: “Investigation of Sulfide
Scavengers in Well Acidizing Fluids”, paper SPE 58712
presented at the X20 SPE International Symposium on
Formation Damage Control held in Lafayette, LA, 23-24
February.
33. Al-Humaidan, A.Y. and Nasr-El-Din, H.A.:
"Optimization of Hydrogen Sulfide Scavengers Used
During Well Stimulation," paper SPE 50765 presented at
the 1999 SPE Oilfield Chemistry held in Houston, TX,
16-19 February.
34. Watkins, D.R. and Roberts, G.E.: “On-site Acidizing Fluid
Analysis Shows HCl and HF Contents Often Varied
Substantially from Specified Amounts,” JPT (May 1983)
865.
35. Levich, G.V.: “Physicochemical Hydrodynamics,”
Englewood Cliffs, N.J.: Prentice-Hall, 1962, 112-116 and
154-157.
10 H.A. NASH-EL-DIN, S.H. AL-MUTAIRI, S.M. AL-DRIWEESH SPE 73706

Table 1: Elemental composition of high pressure coiled Table 3: Concentrations of various elements in the
tubing, L-80 and C-95.a inorganic portion of pipe dope samples.a

Variable CT L-80 C-95 Tubing &

Variable Drill Pipe
Casing
Carbon 0.10-0.14 0.43 max 0.45 max
Zn 17.67 48.20
Manganese 0.70-0.90 1.90 max 1.90 max
Pb 24.14 0.37
Molybdenum 0.21 max - - Si 7.95 8.41

Chromium 0.50-0.70 - - Ca 8.58 3.57

Nickel 0.20 max 0.25 max - Cu 6.39 Trace

Mg 5.43 8.44
Copper 0.25 max 0.35 max -
Al 1.59 1.06
Phosphorous 0.025 max 0.030 max 0.030 max
W - 0.85
Sulfur 0.005 max 0.030 max 0.030 max
S 0.24 0.12
Silicon 0.30-0.50 0.45 max 0.45 max
Fe Trace 0.11

a. All concentrations are expressed in weight percent. The P 0.04 0.04

balance is iron.
K 0.50 0.08

Mo 0.05 0.07
Table 2: Characteristics of pipe dope. Ti 0.06 Trace

Ni, Mn Trace Trace

Variable Tubing & Drill Pipe
Na, Cl Trace -
Casing

Color Brown Gray a. Analysis was conducted using XRF technique.

Organic materiala 26.4 wt%b 39.4 wt%b

Inorganic material 73.6 wt% 60.6 wt%

Average Densityc 4.44 g/cm3 4.23 g/cm3

Acid Solubilityd 25 wt% 75 wt%

a. Solubility in xylene
b. Average of three measurements
c. Density of inorganic material
d. Solubility of the inorganic portion in 20 wt% HCl
SPE 73706 LESSONS LEARNED FROM ACID PICKLE TREATMENTS OF DEEP/SOUR GAS WELLS 11

Table 4: Analysis of the supernatant after acid reaction

with the inorganic portion of pipe dope.

Fresh
Spent Acid
Acid
Variable
Casing and
Both Drill Pipe
Tubing
HCl (wt%) 19.4 15.3 9.2
Zn (mg/L) 2 14,624 71,774
Pb (mg/L) 0 2,839 181
Ca (mg/L) 18 1,296 2,424
Cu (mg/L) 0 431 18

Fe (mg/L) 4 152 114

Mg (mg/L) 1 151 186

Al (mg/L) 0 41 35
Na (mg/L) 0 19 28
Mn (mg/L) 0 2 2
Si (mg/L) 0 0 13
a 3
Density (g/cm ) 1.0945 1.1011 1.1572

a. Measured at room temperature.

Table 5: Pickling sequence for perforated and unperforated wells.

