SPE 94639
Corrosion Control During Acid Fracturing of Deep Gas Wells: Lab Studies and Field
Cases
S.H. Al-Mutairi, SPE, H.A. Nasr-El-Din, SPE, G.A. Al-Muntasheri, SPE, and S.M. Al-Driweesh, SPE, Saudi Aramco
Copyright 2005, Society of Petroleum Engineers Inc.
This paper was prepared for presentation at the SPE International Symposium on Oilfield
Corrosion held in Aberdeen, United Kingdom, 13 May 2005.
This paper was selected for presentation by an SPE Program Committee following review of
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Librarian, SPE, P.O. Box 833836, Richardson, TX 75083-3836, U.S.A., fax 01-972-952-9435.
Abstract
Acid fracturing treatments are used to enhance gas production
from tight, deep carbonate reservoirs in Saudi Arabia. The
produced gas has a regional variation between 0 and 10 mol%
H2S. This variation in H2S content has impacted the
metallurgy of well tubulars used in these areas. Gas wells in
the high H2S area are completed with low-carbon steel (L-80
and C-95); those in the low H2S area are completed with super
Cr-13 tubulars.
Acid systems used to fracture these wells included: regular,
emulsified, and in-situ gelled acids, all based on 28 wt% HCl.
However, 15 wt% HCl – 9 wt% formic acid was used to
stimulate wells completed with super Cr-13 tubing. High
temperatures (275˚F) encountered in deep wells, the presence
of high H2S content and the use of large volumes of
concentrated acids render corrosion control of tubulars a very
difficult task.
Experiments were performed to develop a cost-effective
acid system to enhance the productivity of deep gas wells,
while maintaining the integrity of well tubulars. Acid
fracturing treatments were monitored in the field and well
flow back samples were collected following these treatments.
The concentrations of key ions were measured in these
samples including iron and manganese for completions with
low-carbon steel tubulars and chrome, molybdenum, and
nickel for completions with super Cr-13.
Analysis of flow back samples following the initial acid
fracturing treatments showed that the return samples contained
high concentrations of acid (up to 16 wt% HCl) and total iron
(up to 20,000 mg/l). The presence of iron was a major concern
during acid fracturing treatments. Modifications of the
corrosion inhibitors package, increasing soaking time and over
flush volume resulted in better results. Most importantly, the
integrity of well tubulars was maintained. This paper discusses
lab studies and application of these modifications in the field.
Introduction
Acid fracturing treatments have been conducted in a deep
carbonate gas reservoirs.1 Various acids are used in these
treatments. Almost all of these acids are based on 28 wt%
HCl. Corrosion control during these treatment has been a
major concern. This is because of the use of concentrated
acids, high temperature, and the presence of hydrogen sulfide
in some areas in the gas reservoirs.
During pumping the acid down the tubing, the acid is
continuously depleted from the active ingredients of corrosion
inhibitors by the adsorption and/or polymerization on the
metal surface. The active ingredients of corrosion inhibitor
adsorb to the metal surface and form a thin film that protects
the metal leaving the live acid with less inhibition. When the
acid reaches the formation its inhibition is further reduced by
adsorption on surfaces of rocks. Recovery of the spent acid
back through the well tubing may cause corrosion problems if
the return fluids contained live acid. This is mainly due to the
low levels of corrosion inhibitor in the return fluids. In
addition, surfactants, which are used to disperse the inhibitor
in the acid, also have very high tendency to adsorb on rock
surfaces.2 This, in turn, leaves the return fluids with minimal
dispersivity and poor functionality.
In general, cationic or partially cationic corrosion inhibitors
adsorb to surface of the rock, especially in the case of
sandstone. Nonionic corrosion inhibitors such as acetylenic
alcohol show little if any adsorption on rock surfaces. Several
authors have addressed the problem of corrosion inhibitor
being adsorbed on formation rocks and thereby damaging the
formation, altering wettabilty or causing emulsion problems.3,4
