Journal of Petroleum Science and Engineering 28 2000.

3353
www.elsevier.nlrlocaterjpetscieng

Analysis of acid returns improves efficiency of acid stimulation:

a case history
K.C. Taylor a,) , H.A. Nasr-El-Din a,1, Ragheb B. Dajani b,2
a

Laboratories R & D Center, P.O. Box 62, Saudi Aramco, Dhahran 31311, Saudi Arabia
b
BJ Serice Arabia Ltd., P.O. Box 14037, Dammam 31424, Saudi Arabia
Received 24 June 1999; accepted 26 June 2000

Abstract
Techniques are demonstrated to evaluate acid stimulation treatments based on chemical analysis of the return fluids. The
techniques can provide information about the source of formation damage, the amount and type of scale in the casing, the
efficiency of the acid treatment, and the amount of iron control chemicals required for similar treatments. As an example,
these methods were used for the acid stimulation treatment of a typical seawater injection well Well A. in a large carbonate
reservoir in Saudi Arabia. Over a 2-day period, more than 50 field samples were collected. More than 700 chemical analyses
were eventually made on these samples. Analysis of the casing pickle fluids showed that 235 kg of iron from corrosion
products, as well as a significant amount of acid-insoluble iron carbide, Fe 3 C, was produced. Measurement of iron II. and
iron III. concentrations showed that the iron corrosion products in the casing contained mostly iron oxides such as rust or
mill scale. The pickle treatment prevented the injection of this material into the formation around the wellbore. Otherwise,
the main acid treatment would have flushed all of this material into the reservoir and reduced injectivity. Analysis of the
matrix acid flowback samples showed that iron control chemical concentrations in the acid could be reduced with significant
cost savings. The extent of acid dilution and the amount of unreacted acid were also determined. The results showed that 125
kg of calcium sulfate was dissolved from the near-wellbore region during flowback. Acid stimulation of Well A increased
the injectivity index II. of the well from 0.12 to 0.21 m3rdayrkPa 5 to 9 bblrdayrpsi., an increase of 75%. The acid
stimulation was successful and the evaluation methods provided useful information to improve the success of future
treatments. q 2000 Elsevier Science B.V. All rights reserved.
Keywords: injection well; stimulation; formation damage; iron control chemicals; pickling acid

1. Introduction
)

Corresponding author. Fax: q966-3-876-2811.

E-mail addresses: taylorkc@mail.aramco.com.sa
K.C. Taylor., nasrelha@mail.aramco.com.sa H.A. Nasr-El-Din.,
mdajani@bjservices.co.ae R.B. Dajani..
1
Fax: q966-3-876-2811.
2
Fax: q966-3-858-8128.

The seawater injection system for a large carbonate field in Saudi Arabia has more than 400 km of
pipeline and can supply 0.67 million m3rday 4.2
million barrels per day. of treated seawater. In this

0920-4105r00r$ - see front matter q 2000 Elsevier Science B.V. All rights reserved.
PII: S 0 9 2 0 - 4 1 0 5 0 0 . 0 0 0 6 6 - 8

K.C. Taylor et al.r Journal of Petroleum Science and Engineering 28 (2000) 3353

34

system, corrosion must be maintained at a reasonable

level, and water quality must be high enough to
prevent excessive losses of injectivity Brown et al.,
1979; Bayona, 1993.. Extensive sections of the
pipeline are internally coated to reduce corrosion.
Water quality standards have been established and
are shown in Table 1. Corrosion control in water
injection systems was reviewed by Patton 1993..
Chen and Ahmed 1998. recently gave a review of
the coating effectiveness and water quality.
Even with these measures, injectivity of some
wells in the reservoir has gradually decreased and
acidizing treatments only partially restore injectivity
Bayona, 1993; Chen and Ahmed, 1998.. As the
cumulative water injection increases, the acidizing
effectiveness decreases. To address these trends, a
detailed investigation of an acidizing treatment of a
typical injection well in the field was initiated.
Most water injection wells in this carbonate reservoir are vertical with openhole completions over an
interval of 60 to 120 m 200 to 400 ft.. Static bottom
hole temperatures are 498C to 658C 1208F to 1508F..
Static bottom hole pressure is approximately 27.5
MPa 4000 psig. at 2271 m 7450 ft.. Treated seawater Table 2. is injected to maintain the reservoir
pressure.
To restore injectivity, damaged wells are stimulated using 15 wt.% HCl. Various acid diversion
techniques have been used. Ginest et al. 1993.
evaluated three different acid placement techniques
in the carbonate reservoir. These included conventional bullhead treatments, coiled tubing with nitrogen foam diversion, and coiled tubing without divert-

Table 1
Water quality requirements for seawater injection Bayona, 1993.
Component

Specifications

Total suspended solids

Particle number and size

- 0.2 mgrl
Maximum of 200 particles
greater than 2 mm
per 0.5 ml of water
-10 ppb a
-14 mgrl
7.07.5

Dissolved oxygen
Sulfide
pH b
a

This is in agreement with Patton 1993..

pH is adjusted to prevent the precipitation of calcium
carbonate.
b

Table 2
Analysis of injected seawater and low sulfate water used in
Well A
Component

Injected seawater
mgrl.