WHD-X04 WHD-X28 WSH-X13 WHD-X10

Variable
perforated perforated unperforated unperforated

Gelled water spacer, bbls 10 10 5 5

Surfactant solution, bbls 41 41 32 41

Gelled water spacer, bbls - - - 5

Organic solvent, bbls 4 5.5 5 12

Gelled water spacer, bbls 10 10 5 5

20 wt% HCl, gals 1,300 2,000 2,700 5,000

Gelled water spacer, bbls 10 10 5 5

Field mixing water, bbls 128 - 350 350

12 H.A. NASH-EL-DIN, S.H. AL-MUTAIRI, S.M. AL-DRIWEESH SPE 73706

Table 6: Acid formula for unperforated wells. Table 8: Tubing pickle data.

Concentration Variable WHD-X10 WHW-X14

Gal /1000 gals
Variable
Well status during Pickling Unperforated Perforated
C-1 C-2 C-3
Tubing surface area, ft2 10,519 13,445
Corrosion inhibitor 20 30 20
Liner surface area, ft2 5,486 1,301
Corrosion inhibitor aid 20 50 20
CT External surface area, ft2 5,369 -
Surfactant 2 2 3
Acid concentration, wt% 23.1 21.3
Friction reducer 2 - 2
Acid volume, ft3 668 535
Field mixing water 343 287 342
Pumping rate, ft3/min 7.41 12.13
31 wt% raw HCl acid 613 611 613
Max Fe++, mg/L 3,175 -
a. C-1, C-2, and C-3 are three local service companies.
Max Fe+++, mg/L 23,624 -
Table 7: Analysis of field mixing water & pickling acid.
Max Fe+++/Fe++ 7.4 -

Variable Field Mixing Pickling Max Fe (total), mg/L 26,799 105,488

Watera Acidb
Amount of iron, Kg 56.6 1,027
HCl (wt%) - 21.8

Ca (mg/L) 119 52 Max Zn, mg/L 194 301

Cl (mg/L) - 215,298 Amount of zinc, g 284 1,178

pH 7.8 0 Max Mn, mg/L 266 525

K (mg/L) - 12
Amount manganese, g 143.44 6,584
Si (mg/L) 11 0
Max Pb, mg/L 104 45
Na (mg/L) 206 97
Amount lead, g 256 273
Sr (mg/L) 2 0
Max HCl in flowback, wt% 19.6 21.3
Sulfate (mg/L) 258 184

a. Iron (II) as measured in the field = 0.08 mg/L

b. Total iron of the acid as measured in the field = 77 mg/L.
SPE 73706 LESSONS LEARNED FROM ACID PICKLE TREATMENTS OF DEEP/SOUR GAS WELLS 13

Table 9: XRD of the solids separated from well flow back samples, WHD-X10.

Time (min)
Parameter
89 90 91 111 113 123 125

Sample No. 11 12 13 23 25 28 29
pH 7.9 8 8.1 4.65 3.94 3.6 3.4
Barite-BaSO4, wt% 35 34 37 35 48 75 77
Calcite-CaCO3, wt% 25 27 25 8 - - -
Dolomite-CaMg(CO3)2, wt% 23 23 22 15 - - -

Quartz-SiO2, wt% 9 9 9 12 10 14 11

Magnetite-Fe3O4, wt% 8 7 7 30 - 11 12
Hematite-Fe2O3, wt% - - - - 35 - -
Geothite-FeOOH, wt% - - - - 7 - -

Table 10: XRF of the solids separated from well flow back samples, WHD-X10.

Time (min)
Parameter
89 90 91 111 113 123 125 141
Sample # 11 12 13 23 25 28 29 35
PH 7.9 8 8.1 4.65 3.94 3.6 3.4 0.05
Ba 20.0 19.6 21.2 19.4 21.5 41.2 41.8 14.9
Ca 14.32 15.00 14.32 6.2 0.4 1.12 1.62 0.2
Fe 5.30 4.66 4.72 19.9 22.0 7.43 8.25 3.6
Si 4.23 3.88 3.96 5.0 3.6 5.83 4.93 11.9
S 4.19 3.78 3.96 4.0 5.9 7.92 7.95 9.7
Mg 2.89 2.87 2.80 1.9 0.4 0.94 0.90 0.1
Zn 1.00 0.92 0.97 0.9 0.2 0.27 0.30 0.2
Al 0.78 0.67 0.74 0.4 0.4 1.12 0.88 0.4
 Pb 0.24 0.20 0.20 1.3 1.0 0.99 2.27 0.5
 K 0.21 0.20 0.15 760ppm 720ppm 0.15 0.14 <500ppm
 Sr 0.18 0.20 0.20 0.1 0.2 0.23 0.30 0.1
 Cl 820ppm 680ppm <500ppm 3.6 1.2 0.61 0.44 6.5
 Cu 640ppm <500ppm 520ppm 0.2 0.2 0.38 0.51 1.7
 Cr 520ppm <500ppm <500ppm 0.2 0.1 0.12 0.11 0.7

