SPE 84925
Field Application of HCl-Formic Acid System to Acid Fracture Deep Gas Wells
Completed with Super Cr-13 Tubing in Saudi Arabia
H.A. Nasr-El-Din, SPE, S.M. Driweesh, SPE, G.A. Muntasheri, Saudi Aramco
Copyright 2003, Society of Petroleum Engineers Inc.
This paper was prepared for presentation at the SPE International Improved Oil Recovery
Conference in Asia Pacific held in Kuala Lumpur, Malaysia, 20–21 October 2003.
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, as
presented, have not been reviewed by the Society of Petroleum Engineers and are subject to
correction by the author(s). The material, as presented, does not necessarily reflect any
position of the Society of Petroleum Engineers, its officers, or members. Papers presented at
SPE meetings are subject to publication review by Editorial Committees of the Society of
Petroleum Engineers. Electronic reproduction, distribution, or storage of any part of this paper
for commercial purposes 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 where and by whom the paper was presented. Write Librarian, SPE, P.O.
Box 833836, Richardson, TX 75083-3836 U.S.A., fax 01-972-952-9435.
Abstract
This paper describes optimization of gelled and in-situ gelled
HCl/formic acid systems to stimulate deep gas wells
completed with super Cr-13 tubing. High temperatures
encountered in deep wells and the susceptibility of super Cr-
13 to severe corrosion by concentrated HCl solutions and high
chloride ion concentrations render acid stimulation a very
difficult task. Therefore, extensive experimental and field
studies were performed to develop a cost effective acid system
to enhance the productivity of deep gas wells, while
maintaining the integrity of the super Cr-13 tubing.
Coreflood tests indicated that this acid system can create
deep wormholes in tight reservoir cores (less than 1 md).
Corrosion tests, however, indicated that protecting super Cr-13
tubulars during pumping this acid (15 wt% HCl/9 wt% formic
acid) is not an easy task, especially at downhole temperatures
(275ºF). A very limited number of inhibitor aids were found
to be effective in protecting super Cr-13 at reservoir
conditions. To optimize the corrosion inhibitor package, the
bottom hole temperature was measured in a few wells during
acid injection.
Based on lab tests and field measurements, an acid
treatment was designed and applied in the field. The treated
wells responded positively to the treatment. Most importantly,
the integrity of the super Cr-13 was maintained. This was
confirmed from chemical analysis of well flowback samples
following the treatment and measurement of the tubing inside
diameter before and after the treatment. The maximum Cr
concentration in the flowback sample was less than 2 mg/L.
Molybdenum and nickel concentrations were less than 1 mg/L.
The total iron concentration was less than 200 mg/L. This
value is significantly less than that noted with wells completed
with low-carbon steel tubulars.
Introduction
Non-associated gas is being produced from deep carbonate
reservoirs in Saudi Arabia. The lithology of the formation is
mainly dolomite with some calcite and streaks of anhydrite.
The non-associated gas is sour with hydrogen sulfide content
that varies from 0 to 10 mol%.1 The average reservoir
temperature is 275°F and the initial reservoir pressure is nearly
7,500 psi. Wells that produce sour gas with high levels of
hydrogen sulfide are completed with low-carbon steel tubulars
(L-80 and C-95). To enhance the productivity of these wells
both matrix acidizing and acid fracturing treatments have been
employed.2 The acid systems used are based on 28 wt% HCl
and included: regular,2 emulsified,3 in-situ gelled acid,4,5 and
recently, acids based on visco-elastic surfactants.6
The southern part of this reservoir has CO2 content up to
2.5 mol%. Most of these wells however, have H2 S 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.7,8
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.9 Table 1 gives the elemental composition of super
Cr-13 used in these wells.
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.
Based on extensive lab work, 15 wt% HCl/9 wt% formic
acid was field tested in three wells completed with low-carbon
steel.10 The objectives of this field trial were to examine the
dissolution power of this acid under downhole conditions and
assess its effectiveness to enhance the productivity of the
treated wells. The acid treatment used in low-carbon steel
wells comprised a preflush, main acid, closed-fracture acid,
and a postflush stage. All acids used in this treatment were
based on 15 wt% HCl and 9 wt% formic acid. Viscous pads
2 H . A . N a s r -E-l Din,
were pumped between the acid stages to enhance fracture
propagation and aid in cooling the formation.10
Field data showed that wells treated with 15 wt% HCl/9
wt% formic performed better than those treated with other
acid systems.2 This is mainly due to the relatively weak nature
of formic acid, which will not react with the carbonate rock
until the stronger acid (HCl) is completely spent.
This acid system gave good results in wells completed with
low-carbon steel. The objectives of the present study are to:
(1) Assess its effect on super Cr-13 tubulars under field
conditions; and (2) Optimize the system and make it more cost
effective.
Experimental Studies
Extensive studies were conducted to determine: the
mineralogy of the cores, reaction rate of the 15 wt% HCl/9
wt% formic with reservoir rocks, apparent viscosity of gelled
acid, and corrosion rates using super Cr-13 coupons. Details
of these studies were given in a previous publication.10
Therefore, a brief description will be given this paper. In
addition, corrosion tests conducted for the super Cr-13 will be
discussed.
Table 2 gives the mineralogy (as determined by XRD) of
reservoir cores used in the core flood experiments. The cores