Water used
in Well
A mgrl.

Sodium
Calcium
Magnesium
Sulfate
Chloride
Bicarbonate
Total dissolved solids
Iron
pH
Density, grcm3 at
15.58C 608F.

16,870
700
2,040
4,150
30,040
160
53,960
- 0.01
7.5
1.0418

210
137
48
270
371
210
1,257
1
8
1.0011

ing agents. The goal of the work was to improve the

efficiency of stimulation of the long openhole sections in the formation as a result of drilling mud
damage. They concluded that coiled tubing treatments with nitrogen foam diversion were more effective than conventional bullhead jobs; however, surface washout does not currently allow the use of
coiled tubing in some of the wells in this reservoir.
The gradual injectivity decline observed in these
wells may be a result of near-wellbore plugging or
deep damage by particulates over an extended period
of time. Possible sources of this damage include the
precipitation of iron III. hydroxide from previous
acidizing treatments Crowe, 1985., the formation of
calcium sulfate scale from the seawater that is injected Allaga et al., 1992. or the formation of iron
sulfide and biomass as a result of microbial corrosion reactions Lee et al., 1995.. Allaga et al. 1992.
showed that calcium sulfate precipitation inside a
sandpack resulted in a gradual permeability decline.
Iron sulfide has been identified as a corrosion product in seawater injection systems Chen and Ahmed,
1998; Little et al., 2000.. The plugging of the formation over time with both acid soluble and acid-insoluble particulates would be consistent with the
type of injectivity loss observed by Bayona 1993..
Water injection wells can contain large amounts
of iron scale from pipe corrosion. This corrosion
occurs from oxygen in the injection water or from
microbial action. If acid is bullheaded into a water

K.C. Taylor et al.r Journal of Petroleum Science and Engineering 28 (2000) 3353

injection well, iron scale will rapidly react with the

acid. Total iron concentrations up to 100,000 mgrl
have been reported in acid returns from other water
injection wells Gougler et al., 1985..
Corrosion in the casing can be present in several
forms. If small amounts of oxygen are present in the
injected water, then iron oxides will form. In air, this
rust or mill scale contains three layers of iron oxide
Coburn, 1984.. The outer layer is primarily ferric
oxide, Fe 2 O 3 . The layer closest to the steel is ferrous
oxide, FeO. The intermediate layer can be represented as Fe 3 O4 or FeO P Fe 2 O 3 . In the latter, the
ratio of iron III. to iron II. is two to one. If 15
wt.% HCl reacts with sufficient Fe 3 O4 to give a
solution containing 45,000 mgrl total iron, then the
reacted acid will contain 30,000 mgrl iron III. and
15,000 mgrl iron II.. Acid reaction with rust reduces the acid concentration in this example from 15
to 7 wt.%. This dissolved iron can lead to plugging
in the critical near-wellbore region.
Two reactions can occur with iron III. that can
lead to precipitation of iron compounds. If hydrogen
sulfide is present, then iron III. will react to form
elemental sulfur Crowe, 1985; Taylor and Nasr-ElDin, 1999.. In the absence of hydrogen sulfide, iron
III. hydroxide will precipitate as the pH increases
above 1 Taylor et al., 1999a, Taylor and Nasr-ElDin, 1999.. Iron II. will not precipitate as a hydroxide until the pH increases to a value of about 7
Crowe, 1985..
Iron control chemicals are not able to maintain
iron III. concentrations above 10,000 mgrl in spent
acidizing fluids. For instance, to keep 10,000 mgrl
iron III. in solution at 528C 1258F. requires 22 l of
acetic acid and 12 kg of citric acid per 1000 m3 of
15% HCl Dill and Smolarchuk, 1988.. It is not
recommended to exceed this level of acetic acid and
citric acid, since precipitation of calcium citrate may
occur. Calciumriron complexes with citric acid
formed at high citric acid concentrations in partially
spent acids Taylor et al., 1999a..
Several chemical studies of acid flowback samples have been reported. Gdanski and Peavy 1986.,
Almond et al. 1990., Shuchart 1995. and Nasr-ElDin et al. 1996. examined acid return samples in
sandstone reservoirs. Nasr-El-Din et al. 1999.,
Dahlan and Nasr-El-Din 2000. and Mohamed et al.
1999. examined acid returns in carbonate reservoirs.