The concern of the presence of live acid in well flow back
was first raised by Huizinga and Like.3 A similar work was
done later by Morgenthaler et al.4 Their experimental work
was done on acidizing of sandstone rocks by HCl/HF acid.
Simulated and real spent acids were used to test their effects
on low-carbon steel (L-80) and stainless steel (super Cr-13).
Both studies agree on that spent acid could be corrosive and
may adversely affect the integrity of well tubulars. The extent
of the problem can be addressed by a thorough understanding
of the composition of the spent acid and its effect on various
types of tubing.
The objectives of the present study are to: (1) measure the
concentration of live acid and key elements following acid
fracturing treatments, (2) determine the impact of acid type on
the concentration of live acid and other key ions in well flow
2 SPE 94639
back, and (3) modify the acid treatment to reduce the
concentration of live acid present in well flowback.
Reservoir Description
The Khuff formation is located in the eastern part of Saudi
Arabia. This formation belongs to the late Permian age and is
encountered at an average depth of approximately 11,500 ft.5
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. A layer of anhydrite
caps Khuff B reservoir, whereas a layer of mudstone and
anhydrite separates Khuff B and C reservoirs. A layer of
anhydrite separates Khuff C and D.6
Khuff reservoirs are composed of rich gas and there is no
active water drive associated with Khuff B and C reservoirs.
Lithological studies have shown that the reservoir consists of
limestone intermingled with dolomite and intermittent
anhydrite stringer within the tighter section of the reservoir.
The average initial reservoir pressure is 7,000 psi and average
temperature is 275°F.7 The reservoir has a relatively low
permeability (0.01 – 10.0 mD) and tends to have significant
porosity, but low permeability.8
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.9 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.10
Well Completion
Khuff gas wells are completed with 4.5, 5.5-inch tubing or
combinations of both. C-95 grade tubing with new Vam
connecters was used in these wells. L-80 grade connections or
crossovers were also used in some cases. All wells were
completed with 7-inch or 7x4.5-inch cemented liners. The
perforation density is 6 shot per foot at 60° phasing. The
perforation diameter is 0.32-inch and the length of the
perforation tunnel is 22-inch. Solares gives more details on
well completion and the mechanical strength requirements for
well tubulars for the frac treatments.7
The southern part of this reservoir has CO2 content up to
2.5 mol%. Most of these wells however, have H2S content
less than 100 ppm. Low-carbon steel tubulars cannot be
utilized under these conditions because of excessive corrosion
to the tubing. Corrosion resistant alloys (CRA) are
recommended under these conditions.11,12 To address
corrosion problems in sweet environments, wells in the
southern part of the field were completed with super Cr-13.
Unlike regular Cr-13 tubulars, super Cr-13 contains less
carbon, nickel (4-6 wt%) and molybdenum (nearly 2 wt%),
which increase corrosion resistance of the tubulars.13
Super Cr-13 is a stainless steel because it contains more
than 10.5 wt% chromium. It belongs to the martensitic grade
of the stainless steel group. This range of corrosion resistant
alloys has much lower corrosion rate than that of carbon steels
in the presence of carbon dioxide and chloride.3 This
eliminates the need for corrosion inhibition and lengthens the
life time of the tubing. Table 1 gives the elemental
composition of L-80, C-95 and super Cr-13 that are used in
Khuff gas wells.
Acid Systems
To enhance the productivity of the gas wells in the tight Khuff
reservoirs, acid fracturing treatments have been employed
with various types of acid systems. Most of the acid systems
used are based on 28 wt% HCl and included: regular,
emulsified, and in-situ gelled acid. The following is a brief
description of each acid system.
a) Acids used with Low-Carbon Steel Completions
Stimulation efforts in the Khuff reservoirs are needed to
remove drilling mud filter cake and enhance reservoir
permeability. Both matrix and fracturing acidizing treatment