contained mainly calcite, dolomite, quartz and traces of
anhydrite and clays. It should be mentioned that the
mineralogy of the formation varied from one well to another,
and also varied within the target zone of the same well.
Details on the mineralogy of this formation are given by Al-
Jalal.11 The impact of mineralogy on the outcome of acid
fracture treatments conducted in this field was discussed by
Bartko et al.12 The effect of mineralogy on the acid reaction
rate with the formation rock was examined by Taylor et al.13
Table 3 gives the main components of the gelled
HCl/formic acid used. An acid-soluble polymer at 1.5 vol%
was added to the acid to increase its viscosity and reduce leak-
off during acid injection into the formation.
The apparent viscosity of 15 wt% HCl/9 wt% formic acid
with various additives was measured as a function of shear
rate, using a Brookfield vis cometer. Measurements were
conducted at various temperatures up to 265ºF and a pressure
of 500 psi. Figure 1 shows the apparent viscosity of the gelled
acids at ambient conditions. The acids were prepared
according to the formula given in Table 3. Two potassium
iodide concentrations were tested: 10 and 100 lbs/1,000 gals.
The apparent viscosity of the acid decreased with the shear
rate, indicating the shear thinning behavior of these acids. The
effect of potassium iodide was not significant. This acid
system can be pumped without encountering operational
problems. Figure 2 shows the effect of temperature of the
apparent viscosity of gelled acid that contained potassium
iodide at 10 lb/1,000 gals. The viscosity of the gelled acid
decreased at 265ºF, but the acid behaved as a shear thinning
fluid.
The acid given in Table 3 was injected into several
reservoir cores at reservoir temperatures. The reservoir cores
were 1.5 inches in diameter, 1.5 inches in length and had air
permeability less than 1 md. The tests were conducted at a
temperature of nearly 300ºF, overburden pressure of 3,000 psi,
S., G.A. Muntasheri SPE 84925
and a back pressure of 500 psi. The acid was injected at 1
cm3 /min and was followed by 2 wt% KCl. Photos 1a to 1d
show that this acid created wormholes in the cores. The acid
managed to reduce the pressure drop across the core, hence, it
enhanced core permeability by at least 2.5 folds.
These results, in addition to those presented before,10
indicate that this acid can be used to stimulate deep carbonate
gas reservoirs. A special corrosion inhibition package was
needed to protect the super Cr-13 tubing during pumping the
live acid into the formation, and lifting of the spent acid from
the wellbore area to the surface.
Inhibition of the 15 % HCl/9 % Formic Acid System
Corrosion inhibition of super Cr-13 when the HCl/formic acid
mixture is used was extensively studied.14 To protect the well
tubulars during acid treatment, there is a need to use a suitable
organic inhibitor for mineral acids and an inhibitor aid. The
latter is needed because of the high downhole temperature
(275ºF).
A thorough literature survey indicates that there are four
main intensifiers: formic acid, potassium iodide, antimony
chloride, and copper iodide.15 It was first thought that the
formic acid already present in the acid formula is adequate and
there is no need to use any other intensifier. However,
corrosion tests indicated that this was not the case and there
was a need to use an intensifier other than formic acid. An
extensive study was conducted to select an intensifier from the
remaining ones. The copper based intensifier was not selected
because of its low solubility at ambient conditions, and
potential bi-metallic corrosion.16 The antimony intensifier is
limited to acid concentrations less than 17 wt% HCl and can
cause bi-metallic corrosion. The only intensifier left was
potassium iodide, which was extensively studied.
Corrosion tests were conducted both in our labs and those
of the service companies. Initial tests indicated that the
corrosion rate depends on the composition of the coupons used
to conduct the tests . Therefore, it was decided to prepare
coupons from the same tubing string that will be used in the
field. Corrosion tests were conducted at various conditions
and chemical loadings to determine the composition of the
inhibitor and intensifier needed to protect the super Cr-13
tubing. It should be mentioned that all corrosion tests were
conducted in a nitrogen atmosphere at 3,500 psi and various
temperatures up to 275ºF. The criteria used for accepting a
specific acid formulation are: weight loss less than 0.05 lb/ft 2 ,
no pitting, and no discoloration. It was felt that any pitting
will result in compromising the integrity of the tubing on the
long run.
The data indicate that super Cr-13 tubing can be protected
however, the loading of potassium iodide needed was high
(150 lbs/1,000 gals of acid at 275ºF). Obviously the cost of the
inhibitor package at such loadings was high and means to
reduce the concentrations of the inhibitor/intensifier were
needed.
Optimization of the Corrosion Inhibitor Package
During the final design stage, there were two main concerns:
the cost of chemicals and protection of the tubulars during
lifting the spent acid.17 The first concern was addressed by
SPE 84925 Field Application of HC l-Formic Acid System to Acid Fracture De
examining the cooling effects to the tubulars during acid
pumping. It was noted during the injection of acid at high
pumping rates (i.e., above the fracture pressure of the
formation) that the whole treatment took less than two hours.
Initial pumping rates greater than 20 bbls/min can be achieved
in wells that were not severely damaged by the drilling mud
filter cake. Once the formation wa s fractured, pumping rates in
the order of 60-80 bbls/min were achieved. Pumping the acid
at higher rates will reduce the temperature of the downhole