35

No comprehensive chemical studies of acid flowback samples from water injection wells have been
published, to the best of our knowledge. The objectives of this study are to: 1. demonstrate techniques
to evaluate acid stimulation treatments based on
chemical analysis of the return fluids, 2. use these
techniques in Well A to identify the source of formation damage, the amount and type of scale in the
casing, and the efficiency of the acid treatment, 3.
evaluate the amount and type of iron control chemicals that were used, and 4. make recommendations
to improve future similar treatments.
1.1. Well description
Well A is a seawater injection well in a large
carbonate reservoir in Eastern Saudi Arabia. The
injectivity of this well has been decreasing since
injection began in 1993. The injectivity index decreased from 0.53 m3rdayrkPa 22 bblrdayrpsi.
Nov.r93. to a value of 0.12 m3rdayrkPa 5 bblr
dayrpsi. before the treatment. The damage to this
well is significant and has been occurring over a
number of years.
The well has an openhole completion in the interval from 2215 to 2324 m 7268 to 7626 ft.. The well
was acidized using 3.8 cm 1.5 in.. coiled tubing in
1992 to improve well injectivity. At that time, 15 m3
95 barrels. of 15 wt.% HCl containing a surfactant
0.2 vol.%., a corrosion inhibitor 0.4 vol.%. and a
friction reducer 0.2 vol.%. were injected into the
formation. No iron control chemicals were used and
the well was not flowed back after the treatment.
Instead, the reacted acid was displaced into the
formation using seawater.
A caliper log indicated a washout approximately
0.6 m 25 in.. in the zone from 2215 to 2217 m
6751 to 6757 ft.. A spinner test indicated that most
of the injected water was going into a narrow zone
that extended from 2228 to 2256 m 6791 to 6876
ft..
The well has a 17.8 cm 7 in.. liner from the
openhole section to 742 m 2262 ft.. All of the
casing in the well is J-55 low carbon steel. The
wellbore volume is nearly 61 m3 383 barrels. and
the static bottom hole temperature is 588C 1378F.. A
typical geochemical analysis of the seawater injected
into Well A is given in Table 2.

K.C. Taylor et al.r Journal of Petroleum Science and Engineering 28 (2000) 3353

36

1.2. Description of the treatment

Mixing and water tanks were inspected, and samples were taken of all chemicals on site before the
treatment began. The treatment chemicals collected
at Well A were:
Breakerriron control
Erythorbic acid, reduces iron III. to iron II.
Citric acid, prevents precipitation of iron III. by
forming a soluble complex in spent acid
Cross-linking agent
Surfactant, to improve the contact between the
live and spent acids with reservoir rock
Polymer, to increase the viscosity of the in situ
gelled acid
Mixed samples of the pickle acid containing all
additives
A mixed sample of the 10 wt.% in situ gelled acid
containing all additives
A mixed sample of the 15 wt.% acid containing
all additives
Low salinity water for mixing of acids, pre-flush
and post-flush
The corrosion inhibitor was already present in the
acid when it arrived on site.
On the first day of the treatment, the well was
flowed back using reservoir pressure to flush out the
wellbore. Samples were collected and the flowrate
was determined by measuring the time required to
fill a container of known volume 0.16 m3 .. The rate
was found to be 22.3 m3rh 140 bblrh..

On the second day, the casing was pickled before

the matrix acid stimulation treatment. Compositions
of the fluids that were used in the treatment are
given in Table 3. Treatment stages, volumes, pumping rates and surface pressures are listed in Table 4.
The pickle treatment was performed to remove
rust and scale from the casing. This part of the
treatment was designed so that penetration of the
acid into the formation would be minimal. The acid
8 m3 . was displaced down the casing with 50 m3
315 barrels. of a low salinity low sulfate water until
the acid was close to the openhole section. The well
was then flowed back to flush the spent acid from
the casing. Chemical analysis of the low sulfate
water used in the treatment is given in Table 2.
To enhance acid placement efficiency, matrix
stimulation of the well was carried out in 15 stages
Table 4.. The first stage used low sulfate water as a
spacer between the reservoir water and the acid. This
reduces mixing of the spent acid with seawater.
Seawater contains high concentrations of sulfate,
while spent acid contains high levels of calcium.
Mixing of the two fluids leads to precipitation of
calcium sulfate that can damage the formation in the
critical near-wellbore area.
The low sulfate water pre-flush was followed by
alternating slugs of 10 wt.% in situ gelled HCl and
regular 15 wt.% HCl. The in situ gelled acid uses a
polymer and a cross-linking agent to form a high
viscosity acid over a narrow pH range. The purpose
of the in situ gelled acid was to provide acid diversion and increase the flow of acid into the lower
permeability zones. Approximately 0.96 m3rm 77

Table 3
Acid formulation for Well A
Fluid

Chemical additives

15 wt.% HCl acid for pickling.