were conducted in this field. Regular hydrochloric acid at 28
wt% has been used to stimulate gas wells in this formation.5
However, 28 wt% HCl is very corrosive, especially at the high
temperatures encountered in these deep, sour gas reservoirs.
Regular Acid
Regular acid has a high leak-off rate. Therefore, regular HCl
at 20 wt% was used primarily to remove drilling mud filter
cake. Since this acid will be the first acid to be pumped, it
contained corrosion inhibitor package that corresponds to the
bottom hole static temperature. An H2S scavenger was also
added in wells with H2S (e.g., well U-1801). Table 2 gives the
composition of the spearhead acid that is used in low-carbon
steel wells.
Emulsified Acid
There was a need for acid formulations that have high rock
dissolution power, but less corrosive. One of these acid
formulations is the acid-in-diesel emulsion.14 This acid system
consists of diesel (continuous phase), HCl acid (dispersed
phase), and a suitable emulsifier.
Emulsified acid has been extensively used in acid
fracturing treatments.15,16 Table 3 gives the composition of
this acid. The acid has been used because of its low corrosion
rates. It does not require high concentrations of common
additives, e.g. hydrogen sulfide scavenger and iron control
agents. Most importantly, it creates deep wormholes, which
significantly increase gas production from Khuff gas
reservoirs.
In-situ Gelled Acid
In-situ gelled acids (also known as leak-off control acids) were
extensively used in these treatments. These acids consist of a
synthetic polymer, a cross-linker, and a breaker, and other
common additives. They cross-link over a narrow pH range
where their viscosity increase by several orders of magnitude.
The acid reacts with the carbonate rock its pH increases. At a
pH value of nearly 2, the polymer and cross-linker form a gel.17
As a result, the viscosity of spent acid increases by several orders
of magnitude. High viscosity of the acid will significantly reduce
leak-off into the formation and will result in deeper acid
penetration. Table 4 gives the composition of 28 wt% in-situ
gelled acid.
SPE 94639
b) Acids used with Super Cr-13 Completions
Chrome-based tubulars are effective in sweet corrosion
environments; however, they cannot tolerate concentrated HCl
solutions, especially at high temperatures. As a result, the 28
wt% HCl acids that are commonly used in this field cannot be
utilized in wells completed with super Cr-13 tubulars.
Therefore, a special acid blend and corrosion inhibitor
package had to be developed to effectively stimulate the
carbonate formation.
In order to maintain high acid concentration and good
control, it was decided to examine various combinations of
formic acid and HCl. Formic acid was used with HCl for
high-temperature stimulation by Dill and Keeney in 1978.18 It
is also used as a corrosion inhibitor intensifier in wells
completed with low-carbon steel tubulars.19
Gelled 15 wt% HCl/9 wt% Formic Acid
Based on extensive lab studies,20 it was decided to use 15 wt%
HCl and 9 wt% formic acids. A synthetic polymer was added
to this acid to increase its viscosity and leak-off rate. with
super Cr-13 completions. Table 5 gives the composition of
this acid.
In-situ Gelled HCl/Formic Acid
In-situ gelled acid system that is based on 15 wt% HCl/9 wt%
formic was used to acid fracture several wells. This is simply
a gelled acid that contains a cross-linker, a buffer and a
breaker. The cross-linker reacts with the polymer to form a gel
at pH of nearly 2. The gel breaks at pH value of 4-5. The
breaker is used to help breaking the gel.17 The cross-liker in
this acid is a source of iron (III). This iron should be considered
when examining well flow back samples. Table 6 gives the
composition of this acid.
Corrosion Inhibition Packages
High temperatures and pressures encountered in deep gas
wells and the susceptibility of well tubulars to severe
corrosion by concentrated HCl solutions and high chloride ion
concentrations necessitate using effective corrosion inhibitor
packages. Corrosion inhibitor packages usually consist of
corrosion inhibitor, inhibitor intensifier and some type of
surfactants to solubilize or disperse the inhibitor in the acid.
Corrosion inhibitor is the main component of the corrosion