Mo <500ppm <500ppm <500ppm 0.3 0.2 0.24 0.18 1.0

a. All concentrations are expressed in wt%, except otherwise mentioned.

14 H.A. NASH-EL-DIN, S.H. AL-MUTAIRI, S.M. AL-DRIWEESH SPE 73706

Table 11: Acid formula for perforated wells

Concentration

Variable Gal /1000 gals

C-1a C-2 C-3

Corrosion Inhibitor 8 20 20

Corrosion Inhibitor Aid 20 30 20

Low Surface Tension 2 2 2

Surfactant

H2S Scavenger 10 - 10

Scavenger Aid 1 - -

Friction Reducer 0 2 -

Field Mixing Water 345 355 333

31 wt% Raw HCl Acid 614 591 613

a. C-1, C-2, and C-3 are three local service companies.

SPE 73706 LESSONS LEARNED FROM ACID PICKLE TREATMENTS OF DEEP/SOUR GAS WELLS 15

Photo 1. Casing & Tubing Dope Photo 2. Drill Pipe Dope

Figure 1. Typical Completion for Gas Wells in the Khuff Reservoirs

36", 236#, X-60
30", 234#, X-42

24", 176#, X-42

Nipple
ID = 5.875"
18-5/8", 115#, K-55

7", 32#, C95, NVAM - TUBING

13-3/8", 72#, NKC & C95VT

Btm of 7" tbg / top of 4 1/2" tbg

7" liner hanger

4 1/2", 13.5 #, C95, NVAM - TUBING
7", 35#, L-80, NVAM - LINER # 2

7" TIW tie back assy.

7" TIW Hydro-Hanger

7", 35#, L-80, NVAM - LINER # 1

PBR Assy.

9-5/8", 53.5#, C-95VTS, NVAM

===
=== Khuff "B"
===

===
=== Khuff "C"
===
7", 35#, L-80, NVAM

TD
 16 H.A. NASH-EL-DIN, S.H. AL-MUTAIRI, S.M. AL-DRIWEESH SPE 73706

Figure 2. Chloride Concentration in Flowback Samples of Figure 4. Iron Concentration in Flowback Samples of WHD-
WHD-X10 (Unperforated Well) X10 (Unperforated Well)

250000 30000
Chloride Concentration, mg/L

Initial Acid Concentration = 23.1 wt%

25000

Iron Concentration, mg/L

200000
Fe(total)
20000
150000 Fe(II)
15000
100000
Suspension
10000
Fluid
50000
5000
0
0
0 50 100 150 200 250 300
0 50 100 150 200 250 300
Flowback Time, min
Flowback Time, min

Figure 3. pH & HCl Concentration in Flowback Samples of Figure 5. Zn & Pb Concentrations in Flowback Samples of
WHD-X10 (Unperforated Well) WHD-X10 (Unperforated Well)

25

200
pH & HCl Concentration, wt%

Initial Acid Concentration = 23.1 wt%

20
Concentration, mg/L

160
Pb
15 HCl
Zn
120
pH
10
80
5
40

0
0 50 100 150 200 250 300 0
Flowback Time, min 0 50 100 150 200 250 300
Flowback Time, min
 SPE 73706 LESSONS LEARNED FROM ACID PICKLE TREATMENTS OF DEEP/SOUR GAS WELLS 17