tubulars. This is because the acid has a much low temperature,
95ºF at the surface, than the downhole temperature, 275ºF.
Obviously, reducing the temperature of well tubulars to less
than 200ºF will significantly decrease the loadings of the
inhibitor and intensifier.
To further examine the cooling effect that occurs during
acid pumping, a temperature gauge was placed in the middle
of perforation interval of well “X” and the temperature was
recorded as a function of time. Figure 3 shows that the
downhole temperature decreased from 255 to 140ºF in less
than two hours. Viscous pads and acid stages were pumped at
a rate that increased from 20 to 60 bbl/min. The corrosion
inhibitor package requires much less corrosion inhibitor and
no inhibitor aid at 140ºF. The cooling effect is definitely very
useful and significantly reduces the corrosion inhibitor
loadings. However, extreme care should be taken when this
effect is applied in the field. Any operational problems, e.g.,
pump failure, can lead to severe damage to the tubing if it is
exposed to concentrated acid for long periods of time.
Therefore, the loading of the corrosion inhibitor was kept
constant at 2 vol%. The inhibitor aid, however, was graded to
match the expected downhole temperature. For example, the
spearhead acid contained 150 lb/1000 gals of acid, whereas
the main acid contained 5 lbs/1000 gals of acid. This grading
in the loading of the intensifier has resulted in significant cost
savings. A contingency plan was put in place to lift the spent
acid in case of operational problems. None was encountered.
The treatment was applied in more than ten wells, resulted in
significant enhancement in gas production, while maintain ing
the integrity of the super Cr-13 tubing.
The second concern 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.17 Every effort was made to minimize the presence
of live acid in the flowback samples. Previous studies
conducted in our lab indicated that this can lead to severe
corrosion to well tubulars.4 These efforts included: reasonable
soaking time (typically 2-3 hours), large overflush (600 bbls),
and adding small concentrations of the inhibitor and aid in the
last fluid pumped into the formation. This will be the first
fluid to be produced. It was felt that the addition of corrosion
inhibitor into this fluid may help in protecting the tubing
during lifting the spent acid. These modifications were very
effective as will be shown in the next few sections.
Wells Completed with Super C r-13Tubing 3
Field Treatments
Recently, ten wells were acid fractured using gelled and in-
situ gelled 15 wt% HCl/9 wt% formic acid systems. These
wells are completed with super Cr-13 tubing (20#, 5.5 inches
super Cr-13-95 grade). The perforation density is 6 shots per
foot at 60° phasing.
The pump schedule utilizes a high temperature borate-gel
to initiate a fracture in the formation, followed by alternating
stages of HCl/formic acids and borate gel pads. The viscous
pads cooled the formation, maintained bottom hole pressure,
and controlled leak-off rate. Alternating these stages also
created a viscous fingering effect, which altered the path of the
acid in the fracture, leaving irregular etched patterns along the
fracture face. A final stage of the HCl/formic acid, albeit
without the polymer, was used to enhance the fracture
conductivity around the wellbore area.
The acid fracture treatments incorporated three main acid
formulations. Table 3 gives the formulation of these acids
which are based on 15 wt% HCl/9 wt% formic acid. Table 4
gives the chemical composition of this acid. Each acid
formulation was specifically designed to provide a certain
function. A spearhead acid was used ahead of the main acid
treatment to remove drilling mud filter cake, cool down the
formation, and enhance the injectivity of the treated zone.
This acid was the first one to be injected and, as a result, it
contained the highest loading of inhibitor aid. No polymers
were added to this acid. The main acid is a gelled 15 wt%
HCl/9 wt% formic acid system that is used for deep acid
penetration. A low viscosity 15 wt% HCl/9wt% formic acid
system was the last fluid pumped at a reduced rate and used as
a closed fracture acid (CFA) to ensure that the fracture
conductivity around the wellbore was maximized. It should
be mentioned that the inhibitor of the main acid was much
lower that used in the spearhead acid. This is because of the
cooling effect mentioned earlier.
Some wells were treated with in-situ gelled HCl/formic
acid, Table 5. The acid in this case contained a cross-linker, a
buffer and a breaker in addition to other components. The pH
of the system increases as the acid reacts with the formation.
A gel will form once the pH reaches a critical value of nearly
2. The gel will break once the acid is spent and the pH rises to
a value greater than 4. More details on the gelation
mechanism and apparent viscosity of in-situ gelled acids are
given by Taylor and Nasr-El-Din.18
It is important to note that all fracturing fluids were
pumped through the tubing. Therefore, well tubulars were
thoroughly “pickled” before introducing the treatment fluids
into the formation. The main objective of pickling super Cr-13
tubulars is to remove pipe dope and other greasy material from
the wellbore, before introducing the fracturing fluids. The
pickling procedure was similar to that used in low-carbon
steel,19 however, no acid was used in the case of super Cr-13
tubulars.
Pressure Response to Treating Fluids
Figure 4 shows the surface pressure, pumping rate and
calculated bottom-hole pressure during the acid fracture
treatment of well “I”. This treatment is typical of wells treated
with gelled or in-situ HCl/formic acid. The well has nearly 77
4 H.A. Nasr
-l -Din, S.M. Driweesh, G.A. Muntasheri