inhibition package. It is added in small concentrations in order
to minimize acid reactions with well tubulars and coiled
tubing. The basic types of corrosion inhibitors are organic and
inorganic. Organic inhibitors include complex compounds
with one or more polar groups made of sulfur, oxygen or
nitrogen. Inorganic corrosion inhibitors include the salt of
zinc, nickel, copper, arsenic, antimony and other metals.
Organic corrosion inhibitors retard corrosion by forming a
protective film that separates the metal and the acid. Inorganic
corrosion inhibitors coat the metal by forming precipitates on
the surface of well tubulars.
Corrosion inhibitor intensifiers are used to: (1) extend the
inhibition time and provide safe contact time for the treatment,
(2) allow the inhibitor to function in strong acids, (3) allow the
inhibitor to be used with stainless steels,21 and (4) allow the
inhibitor to work with high downhole temperatures.22 The
3
intensifier may consist of metal ions, halide ions, or certain
organic compounds.21
For stimulation treatments, literature indicates that there are
four main intensifiers: formic acid, potassium iodide,
antimony chloride, and copper iodide.21,22 The copper-based
intensifier is known for its low solubility at ambient
conditions, and potential bi-metallic corrosion. The antimony
intensifier is limited to acid concentrations less than 17 wt%
HCl and can also cause bi-metallic corrosion.22,23 Potassium
iodide and cuprous iodide have been proven to be very
effective inhibitor intensifiers in high temperature
environments; especially for hydrochloric-formic acid
mixture.21, 22, 24
In order to provide the best protection of the well tubulars,
corrosion testing of representative metal samples with the acid
systems to be pumped was conducted. These tests were
performed using normal corrosion testing methods.25 The test
temperatures varied from 250 to 300°F and the tests were
conducted for 3 to 6 hours under 3,500 to 4,000 psi of
pressure. Because of variations in steel types and grades,
several types of metals were evaluated. The low-carbon steel
N-80 was selected to represent C-95 and L-80. The criteria for
acceptable corrosion rates for low-carbon steel were less than
0.05 lb/ft2 and a pitting index of zero.
Coupons of SCr-13 were prepared from a section of tubing
that is used in well completion. The criteria for acceptable
corrosion rates for this type of steel are < 0.03 lb/ft2, no
coloration and zero pitting.20
Corrosion inhibitor for 15 wt% HCl and 9 wt% formic
acid was extensively studied. Based on extensive lab testing,
potassium iodide was selected as an inhibitor intensifier.
Potassium iodide is expensive and the concentration required
to protect super Cr-13 tubing was greater than 100 lbs/1000
gals.20
To address high cost of inhibitor intensifier, the cooling
effect that occurs while pumping the acid at rates greater than
20 bbl/min was utilized. To verify this effect, a bottomhole
temperature gauge was installed downhole as shown in Fig. 1.
Because of this cooling effect, the loading of corrosion
inhibitor intensifier was greatly reduced, which resulted in a
significant cost saving.
It is important to note that wells stimulated with this acid
system have shown significant increase in gas production
which lasted for a long period of time.1
Field Cases
The flow back of more than 30 wells was thoroughly
examined. However, data from four wells will be discussed in
the present paper. These wells are denoted A, B, C and D.
The concentration of acidic components (CO2 and H2S) in the
produced gases is given in Table 7. The type and dimension
of production tubing and type and volume of acids used zero
given in Table 8. It is important to note that wells A and B
were completed with low carbon steel, whereas wells C and D
were completed with super Cr-13. Well A was acid fractured
suing 28 wt% HCl, whereas the other three wells were acid
fractured using 15 wt% HCl and 9 wt% formic acid.
4 SPE 94639
Analysis of Flow Back Samples
Well A is completed using low-carbon steel tubulars. It was
acid fractured using 28 wt% HCl. Figures 2 to 4 show the
concentration of acid, total iron, pH and other key ions. The
first observation is that spent acid is highly acidic, which
means that a portion of the acid did not react with the