Figure 6. Iron & Manganese Concentrations in Flowback Figure 8. Chloride Concentration in Flowback Samples
Samples of WHD-X10 (Unperforated Well) of WHW-X14 (Perforated Well)

30000 300 250000

Chloride Concentration, mg/L

Initial Acid Concentration = 21.3 wt%

Mn Concentration, mg/L
Fe Concentration, mg/L

25000 250
Fe ( Total) 200000

20000 Mn 200
150000
15000 150
100000
10000 100

50000
5000 50

0 0 0
0 100 200 300 0 50 100 150
Flowback Time, min Flowback Time, min

Figure 7. Ca & Na Concentrations in Flowback Samples of Figure 9. pH & HCl Concentration in Flowback Samples of
WHD-X10 (Unperforated Well) WHW-X14 (Perforated Well)

100000 25
Ca & Na Concentrations, mg/L

Suspension Fluid Initial Acid Concentration = 21.3 wt%

Ca
pH & HCl Concentration, wt%

Na 20
10000

Initial Acid Concentration = 23.1 wt% HCl

15
1000
10

100
5 pH

10 0
0 50 100 150
0 50 100 150 200 250 300
Flowback Time, min
Flow-Back Time, min
 18 H.A. NASH-EL-DIN, S.H. AL-MUTAIRI, S.M. AL-DRIWEESH SPE 73706

Figure 10. Iron Concentration in Flowback Samples Figure 12. Zn & Pb Concentrations in Flowback Samples of
of WHW-X14 (Perforated Well) WHW-X14 (Perforated Well)

120000 350
Total Iron Concentration, mg/L

300

Concentration, mg/L
Pb
250
80000 Zn
200

150
40000
100

50

0 0
0 50 100 150 0 50 100 150
Flowback Time, min Flowback Time, min

Figure 11. Iron Concentrations in Flowback Samples of Figure 13. Iron & Manganese Concentrations in Flowback
WUT-X20 (Perforated Well) Samples of WHW-X14 (Perforated Well)

80000
1000000
Iron Concentration, mg/L

Mn
60000 Fe(total) 100000 Fe(total)
Concentration, mg/L

Fe(II) 10000

40000
1000

100
20000
10

0 1
0 50 100 150
0 10 20 30 40 50
Flowback Time, min
Flowback Time, min
 SPE 73706 LESSONS LEARNED FROM ACID PICKLE TREATMENTS OF DEEP/SOUR GAS WELLS 19

Figure 14. Ca & Na Concentrations in Flowback Samples of Figure 16. Fe & HCl Concentrations in Flowback Samples
WHW-X14 (Perforated Well) of WHW-X14 (Perforated Well)

1200 120000 24

100000 Fe (Total) 20

HCl Concentration, wt%

Fe Concentration, mg/L
Concentration, mg/L

Ca HCl
800 80000 16
Na

60000 12

400 40000 8

20000 4

0 0 0
0 50 100 150 0 50 100 150
Flowback Time, min Flowback Time, min

Figure 15. Fe & HCl Concentrations in Flowback Samples of Figure 17. Normalized Concentration of Cl- in Flowback
WHD-X10 (Unperforated Well) Samples of WHD-X10 (Unperforated Well)

30000 24 1.2
Co (Initial Cl- Concentration) = 187,699 mg/L
HCl Concentration, wt%

1
Fe Concentration, mg/L

25000 20
Fe(total)
20000 HCl 16 0.8
C/Co

15000 12 0.6

10000 8 0.4

5000 4 0.2

0 0 0
0 50 100 150 200 250 300 0 50 100 150 200 250 300
Flowback Time, min
Flowback Time, min
 20 H.A. NASH-EL-DIN, S.H. AL-MUTAIRI, S.M. AL-DRIWEESH SPE 73706

Figure 18. Normalized Concentration of Cl- in Flowback

Samples of WHW-X14 (Perforated Well)

1.2
Co (Initial Cl- Concentration) = 215,473 mg/L
1

0.8
C/Co

0.6

0.4

0.2

0
0 50 100 150
Flowback Time, min