ft of perforations. The bottom-hole static temperature and
pressure are 250ºF and 7,290 psi, respectively. The
permeability of the target zone was less than 2 md, whereas
the porosity was less than 15 vol%. The treatment started with
5,000 gals of “slick” 15-wt% HCl/9 wt% formic acid, as a
spearhead acid. This was followed by three stages of gelled
15 wt% HCl/9 wt% formic acid. The volume of first and
second stages was 28,000 gals each. The volume of the third
stage was 40,500 gals. Acid stages were separated with two
viscous pads of 20,000 gals. The bottom hole pressure
decreased each time the acid reached the formation and
reacted with the carbonate minerals. The bottom hole pressure
increased once the viscous pad (non-reactive) reached the
formation. The acid and pads were injected at the highest
possible rate (55 bbls/min) such that the bottomhole pressure
did not exceed 16,000 psi. The type of well tubulars used in
these wells establishes this pressure limit.
After displacing all acid stages into the formation, the
pumps were shut-down to allow the fracture to heal. Then the
closed fracture acid (CFA) was pumped at 10 bbls/min, i.e.,
below the fracture pressure of the formation. The volume of
the CFA was 11,000 gals. Finally, a postflush of linear gelled
water was injected to displace all acids into the formation. It
should be mentioned that the fluid in the tubing-casing
annulus was diesel. The annulus pressure was maintained at
5,500-6,000 psi during the treatment to reduce the differential
pressure across the tubing.
Analysis of Flowback Samples
To assess the performance of the acid fracture treatments,
samples of well flowback were collected and the
concentrations of key ions were measured. The aqueous phase
in these samples was separated and analyzed for key ions.
Calcium, magnesium, molybdenum, nickel, chromium, and
total iron concentrations were measured by inductively
coupled argon plasma emission spectroscopy (ICAP). Ferrous
ion concentration was measured on site following the
procedure of Taylor et al.20 Acid concentration was
determined using acid-base titration. Chloride ion was
measured by titration using a 0.1 N silver nitrate solution. To
measure pH, an Orion model 250A meter and Cole Parmer
Ag/AgCl single junction pH electrode were used. Formate ion
concentration was measured following the procedure of Taylor
et al.21
Gelled HCl/Formic
The first set of wells was acid fractured using gelled
HCl/formic acid, whereas an in situ gelled HCl/formic acid
was used in the second set of wells . Well “H” was acid
fractured using gelled HCl/formic acid. The well has nearly 64
ft of perforations. Following fracture initiation with gelled
water, the acid treatment started with 4,000 gals of “slick” 15-
wt% HCl/9-wt% formic acid, as a spearhead acid. This was
followed by six stages of gelled 15 wt% HCl/9 wt% formic
acid. The volume of each acid stage was 20,000 gals. The
first four acid stages were separated with four viscous pads of
18,000 gals ; whereas the last two acid stages were separated
by two viscous pads 15,000 gals each.
Figure 5 plots the acid concentration and pH as a function
SPE 84925
of flowback time for well “H”. There was no live acid present
in the flowback samples. It is evident from these results that
the soaking time and overflush were effective in reducing the
concentration of HCl in the flowback samples. Previous work
conducted on the same field using 28 wt% HCl-based acids
indicated that the flowback samples contained live HCl, which
caused significant corrosion to low-carbon steel tubulars (C-
95).4 This problem did not occur in these treatments.
The pH of the well flowback samples was nearly 4, which
confirms that all HCl was spent in the formation. To further
support this finding, the concentrations of total iron and Fe(II)
were monitored (Fig. 6). The initial total iron concentration
was 190 mg/L, then it gradually decreased with time. Most of
this iron was present in the form of Fe(II). These levels of
iron are very low and indicate that the acid did not attack the
super Cr-13 tubing. This point will be discussed later in this
paper.
Figure 7 reflects the analysis of recovered fluids for the
presence of the formate ion. The live acid contained 9 wt%
formic acid and the anticipated concentration of formate ions
was expected to be approximately 90,000 mg/L. However,
formic acid concentration in the live acid was 102,260 mg/L.
Formic acid and formamide in the corrosion inhibitor increase
the formic acid concentration in the live acid above 9 wt%.
The concentration of formic acid in the flowback samples,
Fig. 7, is roughly half of that expected. This can be attributed
to either dilution of the injected acid with reservoir fluids or
decomposition of formic acid at high bottom hole
temepratures.15 To further investigate this point, the
concentration of chloride ion in the flowback samples was
measured, Fig. 7. The concentration of the chloride ion in live
acid was nearly 160,000 mg/L. Chloride in the additives
increases the initial chloride concentration above the expected
value obtained with 15 wt% HCl. The chloride concentration
in the flowback sample was nearly 80,000 mg/L. These
results indicate that the chloride ion in the flowback is nearly
50% of that present on the live acid. This means that the low
values of formate ion in the flowback samples is mainly due to
dilution of the acid with reservoir fluids, including the
preflush and postflush.
The target zone contains calcite (CaCO3 ) and dolomite
CaMg(CO3 )2 . Therefore, it is of interest to measure the
concentrations of calcium and magnesium in the flowback
samples. Figure 8 shows that the concentration of both cations
in the flow back samples. The concentration of calcium was
significantly high than that of magnesium. However, both
concentrations increased with time during the later stages of