formation rock. The maximum HCl concentration noted in the
flow back samples was 21.2 wt%. This concentration of live
acid is high, and obviously can cause severe corrosion to well
tubulars as shown in Fig. 2. The presence of live acid and
high iron concentration was noted in other wells also, as
shown in Table 9.
Figure 3 shows the concentrations of Ca, Mg and Cl in the
flow back samples. The concentrations of the three ions were
low during producing the postflush. Then they sharply
increased marking the arrival of the spent 28 wt% HCl.
The most important observation is that the well flowback
samples contained high levels of iron. Possible sources of iron
are: (1) reservoir fluids and rock, (2) injected acids, and (3)
well tubulars. Chemical analysis of formation waters indicated
that these waters contain very low concentration of iron,
Table 10.
Rock samples from the producing zones were examined
using XRD analysis. The results indicated that there is no
source of iron containing mineral in the formation.26 As for
pumped acids, strict QA/QC procedures were followed
including: (1) use of clean tanks, (2) mixing the acid with field
water than contains less than 2 mg/l of total iron, Table 11,
and (3) maximum allowable iron in the mixed acid should not
exceed 50 mg/l. It should be mentioned that in-situ gelled acid
contained 400-500 mg/l Fe (III). As a result, it was exempted
from the 50 mg/l requirements.
Gas wells are pickled with organic solvents followed by
15-20 wt% HCl if they were completed with low-carbon steel
tubings and liners. Details of these pickling procedures were
given by Nasr-El-Din et al.27 Wells completed with super Cr-
13 tubulars were pickled using organic solvents. The pickling
procedures were performed in a way such that the well was
left clean and that almost of the mill scale and pipe dope were
removed.
The above discussion indicates that the major source of the
iron in the flowback samples is the live acid present in these
samples. In other words, the acid is attacking the base metal. If
this is the case, some other elements should accompany the
iron. For example manganese should appear with the iron in
wells completed with low-carbon steels. This was clear in the
case of well A, where high levels of Mn were noted, Fig. 4.
Figure 5 shows the ratio of Mn to total iron. The ratio of
Mn to total iron was significantly higher than that present in
low-carbon steel (Table 1). This means that the acid dissolve
the base metal. The presence of higher Mn concentration was
not expected. More work is underway to better explain this
trend.
Well B is also completed using low-carbon steel tubulars,
however, it was acid fractured using 15 wt% HCl and 9 wt%
formic acid. Figures 6 to 9 show the concentration of acid,
total iron, pH and other key ions. Several important trends can
be seen in these figures. The first observation is that the acid
and iron concentrations were significantly smaller than those
noted with well A. The concentration of Mn is less than 5
mg/l. And the ratio of Mn/Fe is close to that of the base
tubing.
Modifications to Reduce Live Acid in Well Flowback
The main focus of this work was protecting the downhole
tubulars during lifting the spent acid. Several researchers have
raised the corrosive nature of spent acids, especially if they
contain live HCl.2,3 Every effort was made to minimize the
presence of live acid in the flowback samples. Previous
studies indicated that this can lead to severe corrosion to well
tubulars.28 The presence of live acid in flowback of well
completed with SCr-13 was a major concern, because of
potential corrosion to expensive well tubulars
The following three modifications were implemented to
reduce the concentration of live acid in the produced fluids
following acid treatments: (1) Increase the soaking time, (2)
Increase the post flush volume, and (3) Adding corrosion
inhibitor and inhibitor aid to the last fluid pumped into the
formation.
The soaking time was increased to 2-3 hours to ensure that
the injected acids reacted with the formation rock. A large
over flush (600 bbls) was also used in order to displace acid
deep into the formation. Finally, small amounts of the
inhibitor and inhibitor aid were added to the last fluid pumped