Pre-flush
15 wt.% HCl
In situ gelled 10 wt.% HCl

0.3 vol.% corrosion inhibitor

0.2 vol.% surfactant in low sulfate water a
0.3 vol.% corrosion inhibitor, 1.1 vol.% acetic acid b , 0.56 wt.% citric acid b , 0.2 vol.% surfactant
0.3 vol.% corrosion inhibitor, 2.0 vol.% gelling agent, 0.045 wt.% breakerriron control,
0.2 vol.% buffer, 0.45 wt.% cross-linker
Low sulfate water a

Overflush
a

Composition of low sulfate water is given in Table 2.

This amount of acetic acid and citric acid can keep approximately 5000 mgrl of iron III. in solution in spent acid at reservoir
temperature.
b

K.C. Taylor et al.r Journal of Petroleum Science and Engineering 28 (2000) 3353

37

Table 4
Treatment stages, volumes, rates and surface pressures for Well A
Stage of treatment

Fluid

Well pickle
15 wt.% HCl
Pickle post-flush
Low sulfate water
Pre-flush
Low sulfate water
1
15 wt.% HCl
2
10 wt.% gelled acid
3
15 wt.% HCl
4
10 wt.% gelled acid
5
15 wt.% HCl
6
10 wt.% gelled acid
7
15 wt.% HCl
8
10 wt.% gelled acid
9
15 wt.% HCl
10
10 wt.% gelled acid
11
15 wt.% HCl
12
10 wt.% gelled acid
13
15 wt.% HCl
14
Overflush
Total 15 wt.% acid m3 .
Total in situ gelled 10 wt.% acid m3 .

Volume m3 .

Pumping rate m3rmin.

Surface pressure MPa.

8.0
50
60
2.2
1.9
2.7
2.2
4.5
4.0
5.1
4.5
5.7
5.1
4.5
5.7
10.6
77
37
23

1.1
2.4
3.2
1.3
1.3
1.4
1.6
1.7
1.9
1.9
1.9
2.1
1.9
2.1
1.9
2.1
1.33.3

7.6
12.8
4.1
15.2
14.5
14.5
14.5
14.8
15.2
15.2
15.2
15.2
15.2
15.5
15.5
15.5
16.5

galrfoot. of acid was injected into the openhole

section. The treatment was followed by injection of
approximately 77 m3 483 barrels. of low sulfate
water. The well was shut in for 70 min for reaction
of the acid with the formation before it was flowed
back.
Over a 2-day period, more than 50 field samples
were collected. More than 700 chemical analyses
were eventually made on these samples.

2. Experimental studies
2.1. Field measurements
Total dissolved iron and ferrous iron were measured at the wellsite using the procedure of Taylor et
al. 1999b.. Ferrous iron was measured in the field
because iron II. is rapidly oxidized to iron III. in
the presence of air. Acid content of the injected acids
was measured by titration of a known acid volume
with 1 N sodium hydroxide solution to a phenolphthalein endpoint pH 9.. Accurate volumes were
measured using calibrated autopipettes. Density was
measured with a portable densitometer. A portable

pH meter was used at the well site and was calibrated with buffers pH 4 and pH 7. before sample
measurement.
2.2. Laboratory measurements
Calcium, magnesium, iron, sodium, aluminum and
zirconium concentrations were measured by inductively coupled argon plasma emission spectroscopy
ICP.. Acid content of flowback samples was measured by titration of a known acid volume with 0.1 N
sodium hydroxide solution to an endpoint of pH 4.2
using an autotitrator. Chloride ion was measured
with an autotitrator using 0.1 N silver nitrate solution. Sulfate ion was measured by turbidity with 0.1
N barium chloride solution. Density measurements
were made with a digital density meter at 15.58C.
The pH was measured with an AgrAgCl single
junction pH electrode. Total dissolved solids were
determined by addition of the concentration of the
chemical species measured. Analysis of filtered suspended solids was done using X-ray diffraction
XRD. and by the energy dispersive X-ray spectrometer attachment of a scanning electron microscope
SEM..

38

K.C. Taylor et al.r Journal of Petroleum Science and Engineering 28 (2000) 3353

3. Results and discussion

3.1. Chemicals used during the treatment
Water of low salinity and sulfate content Table
2. was used in the treatment for the pre-flush, for
mixing the acids and for the post-flush. The chemical
composition of the injected fluids is shown in Table
5. Two different samples of the pickling acid were
taken after it was mixed to demonstrate the reproducibility of the measurement methods. The acid
concentration was very close to the target value of
15 wt.%, and the measurement made at the well site
was in good agreement with the value measured in
the lab.
The 10 wt.% in situ gelled acid contained 180
mgrl aluminum and 325 mgrl zirconium from the
cross-linking additive. The sulfate concentration, at
924 mgrl, was much higher than the value of 270
mgrl found in the mixing water. This additional
sulfate is either from the acid additives or from an
interference in the method.
All four of the injected acid samples had low iron
concentrations with values from 44 to 84 mgrl. This
shows that some iron contamination occurred during
transport and mixing of hydrochloric acid.
3.2. Well flowback (before acid treatment)
This stage of the treatment was included to flush
out any suspended material in the wellbore. Flow
rate was measured at the beginning and at the end of
the flowback, and was 22.3 " 1.5 m3rh 140 " 10