flow back. This is most likely due to the retarded effect of
formic acid which is expected to react once the HCl is
completely spent.
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.18
SPE 84925 H.A.
l Nasr
-Din,
- S.M. Driweesh, G.A. Muntasheri
In-situ gelled acid used contained iron (III) as a cross-
linker. It is expected to observe this iron in the flowback
samples. To illustrate this point, the total iron concentration
was measured in the flowback samples of well “D” . This well
was treated with 4,000 gals of spearhead acid, then stages of
main acid with total volume of 40,000 gals, which was
followed by 11,000 gals of CFA. A postflush was used to
place all of the treatment fluids into the formation. Figure 9
shows the chloride and total iron concentrations in the well
flowback samples. The first few samples contained relatively
low chloride concentration. This is mainly due to the
postflush water, which contain ed 400- 500 mg/L chloride. The
chloride concentration significantly increased to nearly 73,000
mg/L indicating the arrival of the spent acid. Chloride
concentration remained relatively high, until the end of the
flowback. The total iron concentration was low during the
initial stages of well flowback (during the production of the
postflush). It increased to nearly 220 mg/L during the
flowback of the spent acid, and then gradually decreased. As
mentioned before, the in-situ gelled acid contained Fe(III) as a
cross-linker. The cross-linker, Fe(III), produced with the
spent acid. In other words, the source of iron in the flowback
sample is not corrosion of the tubing, but the iron used as a
cross-linker with the in-situ gelled acid.
Calcite Content from Well Flowback Samples
The concentrations of calcium and magnesium in the flowback
samples can be used to determine the average calcite and
dolomite contents of the treated zone. Obviously, the main
source of magnesium in the formation rock is dolomite. The
weight ratio of calcium to magnesium in pure dolomite is
1.67. It should be noted that all fluids used in fracturing
treatments were prepared using low-salt content water, less
than 1,200 mg/L. In other words, the acids used in the
fracturing treatments did not contain significant amounts of Ca
or Mg ions (Table 5). In addition, all of the treated wells did
not produce formation water before or after the treatment. As
a result, the main source of calcium and magnesium in the
well flowback samples is the formation rock.
Calcite and dolomite are the two main minerals that can
produce calcium and magnesium in the flowback samples.
Other possible sources of calcium and magnesium in the
formation include ankerite (CaMgFe(CO3 )2 ) and anhydrite
(CaSO4 ). However, the former mineral was not detected in
any significant amounts when reservoir cores were examined
using XRD analysis.13 The latter has a very low solubility in
mineral acids. Therefore, magnesium and calcium ions
released in the flowback samples from minerals other than
calcite and dolomite were neglected.
To determine calcite and dolomite content in the
formation, several steps were taken. Calcium and magnesium
concentrations were measured in the flowback samples and
the weight ratio of Ca to Mg was determined. The first few
measurements were excluded because they presented the
overflush. The number of these samples was determined based
on the concentration of chloride in the flowback samples. To
illustrate this procedure, the calcium and magnesium weight
ratio was determined for flowback samples of well “H”, Fig.
10. Based on this analysis, the target zone in well “H” has 30
wt% calcite.
5
Treatment Evaluation
A total of ten wells were fractured using gelled and in-situ
gelled 15 wt% HCl/9 wt% formic acid systems. All wells
responded positively to the treatment. Gas production and
flowing wellhead pressure were increased for all treatments,
Figs. 11 & 12. In addition, wells treated with HCl/formic acid
showed better performance than wells treated with other acid
systems.2 It should be mentioned that production increases
noted with some of the wells (e.g., wells C and I) treated with
gelled acid were less than those observed with wells treated
with in-situ gelled acid. All wells treated with in-situ gelled
acids showed significant increases in gas production and
flowing wellhead pressure. A plausible explanation for this
trend could be the higher viscosity that is generated by the in-
situ gelled acid. This high viscosity means lower leak-off and
deeper acid penetration. More work is underway to fully
understand this trend.
The most important issue in this study was the integrity of
the super Cr-13 tubing. According to Table 1, the main
elements present in the tubing besides iron are Cr, Ni, and Mo.
The concentrations of these elements were measured for all
wells treated with the HCl/formic acid. Table 6 shows that the
concentrations of these elements were very low. These data
clearly indicate that the acid did not attack the tubing.
In addition to these data, the inside diameter of the tubing
was measured for several wells that were treated with the
HCl/formic acid. These measurements were conducted using
a production multi-fingering imaging tool (PMIT). This tool
is equipped with 40 arms and has a radial accuracy of ± 0.03
inch. The results obtained from this tool indicated that the
effect of acid on the tubing inside diameter was not
significant. In addition, there was no evidence of pitting or
deposition of scale products (iron sulfide or iron carbonate) on
the internal surface of the tubing.
Based on the field data obtained, 15 wt% HCl/9 wt%
formic acid systems were effective in stimulating the treated
wells. Moreover, the corrosion inhibitor package, soaking
time, and overflush were effective in maintaining the integrity
of the super Cr-13 tubing.
Conclusions
1. A gelled 15 wt% HCl/9 wt% formic acid system was