into the formation. It was felt that the addition of corrosion
inhibitor into this fluid may help in protecting the tubing
during lifting the spent acid.
Well C is completed using super Cr-13. It was fractured
using 15 wt% HCl and 9 wt% formic acid. Figures 10 to 13
show the concentration of acid, total iron, pH and other key
ions, including Cr and Mo. No live acid was detected in the
flow back samples collected from this well. The
concentrations of iron and Cr were in general low and indicate
that the acid was consumed in the formation. No acid reacted
with the base pipe.
Well D is also completed with SCr-13 tubing and was
fractured using 15 wt%% and 9 wt% formic acid. Similar to
the resulted obtained with well C, the data shown in Figs. 14
to 17 indicate that the above modifications significantly
reduced the concentration of live acid in the produced fluids.
They also reduce the concentration of total iron, Cr, Mo, and
Ni in the acid flow back samples. In other words, these
modifications protected the SCr-13 tubing during acid
fracturing treatments.
Conclusions
1. The cooling effect encountered during pumping the
acid was effectively used to optimize the loading of
the intensifier.
2. Increasing acid soaking time to three hours, and
increasing the volume of the overflush successfully
eliminated the return of live acid after the treatment.
3. Acceptable corrosion rates were observed during and
after the fracturing treatments.
4. Analysis of flowback samples is useful in optimizing
future fracturing treatments.
SPE 94639
Acknowledgments
The authors wish to acknowledge the Saudi Arabian Oil
Company (Saudi Aramco) for granting permission to present
and publish this paper. Udhailiyah Lab Unit, SALD and the
Chemistry Unit and Advanced Instruments Unit of the R&D
Center, Saudi Aramco were very helpful in their field
monitoring and analysis of the spent acids, respectively.
Members of the stimulation group, R&DC are acknowledged
for processing well flow back samples. F. Al-Dawood and the
Corrosion Unit are acknowledged for conducting the corrosion
tests. All engineers in Gas Production Engineering Division
and local service companies are acknowledged for many
useful discussions.
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Improved Oil Recovery Conference in Asia Pacific Manganese 0.5 max 1.90 max 1.90 max
held in Kuala Lumpur, Malaysia, 20–21 October.
23. Do Carmo Marques, L.C. and Mainier, F.B.: Molybdenum 2.0 max - -
“Corrosion Problems Associated with the Use of
Copper-Based Corrosion Inhibitor Intensifier in Acid Chromium 12.2 max - -
Stimulation Treatments,” paper SPE 23634 presented
at the 1992 Latin American Petroleum Engineering Nickel 6.0 max 0.25 max -
Conference held in Caracas, Venezuela, 8-11 March.
24. Keeney, B.R.: “Acid Corrosion Inhibition Using Copper - 0.35 max -
Metal Halide-Organo Inhibitor Systems,” Materials
Protection and Performance, September 1973, 12,
Phosphorous 0.02 max 0.030 max 0.030 max
No. 9, 13-15.
25. Metcalf, A.S.: “Environment and Coiled Tubing:
both can be Protected,” paper SPE 51095 presented at Sulfur 0.001 max 0.030 max 0.030 max
the 1998 SPE Eastern Regional Meeting, Pittsburgh,
Nov. 9-11. Silicon 0.2 max 0.45 max 0.45 max
26. Taylor, K.C., Al-Ghamdi, A.H., and Nasr-El-Din,
H.A.: “Effect of Rock Type and Acidizing Additives
a. All concentrations are expressed in weight percent.
on Acid Reaction Rates Using the Rotating Disk
The balance is iron.
Instrument,” paper CIM2003/068 presented at the
2003 Petroleum Society’s Canadian International
Table 2. Formula for 20 wt% HCl spearhead acid.
Petroleum Conference, Calgary, Alberta, Canada, 11
– 13, June. Variable Concentration, gpt
27. Nasr-El-Din, H.A., Al-Mutairi, S.H. and Al-
Driweesh, S.M.: “Lessons Learned from Acid Pickle Corrosion inhibitor 8
Treatments of Deep/Sour Gas Wells,” paper SPE
73706 presented at the 2002 SPE Int. Symposium on
Corrosion inhibitor aid 20
Formation Damage Control, Lafayette, LA, February
20-21.
28. Nasr-El-Din, H.A., Al-Mutairi, S.H., Al-Jari, M., Surfactant 2
Metcalf, S., and Wallace, W.: “Stimulation of a Deep
Sour Gas Reservoir Using Gelled Acid,” paper SPE H2S Scavenger 10
75501 presented at the 2002 SPE Gas Technology
Symposium held in Calgary, AB, Canada, 30 April to H2S Scavenger aid 1
02 May.
Iron control agent 30a