barrelsrh.. This measurement was extremely useful

in later calculations of the casing pickle fluid returns.
If the flowrate of the well is known, then material
balance calculations can be conducted using the concentrations of produced chemical species. Based on
the well flowrate, 2.75 h should be required to flush
out the wellbore volume of 383 bbls.
Fig. 1 shows the concentrations of sulfate, magnesium, calcium and bicarbonate in the produced fluids. The sulfate concentration shows a large increase
after 1.4 h of production. The concentration of sulfate in injected seawater is approximately 4150 mgrl
and is shown in the figure. An increase in calcium
concentration also occurs 1.5 h after flowback. The
value increases from approximately 650 mgrl the
value expected in seawater. to approximately 1500
mgrl. In addition, an increase in density of the
flowback fluids Fig. 2. and the TDS occurs at the
same time as the increase in the calcium and the
sulfate concentrations. No change is observed in the
magnesium or bicarbonate concentrations. At the
same time as the density increase, the pH measured
at the wellsite. gradually decreases Fig. 2.. If the
observed increases in sulfate concentration was due
only to calcium sulfate, then the calcium concentration would increase by approximately 875 mgrl.
This value is very close to the increase of 850 mgrl
that was observed. Therefore, it is likely that the
increase in the calcium and sulfate concentrations is
due to the dissolution of calcium sulfate. The concentration of calcium sulfate increased at 1.5 h after
flowback started, corresponding to 33.4 m3 210
barrels. of brine production. This is lower than the

Table 5
Chemical analysis of acid injection fluids
Variable

Pickle acid a1

Pickle acid a2

10 wt.% in situ gelled acid

15 wt.% acid

Aluminum mgrl.
Calcium mgrl.
Magnesium mgrl.
Sodium mgrl.
Chloride mgrl.
Sulfate mgrl.
Zirconium mgrl.
Total iron mgrl.
Density at 15.58C grcm3 .
Wtrwt.% HCl at wellsite
Wtrwt.% HCl at lab

- 10
116
30
146
148,544
535
- 10
44
1.0722
14.21
14.21

- 10
110
30
146
148,125
481
- 10
44
1.0723
14.75
14.20

180
214
39
418
85,599
924
325
59
1.0561
9.67
9.67

- 10
112
30
145
138,928
438
- 10
84
1.0716
13.50
13.50

K.C. Taylor et al.r Journal of Petroleum Science and Engineering 28 (2000) 3353

39

Fig. 1. Flowback analysis before acid treatment.: sulfate, calcium, magnesium and bicarbonate.

volume of the wellbore 60.9 m3 383 barrels..,

indicating that the calcium sulfate may be present as
a scale on the lower part of the casing. Calcium
sulfate may form a scale due to the temperature
increase that occurs when the seawater flows down

the wellbore to the formation. The solubility of

calcium sulfate in seawater gradually decreases as
the temperature is increased Silcock, 1979.. In desalination plants, untreated seawater will usually produce a calcium sulfate scale when heated above 778C

Fig. 2. Flowback analysis before acid treatment.: pH and density.

40

K.C. Taylor et al.r Journal of Petroleum Science and Engineering 28 (2000) 3353

1708F. Cowan and Weintritt, 1976.. The reservoir

temperature is 938C 2008F., but the bottomhole
temperature at well A is now only 588C 1378F. due
to long-term water injection. If water is produced
from the well, then the seawater in the formation
flowing back to the wellbore will be cooled. If it
flows through an area of precipitated calcium sulfate
or anhydrite, then it will dissolve some of it. It is
then possible for the seawater flowing out of the
formation to contain more calcium and sulfate than
the concentration seen in the injected seawater.
The amount of calcium sulfate dissolved by the
flowback fluid was calculated as 125 kg. The calculation used a flow rate of 22.3 m3rh 140 bblrh.
and an injection water sulfate concentration of 4150
mgrl.
Chloride and sodium concentrations in the flowback samples did not change significantly during the
flowback, and were very close to those expected in
seawater Table 2.. During the last hour of the well
flowback stage, the average chloride and sodium
concentrations were 30,873 and 16,972 mgrl, respectively. The weight ratio of chloride to sodium in
the injected brine is 1.82 to 1, based on these values.
Total iron and ferrous iron concentrations in the
produced fluids were measured and were less than
10 mgrl. No suspended solids were present in the

flowback samples. In general, the samples were clear.