successfully used to acid fracture ten vertical wells in
deep gas reservoirs.
2. The corrosion inhibitor package maintained the
integrity the super Cr-13 tubing, with no significant
uniform or pitting corrosion.
3. No operational problems were encountered during
mixing or pumping the acid.
4. Substantial increases in gas production and flowing
wellhead pressures were obtained from the gelled and
in-situ gelled 15 wt% HCl/9 wt% formic acid
treatments
5. The cooling effect encountered during pumping the
acid was effectively used to optimize the loading of
the intensifier.
6. Increasing acid soaking time to three hours, and
increasing the volume of the overflush successfully
eliminated the return of live acid after the treatment.
6 H.A. Nasr
-l -Din, S.M. Driweesh, G.A. Muntasheri
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 K. Bartko for
useful discussions, A. Al-Zahrani, F. Al-Dawood, H.H. Al-
Hajji, and R. Al-Helal for conducting most of the experiments
presented in this study. Udhailiyah Lab Unit, SALD, the
Chemistry Unit and the Corrosion Unit of the R&D Center,
Saudi Aramco were helpful in their field monitoring, analysis
of the spent acids, and conducting corrosion tests,
respectively. Members of the stimulation group, R&DC are
acknowledged for processing well flowback samples.
Engineers in Gas Production Engineering Division are
acknowledged for useful discussions. Members of local
service companies are acknowledged for conducting corrosion
tests and for many useful discussions.
References
1. 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.
2. Rahim, Z., Bartko, K., and Al-Qahtani, M.:
“Hydraulic Fracturing Case Histories in the
Carbonate and Sandstone Reservoirs of Khuff and
Pre-Khuff Formations, Ghawar Field, Saudi Arabia,”
paper SPE 77677 presented at the 2002 SPE Annual
Technical Conference and Exhibition held in San
Antonio, TX, 29 September – 2 October.
3. Nasr-El-Din, H.A., Solares, J.R., Al-Mutairi, S.H.,
and Mahoney, M.D.: “Field Application of
Emulsified Acid-Based System to Stimulate Deep,
Sour Gas Reservoirs in Saudi Arabia,” paper SPE
71693 presented at the 2001 SPE Annual Conference
and Exhibition held in New Orleans, LA, September
30 to October 3.
4. Nasr-El-Din, H.A., Al-Mutairi, S.H., Al-Jari, M.,
Metcalf, S., and Wallace, W.: “Stimulation of a Deep
Sour Gas Reservoir Using Gelled Acid,” paper SPE
75501 presented at the 2002 SPE Gas Technology
Symposium held in Calgary, AB, Canada, 30 April to
02 May.
5. Lynn, J.D. and Nasr-El-Din, H.A.: “A Core -Based
Comparis on of the Reaction Characteristics of
Emulsified and In-Situ Gelled Acids in Low-
Permeability, High Temperature, Gas Bearing
Carbonates,” paper SPE 65386 presented at the 2001
SPE Oilfield Chemistry, Houston, TX, 13-16
February.
6. Nasr-El-Din, H.A., Al-Driweesh, S., Al-Muntasheri,
G., Marcinew, R., Daniels, J., and Samuel, M.: "Acid
Fracturing HT/HP Gas Wells Using a Novel
Surfactant Based Fluid System," paper SPE 84516
presented at the 2003 SPE Annual Meeting and
Exhibition held in Denver, CO, 5-8 October.
7. Cayard, M.S., Kane, R.D. and Kaneta, H.:
“Serviceability of 13Cr Tubulars in Oil and Gas
SPE 84925
Production Environments,” paper NACE 112
presented at the 1998 NACE International Annual
Conference and Exposition.
8. Sakamoto, S., Maruyama, K.: “Corrosion Property of
API and Modified 13Cr Steels in Oil and Gas
Environment,” paper NACE 77 presented at the 1996
NACE International Annual Conference and
Exposition.
9. Asahi, H., Hara, T., Sugiyama, M.: “Corrosion
Performance of Modified 13Cr OCTG,” paper NACE
# 61 presented at the 1996 NACE International Annual
Conference and Exposition.
10. Nasr-El-Din, H.A., Al-Mutairi, S.H., Al-Malki, M.,
Metcalf, S., and Wallace, W.: “Stimulation of Deep
Gas Wells Using HCl/Formic Acid System: Lab
Studies and Field Application,” paper CIM2002/289
presented at the 2002 Petroleum Society’s Canadian
International Petroleum Conference, Calgary,
Alberta, Canada, 11 – 13 June.
11. Al-Jalal, I.A.: “Diagenetic Effects on Reservoir
Properties of the Permian Khuff Formation in Eastern
Saudi Arabia,” paper SPE 15745 presented at 1987
SPE Middle East Oil Show held in Bahrain, 7-10
March.
12. Bartko, K., Nasr-El-Din, H.A., Rahim, Z., and Al-
Muntasheri, G.: “Acid Fracturing of a Carbonate Gas
Reservoir: The Impact of Acid Type and Lithology
on Fracture Half Length and Width,” paper SPE
84130 presented at the 2003 SPE Annual Conference
and Exhibition, Denver, CO, 5 - 8 October.
13. Taylor, K.C., Al-Ghamdi, A.H., and Nasr-El-Din,
H.A.: “Effect of Rock Type and Acidizing Additives
on Acid Reaction Rates Using the Rotating Disk
Instrument,” CIM2003/068 presented at the 2003
Petroleum Society’s Canadian International
Petroleum Conference, Calgary, Alberta, Canada, 11
– 13, June.
14. Nasr-El-Din, H.A., Al-Khuraidah, A., Krizler, T. and
Cassidy, J.: “Recent Development in High-
Temp erature Acidizing with Super Cr-13
Completions: Laboratory Testing,” paper SPE 78557
presented at the 2002 SPE/ADIPEC Conference held
in Abu Dhabi, UAE, 13-16 October.
15. Brezinski, M.M.: “New Environmental Options for
Corrosion Inhibitor Intensifiers,” paper SPE 52707
presented at the 1999 SPE/EPA Exploration and
Production Environmental Conference held in
Austin, TX, 28 February-3 March.
16. Do Carmo Marques, L.C. and Mainier, F.B.:
“Corrosion Problems Associated with the Use of
Copper-Based Corrosion Inhibitor Intensifier in Acid
Stimulation Treatments,” paper SPE 23634 presented
at the 1992 Latin American Petroleum Engineering
Conference held in Caracas, Venezuela, 8-11 March.
17. Huizinga, S. and Liek, W.E.: “Corrosion Behavior of
13% Chromium Steel in Acid Stimu lations,”
Corrosion, 50 (1994) 555-566.
18. Taylor, K.C. and Nasr-El-Din, H.A.: “Laboratory
Evaluation of In-Situ Gelled Acids for Carbonate
SPE 84925 H.A.
l Nasr
-Din,
- S.M. Driweesh, G.A. Muntasheri 7