Acid (31 wt% HCl) 614

Water 345

a. Ibs/1000 gals
SPE 94639 7

Table 3. Formula for 28 wt% HCl emulsified acid. Table 5. Formula for 15 wt% HCl/9 wt% formic acid
– gelled acid.

Variable Concentration, gpt Variable Concentration, gpt

Corrosion inhibitor 8 Corrosion inhibitor 20

Inhibitor aid 20 Formic acid 90

Emulsifier 30 Iron control agent 10a

Diesel 300 Surfactant 2

Acid (31 wt% HCl) 623 Acid gelling agent 15

Water 49 Acid (31 wt% HCl) 451

Water 422

a. Ibs/1000 gals

Table 4. Formula of 28 wt% HCl in-situ gelled acid. Table 6. Formula for 15 wt% HCl/9 wt% formic acid.
In-situ gelled acid

Variable Concentration, gpt

Variable Concentration, gpt
Corrosion inhibitor 20
Corrosion inhibitor 6
Corrosion inhibitor aid 90
Inhibitor aid 20
Inhibitor aid 10a
Surfactant 2
Gelling agent 15
Acid gelling agent 30
Surfactant 1
Iron control agent 10a
Acid (31 wt% HCl) 474
Cross-linker 2.5
Water 399
Acid (31 wt% HCl) 890
a. Ibs/1000 gals
Water 40
Table 7. Concentrations of acidic gases in examined wells
a. Ibs/1000 gals
Well # CO2 (mol%) H2S (mol%)
A 5.48 2.5
B 0.65 0
C 0.51 0
D 0.65 0
8 SPE 94639

Table 8. Key parameters of examined wells.

Variable A B C D

Tubing Length, ft 10,040 8,802 8,940 10,466

Tubing Type C-95 C-95 SCr-13 SCr-13

Tubing Diameter, in 5-1/2 5-1/2 5-1/2 5-1/2

Liner Length, ft 2,870 3,318 840 1,434

2,250

Liner Type C-95 C-95 Cr-13 Cr-13

Liner Diameter, in 7 7 7x5-1/2 7

Main Acid System (D) (A) (B) (B)

CFA Type (C) (A) (B) (B)

CFA Volume, gals 10,000 10,000 10,000 10,000

Overflush Volume, gals 15,157 16,000 45,070 39,277

Soaking Time, hours <1 <1 <1 2

(A) 15 wt% HCl/9 wt% Formic

(B) Gelled 15 wt% HCl/9 wt% Formic
(C) Gelled 28 wt% HCl
(D) Emulsified 28 wt% HCl
SPE 94639 9

Table 9. Chemical analysis of the sample that contained the highest spent acid concentration.

I H G F B E A

HCl 3.4 0 2.23 3.95 0.63 21.2 15.8

pH 0 3.3 0 0 1 0 0

Cl 29,064 11,029 126,386 39,517 6,464 217,385 170,181

Fe 1,064 1,524 1,998 61 321 793 1,717

Cr - - - - - - -

Ba 0 1 1 0 0 5 4

Ca 119 2,561 34,058 155 141 71 547

Pb 0 0 0 0 0 - 0

Mg 42 1,809 20,949 42 51 21 289

Mn 5 8 22 0 1 3 11

K 43 157 128 42 654 13 25

Zn 0 0 23 0 0 2 0

Na 583 1,138 583 604 675 473 233

Acetate 0 0 - - 0 - -

Formate 18,080 5,503 - - 345 - -

Si 14 22 36 14 17 - 0
10 SPE 94639

Table 10. Chemical analysis of formation water.a Table 11. Chemical analysis of field mixing water.

Variable B E J Ion A B F

Na 15,100 81 4,970 Ca 138 30 134

Ca 3,880 36 7,770 Fe 2 <1 <1
Mg 540 12 1,330 Mg 62 43 45
Sr 230 1.6 220 Na 350 299 275
K 660 2 320 K 27 22 25
Ba 1.9 1 10 Cl 789 442 449
SO4 240 15 130
b
Cl 31,500 212 25,200
TDS 51,260 356 39,400
S.G. 1.0421 1.0031 1.032
a. All concentrations are expressed in mg/l
b. Concentrations of total iron, carbonate, bicarbonate
and hydroxide ions were below detection limit.
SPE 94639 11

Figure 1. Bottomhole temperature during pumping HCl/formic acid, well “X”

250
Tem perature, o F

220 Frac Start

190

160

130
0 10 20 30 40 50 60 70
Time, hours
12 SPE 94639

20 25,000 0.8 400

Total Iron Conc., mg/l

HCl

HCl Concentration, wt%

HCl

Total Iron Conc., mg/l

HCl Concentration,

16 20,000 0.6 Total Fe 300

Total Fe
12 15,000
wt%

0.4 200
8 10,000

4 5,000 0.2 100

0 0 0 0
10 100 1000 0 50 100 150
Flowback Time, min. Flowback Time, min.