Sulfate-reducing bacteria SRB. are known to be
present in the seawater injection system Bayona,
1993.. The samples collected from 3 h until the end
of the flowback were initially clear and had a slight
odor of hydrogen sulfide. The iron concentration in
these samples was 2 mgrl or less. Within 2 days,
they had become cloudy with a light yellow color. It
is likely that this material was elemental sulfur
formed by the oxidation of hydrogen sulfide by
oxygen, see for example Little et al. 2000..
3.3. Casing pickle fluid returns
The pickling acid contained only a corrosion inhibitor as an additive, and the acid concentration was
nearly 15 wt.%. The chemical composition of the
pickling acid is shown in Table 5.
Fig. 3 shows the acid concentration and the total
iron concentration in the flowback samples. The
maximum acid concentration in the samples was 9.7
wt.%, while the maximum total iron concentration
was 23,600 mgrl. The dissolution of rust from the
casing can account for most of the decrease noted in
the acid concentration, as will be described in the
next paragraph. This means that the acid was not

Fig. 3. Flowback analysis pickle treatment.: hydrochloric acid and total iron.

K.C. Taylor et al.r Journal of Petroleum Science and Engineering 28 (2000) 3353

significantly diluted during the pickle treatment.

Some dispersion is observed in Fig. 3 as the acid
concentration profile is slightly broadened. The flow
was turbulent as the acid was pumped into the casing
and during the flowback.
The composition of the dissolved iron that flowed
back following the pickle treatment is shown in Fig.
3. The total iron content was measured by two
different methods. ICP spectroscopy was used in the
lab analyses. Total iron and iron II. concentrations
were also measured by the field method of Taylor et
al. 1999b. after the samples were brought back to
the lab. The results obtained by the field method are
in excellent agreement with the ICP method. Maximum concentration of iron II. was 10,000 mgrl.
Measurements in the field with and without sample
filtration gave results that agreed within 5%. The
measured maximum iron concentrations give a ratio
of iron II. to iron III. of 0.67 to 1, compared to a
theoretical ratio of 0.5 to 1 in Fe 3 O4 FeO P Fe 2 O 3 ..
The ratio of iron II. to iron III. produced during the
entire flowback of the pickle fluids was 0.9 to 1.
This was calculated using the iron concentrations in
the produced fluids and the flowback rate of the
well. The source of this iron could be gradual surface
corrosion before the pickle treatment, or from rust
that was already present in the casing. In addition to
millscale or rust, a source of iron II. may be present, most likely as FeS. The latter is usually present
as a byproduct in systems contaminated with SRB
Nasr-El-Din et al., 1996; Little et al., 2000..
Several research groups have reported the measurement of ratios of iron II. to iron III. during
various acidizing operations. In field samples, Smith
et al. 1969. observed that the ratio of iron II. to
iron III. in spent acidizing fluids varied from 5:1 to
10:1. In contrast, Well A showed an average ratio of
iron II. to iron III. of 0.9 to 1. The relative amount
of iron III. in this well was much higher than
previously reported results. More details on iron II.
to iron III. ratios are given by Loewen et al. 1990.
and Taylor et al. 1999b..
From Fig. 3, the mass of iron dissolved from
corrosion products during the pickle treatment can be
calculated, since the flow rate of the well during
flowback is known. A total of 235 kg of iron was
produced in the pickle flowback samples. Less than
0.5 kg of iron was present in the injected pickle acid.

41

Scale deposits on the casing were dissolved by the

acid, since direct reaction of steel and hydrochloric
acid produces only iron II. Kaesche, 1985.. If iron
sulfide was the dissolved corrosion product, then
only iron II. would be produced. The high amount
of iron III. present clearly indicates that an oxygencontaining corrosion product was present as the major scale component. This corrosion product could
have been present as mill scale when the casing was
originally put in place. If oxygen was present in the
injection water, rust could also have formed over
long periods of time.
The returning acid samples were black in color
and contained suspended solids. These solids were
isolated by filtration 0.45 mm., dried, weighed, and
analyzed. Fig. 4 shows the concentration of solids by
filtration together with the acid concentration in the
produced fluids. The filtered material was a fine
black powder and was collected from samples with
acid concentrations up to nearly 10 wt.%. XRD
analyses of selected samples are shown in Table 6. It
is important to emphasize that the XRD results show
crystalline material only. Based on these tests, many
of the samples contained iron carbide as a major
component. However, the sample at 2.2 h into the
flowback contained major amounts of akaganeite
-FeOOH... This mineral should be acid soluble. It
may have occurred in the sample by oxidation of an
iron compound after the sample was isolated. At 2.9
h into the flowback, acid is no longer produced and
the solids contain mostly silica, gypsum, and clays.
The approximate compositions of the suspended
solids are shown in Table 7. These results were made
by energy dispersive X-ray spectrometry. This
method gives an approximate elemental composition
for atomic weights greater than 16 oxygen.. The
method does not distinguish between crystalline and
amorphous materials. In all cases, iron was the major
component. Sulfur was a significant component in
some cases, meaning that iron sulfide could be a
component of the suspended solids.
Iron carbide Fe 3 C. is known as cementite or
cohenite and is a component of carbon steel Dugstad et al., 2000.. Cron et al. 1971. studied the
reaction of various acids and bases with low carbon
steels. The mode of acid attack was found to be a
function of the applied potential, pH of the environment, and the anion present. Either the ferrite or the