Reservoirs,” paper SPE 71694 presented at the 2001

SPE Annual Technical Meeting and Exhibition, New
Orleans, LA, 30 September – 3 October.
19. Nasr-El-Din, H.A., Al-Mutairi, S.H., and Al-
Driweesh, S.M.: “Lessons Learned from Acid Pickle
Treatments of Deep/Sour Gas Wells,” paper SPE
73706 presented at the 2002 SPE Int. Symposium on Table 3. Formulation of gelled HCl/formic acid
Formation Damage Control, Lafayette, LA, 20-21
February. Chemical Concentration
20. Taylor, K.C., Nasr-El-Din, H.A. and Al-Alawi, M.J.: HCl 15 wt%
“Field Test Measures Amount and Type of Iron in Formic 9 wt%
Spent Acids,” paper SPE 50780 presented at the 1999 Corrosion Inhibitor 2.0 vol%
SPE International Symposium on Oilfield Chemistry, Corrosion Inhibitor Intensifier Variable
Houston, TX, 16-19 February. Surfactant 0.1 vol%
21. Taylor, K.C., Al-Katheeri, M.I., and Nasr-El-Din, Gelling Agent 1.5 vol%
H.A.: “Development and Field Application of a New
Measurement Technique for Organic Acid Additives
in Stimulation Fluids,” paper SPE 58801 presented at
the 2000 SPE International Symposium on Formation
Damage Control, Lafayette, LA , 23-24 February.

Table 4. Chemical analysis of gelled HCl/formic acid a

Variable Concentration
HCl 14.8, wt%
Ca 89
Table 1. Elemental composition of low-carbon steel Mg 30
(L-80 and C-95) and super Cr-13.a Na 409
K 146
Element L-80 C-95 Super 13-Cr Cr, Ni, Mo <1
Carbon 0.43 0.45 0.2 Fe (total) 7
Manganese 1.9 1.9 0.5
Cl 150,323
Molybdenum - - 2.0
a. All ion concentrations are expressed in mg/L
Chromium - - 12.2
Nickel 0.25 - 6.0
Copper 0.35 - -
Phosphorous 0.03 0.03 0.02
Sulfur 0.03 0.03 0.001
Silicon 0.045 0.03 0.2 Table 5. Formulation of in-situ gelled HCl/formic acid
a. All concentrations are expressed in wt%
Chemical Concentration
HCl 15 wt%
Formic 9 wt%
Corrosion Inhibitor 20 gpt
Corrosion Inhibitor Intensifier Variable
Surfactant 1 gpt
Gelling Agent 15 gpt
Cross-linker 10 gpt
Table 2. Mineralogy of reservoir cores
Breaker 4 ppt
Buffer 2 gpt
Mineral Concentration, wt%
Calcite 80
Dol omite 18
Quartz 2
Sylvite Trace
Albeit Trace
Anhydrite Trace
8 H.A. Nasr
-l -Din, S.M. Driweesh, G.A. Muntasheri SPE 84925

Table 6. Concentrations of key ions in the flowback Samples.