Fig. 6: HCl and total iron – Well B, Khuff-C.

Fig. 2: HCl and total iron – Well A, Khuff-B.

1,000,000 100,000

Ca, Mg &Cl Conc., mg/l

100,000 10,000
Concentration, mg/l

10,000 1,000

1,000
Ca 100 Ca
100 Mg
Mg 10
10 Cl Cl
1
1
0 50 100 150
10 100 1000
Flowback Time, min.
Flowback Time, min.

Fig. 3: Ca, Mg and Cl ions – Well A, Khuff-B. Fig. 7: Ca, Mg, and Cl ions – Well B, Khuff-C.
800 5 4 5
4 4
600
Mn Conc., mg/l
Mn Conc., mg/l

3
3 3
pH

400

pH
2
2 2
200 Mn
1 1 Mn
pH 1
pH
0 0 0 0
10 100 1000 0 50 100 150
Flowback Time, min. Flowback Time, min.
Fig. 4. Mn and pH – Well A, Khuff-B. Fig. 8: Mn and pH – Well B, Khuff-C.
1000 0.04

100 0.03
Mn/Total Fe

10
Mn/Fe

0.02
1
Mn/Fe 0.01 Mn/Fe
0.1
Mn/Fe in Base Metal Mn/Fe in Base Metal
0.01 0
10 100 1000 0 50 100 150
Flowback Time, min. Flowback Time, min.

Fig. 5: Mn/Fe – Well A, Khuff-B. Fig. 9: Mn/Fe – Well B, Khuff-C.

SPE 94639 13

200 2.5

Cr Concentration, mg/l
6 500
2

Total Iron Conc., mg/l

150

Cr & Mn Conc., mg/l

Total Fe, mg/l

400
1.5 4
100 300
1
Mn 200
50 2
0.5 Cr
100
Total Fe
0 0
0 0
0 100 200 300 400
Flowback Time, min 1 10 100 1,000 10,000
Flowback Time, min.
Fig. 10: HCl and total iron – Well C, Khuff-
B Figure 14: Cr, Mn, Fe – Well D, Khuff-C.

100,000 100,000

Concentration, mg/l
80,000 80,000 Ca
Concentration, mg/l

Ca
60,000 Mg
60,000 Mg
Cl
Cl 40,000
40,000

20,000 20,000

0 0
0 100 200 300 400 1 10 100 1,000 10,000
Flowback Time, min.
Flowback Time, min

Fig. 15: Ca, Mg, and Cl ions, Well D, Khuff-C

Fig. 11: Ca, Mg, and Cl ions – Well C, Khuff-B.
6 8
5 Mn
pH & Cr Conc., mg/l

5
Cr & Mn Conc.,

4 pH Cr
4 6.5
Cr pH
3
mg/l

pH
3
2 2 5
1 1
0 0 3.5
0 100 200 300 400 1 10 100 1000 10000
Flowback Time, min.
Flowback Time, min

Fig. 12: Cr and pH – Well C, Khuff-B.

Fig. 16: Cr, Mn and pH, Well D, Khuff-C
1
0.2

0.15 0.1
Cr/Total Fe

Cr/Fe

Cr/Fe
0.1 Cr/Total Fe Cr/Fe in Base Metal
0.01
0.05 Cr/Total Fe in Base Metal
0.001
0
1 10 100 1,000 10,000
0 100 200 300 400
Flowback Time, min.
Flowback Time, min
Fig. 17: Cr/Fe, Well D, Khuff-C.
Fig. 13: Cr/Fe – Well C, Khuff-B.