42

K.C. Taylor et al.r Journal of Petroleum Science and Engineering 28 (2000) 3353

Fig. 4. Flowback analysis pickle treatment.: suspended solids and HCl concentration.

carbide phases could be reactive or non-reactive,

depending on the electrochemical conditions. In Well
A, it is likely that the iron in the steel casing was
corroded and the acid dissolved the corrosion products, but left small particles of iron carbide behind.
Table 6
XRD analysis of solids from pickle flowback

Major: ) 20 wt.%.
Minor: 1 to 20 wt.%.
Trace: 0 to 1 wt.%.
Shaded area shows samples that contained HCl when collected.

The results shown in Fig. 4 also support this hypothesis. If the solids were 100% Fe 3 C, then it can be
calculated that 1500 mgrl of the solids would contain nearly 100 mgrl of carbon. If a flowback
sample contains 25,000 mgrl total iron, then the

K.C. Taylor et al.r Journal of Petroleum Science and Engineering 28 (2000) 3353

43

Table 7
Energy dispersive X-ray spectrometry of solids from pickle flowback concentration, wt.%.

Shaded area shows samples that contained HCl when collected.

percentage of carbon in the iron is 0.4 wt.%. This is

remarkably close to the amount of carbon expected
in low carbon steel, typically 0.4 to 0.5 wt.%. In the
conditions of the casing pickle treatment, it appears
that the iron carbide was not soluble in the acid. It
may have been coated with a non-soluble material or
with biomass.
The chloride concentration in the flowback samples reached a maximum of 132,000 mgrl, com-

pared to a value of 148,000 mgrl in the injected

pickle acid sample Table 5.. This result shows that
dispersion led to a small amount of dilution of the
injected pickle acid. The final chloride concentration
in the pickle flowback samples is the value expected
for seawater.
Values of sulfate, calcium and magnesium in the
flowback samples are shown in Fig. 5. The low
values of calcium during the acid flowback 2.0 to

Fig. 5. Flowback analysis pickle treatment.: sulfate, calcium, and magnesium.

44

K.C. Taylor et al.r Journal of Petroleum Science and Engineering 28 (2000) 3353

2.4 h. show that the acid slug did not contact the
formation. The sulfate concentration 2.0 to 2.4 h. in
the pickle acid increases from 590 to 880 mgrl,
higher than the injected value of 510 mgrl. The
solubility of calcium sulfate gypsum. increases in
aqueous solutions at low pH or high ionic strength
Carlberg and Matthews, 1973.. This indicates that
some sulfate scale is being removed from the casing.
Assuming an initial concentration of 510 mgrl sulfate, and using the well flow rate of 22.3 m3rh 140
bblrh., it was calculated that 3.7 kg of gypsum
CaSO4 P 2H 2 0. was dissolved from the casing. After
2.6 h, the calcium and magnesium levels approached
the values of the formation water that were seen in
Fig. 1. These results show that the flowback time
was sufficient to completely lift the pickle acid from
the wellbore.
In Fig. 6, aluminum concentration and pH are
shown for the flowback fluids. The concentration of
zirconium was also measured and found to be less
than the detection limit of the ICP instrument 1
mgrl.. These measurements were made because both
aluminum and zirconium are present in the cross-linker used in the acid diverting stage. It was necessary
to establish a baseline for aluminum and zirconium
concentrations to evaluate results from the matrix

acid treatment. The presence of aluminum in the

pickle flowback samples probably results from acid
interactions with clay minerals Simon and Anderson, 1990.. The source of these clays is the upstream
sand filters. The clays are deposited on the casing
and leached aluminum ion on contact with the acid.
3.4. Matrix acidization fluid returns
Well A was flowed back for 5 h after the matrix
acidization treatment. The pH values of the produced
fluids are shown in Fig. 7. Values measured at the
wellsite and in the lab were in good agreement. The
high pH values measured at the start of the flowback
are due to sodium carbonate used at the very end of
the treatment to flush out the surface lines. This high
pH fluid did not reach the formation. From Fig. 7, a
minimum pH value was reached at 2.7 h after the
start of the flowback. The pH was above a value of
five for two consecutive samples after 5 h. The
flowback was terminated at this stage, as planned.
The hydrochloric acid concentration of the matrix
acid flowback samples is shown in Fig. 7. A maximum concentration of 1.7 wt.% HCl was reached at
2.88 h after the start of the flowback. The acid
concentration gradually tapered off to zero after 5 h.

Fig. 6. Flowback analysis pickle treatment.: aluminum and pH.

K.C. Taylor et al.r Journal of Petroleum Science and Engineering 28 (2000) 3353

45

Fig. 7. Flowback analysis matrix treatment.: acid concentration and pH.