Time (min) Cr Mo Ni
0 1 <10 <1
6 <1 <10 <1
12 <1 <10 <1
18 <1 <10 <1
24 1 <10 <1
30 <1 <10 <1
36 <1 <10 <1
42 <1 <10 <1
48 <1 <10 <1
54 <1 <10 <1
60 <1 <10 <1
66 <1 <10 <1
72 <1 <10 <1
78 <1 <10 <1
84 <1 <10 <1
90 2 <10 <1
96 <1 <10 <1
102 <1 <10 <1
113 <1 <10 <1
128 <1 <10 <1
143 <1 <10 <1
158 <1 <10 <1
173 <1 <10 <1
188 <1 <10 <1
203 <1 <10 <1
218 <1 <10 <1
233 <1 <10 <1
248 <1 <10 <1
263 <1 <10 <1
278 <1 <10 <1
293 <1 <10 <1
SPE 84925 H.A.
l Nasr
-Din,
- S.M. Driweesh, G.A. Muntasheri 9

Photo 1. Photos of core plug before and after

Injection of 1 PV of 15% HCl/9% formic acid

Core Inlet Face

1a. Before 1b. After

Core Outlet Face

Wormholes

1c. Before 1d. After

10 H.A. Nasr
-l -Din, S.M. Driweesh, G.A. Muntasheri SPE 84925

Fig. 1. Effect of potassium iodide (intensifier) on the apparent viscosity of gelled 15% HCl/9% formic acid

100

T = 25 oC
Viscosity, cP

10 Potossium Iodide

10 lbs/1000 gals

100 lbs/1000 gal

1
10 100 1000 10000
-1
Shear Rate, S

Fig. 2. Effect of temperature on the apparent viscosity of gelled 15% HCl/9% formic acid

100

o
77 F

o
265 F
Viscosity, cP

10

Potossium Iodide= 10 Ib/1000 gals

1
10 100 1000 10000
-1
Shear Rate, s
SPE 84925 H.A.
l Nasr
-Din,
- S.M. Driweesh, G.A. Muntasheri 11

Fig. 3. Bottomhole temperature during pumping th4e HCl/formic acid, well “X”

250
o
F

220 Frac Start

Temperature,

190

160

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

Fig. 4. Pressure response and pumping rate during acid fracture treatment of well “I”

16000 100
STP (psi)
Establish Rate with
Calc BHTP (psi)
Acid on Formation
Rate (bpm) 90
14000

80
12000
70

10000 Shut Down

Pressure (psi)

60
Rate (bpm)

Between CFA's

8000 50

40
6000

30
CFA Stage, Over flush
4000
20

2000
10

0 0
Start Job
0.0 50.0 100.0 150.0 200.0 250.0
Treatment Time, Minutes
12 H.A. Nasr
-l -Din, S.M. Driweesh, G.A. Muntasheri SPE 84925

Fig. 5. pH and HCl concentration in the flowback samp les of well “H”.

4
pH & HCl, wt%

pH
3
HCl

0
0 50 100 150 200 250 300
Flowback Time, Minutes

Fig. 6. Total iron and Fe(II) concentration in the flowback samples of well “H”.

200

Total Iron
Iron Concentration, mg/L

160

120

80 Fe(II)

40

0
0 200 400 600 800 1000 1200 1400 1600
Flowback Time, Minutes
SPE 84925 Field Application of HC l-Formic Acid System to Acid Fracture Deep Gas Wells Complete er C r-13Tubing 13

Fig. 7. Chloride and formate ion concentrations in the flowback samples of well “H”.

100000

80000

Cl
Formate & Cl, mg/L

60000

Formate

40000

20000

0
0 50 100 150 200 250 300
Flowback Time, Minutes

Fig. 8. Calcium and magnesium ion concentrations in the flowback samples of well “H”.

50000

Ca
40000
Ca&Mg,mg/L

30000

20000
Mg

10000
0 50 100 150 200 250 300
Flowback Time, Minutes
14 H.A. Nasr
-l -Din, S.M. Driweesh, G.A. Muntasheri SPE 84925

Fig. 9. Total iron and chloride concentration in the flowback samples of well “D”

100000
Total Iron & Chloride, mg/L

10000
Total Fe

1000

Cl
100

10

1
0 200 400 600 800 1000 1200 1400 1600
Flowback Time, Minutes

Fig. 10. Ca/Mg weight ratio in the flowback samples of well “H’

4
Ca/Mg, Wieght Ratio

Pure Dolomite
1

0
0 50 100 150 200 250

Flowback Time, Minutes

SPE 84925 Field Application of HC l-Formic Acid System to Acid Deep Gas Wells Completed with Super C r-13Tubing 15

Fig. 11. Gas production rates before and after acid fracture treatments using 15% HCl/9% formic acid

70

Post-Frac
60
Pre-Frac

50
Gas Rate, MMSCFD

40

J
30

20

10

0
B C D E F G H I J
A 1

Well#

Fig. 12. Flowing wellhead pressure before and after acid fracture treatments using 15% HCl/9% formic acid

5000

4500 Post-Frac

Pre-Frac
4000

3500
FWHP, psig

3000

2500

2000

1500

1000

500

0 A B C D E F G H I J
1

Well#