If the flow rate is estimated to be 22.3 m3rh 140

barrelsrh., the area under the curve can be integrated to show that 1.9 m3 12 barrels. of 15 wt.%
HCl did not react with the formation and was flowed

back from the well. It is likely that this unreacted

acid was in a cavity or washout and was not in direct
contact with the formation. The unreacted acid is
only 1% of the total volume of acid that was in-

Fig. 8. Flowback analysis matrix treatment.: total iron.

46

K.C. Taylor et al.r Journal of Petroleum Science and Engineering 28 (2000) 3353

jected. Increasing the soaking time from 70 min is

not likely to have a large effect on the amount of
unreacted acid.
Iron concentrations in the flowback samples were
measured, Fig. 8. Iron II. was measured at the
wellsite and is compared to total iron measured by
ICP in the lab. The maximum iron concentration of
170 mgrl occurred at 2.5 h and was almost entirely
in the iron II. form. The values of iron II. measured in the field are higher than some of the total
iron measurements made in the lab due to experimental errors sample oxidation.. Using the well
flowrate and the data in Fig. 8, a total of 6 kg of iron
was produced in this stage. No solids were produced
with the samples containing iron. These iron concentrations are relatively low, and since iron II. is the
predominant species, very little iron control chemicals are required. For future treatments in similar
water injection wells, when a pickle treatment is
used, citric acid can be used as the iron control
chemical at a concentration of 0.22 wt.%. This quantity of citric acid is sufficient for iron III. concentrations up to 500 mgrl at temperatures up to 658C
1508F. Taylor et al., 1999a..
The density of the produced fluids was measured
as a function of flowback time. At 2.5 h, the density
rapidly increases then stabilizes near 1.041 grcm3,

indicating that the spent acid begins to flow back at

that point. However, the density then increased to a
maximum of 1.065 grcm3 at 5 h, in contrast to the
density of the seawater 1.044 grcm3 .. At 5 h, the
pH value increased to more than 5 Fig. 7.. It is clear
that the flowback time was not sufficient, and that
the pH value is not effective for determining the
length of the flowback time. Measurement of the
density of the produced fluids should be used to
determine the optimum flowback time.
Chloride and sodium concentrations in the flowback samples are shown in Fig. 9. The mass average
injected chloride concentration was 118,300 mgrl,
based on both the concentrations and relative volumes of the 10 wt.% in situ gelled acid and the 15
wt.% regular acid. The acid that initially flowed back
was diluted with both the low sulfate water chloride
concentration of 370 mgrl. and seawater chloride
concentration of 30,000 mgrl.. This dilution factor
can be calculated, because the sodium concentration
should result only from the injected seawater. The
weight ratio of chloride to sodium in the seawater
was reported as 1.82 to 1, as mentioned previously in
the section on the initial well flowback before acid
treatment..
Fig. 10 shows the results of the calculations that
can be made using the total chloride concentration,

Fig. 9. Flowback analysis matrix treatment.: chloride and sodium.

K.C. Taylor et al.r Journal of Petroleum Science and Engineering 28 (2000) 3353

47

Fig. 10. Flowback analysis matrix treatment.: measured and calculated chloride values.

the sodium concentration, and the measured acid

concentration. The chloride from the live acid decreases from approximately 17,000 to 1800 mgrl.
This is calculated from the measured hydrochloric
acid concentration. At the same time, the chloride
contributed from the seawater increased from 9000
to 26,000 mgrl. The remaining chloride was contributed from the acid that reacted with the formation, which decreases slightly from 6700 to 5600
mgrl. By using the well flowback rate and the
concentration values of chloride that reacted with the
formation, it can be calculated that less than 7% of
the injected acid was produced. The same technique
could be used on calcium and magnesium to calculate the amount of dolomite that reacted with the
acid Dahlan and Nasr-El-Din, 2000.. For Well A,
however, insufficient spent acid was produced for
these calculations. This occurred because pH was
used to determine the amount of time the well should
flow back after the treatment. The flowback time
should be increased and the optimum time determined using a portable density meter.
The acid flowing back from the well was significantly diluted Fig. 11.. At 2.70 h when acid first
flowed back from the well, it had been diluted to
20% of the injected concentration a dilution factor

of five. by mixing with injected seawater and the

overflush. By 4.1 h, the produced acid was at 6%, a
dilution factor of 17. When the fluids flowed back,
they were a mixture of spent and live acids. Fig. 11
also shows how much of the acid produced from the
formation did not react with it. Initially, 70% of the
acid was unreacted and that amount decreased to
25% by 4.1 h. At 4.1 h, the acid was extremely
diluted by a factor of 17. and 25% of this acid had
not reacted with the formation. This agrees with well
logs that show a large washout zone or cavity is
present in the well below the casing shoe. This
washout zone, at the top of the openhole section,
occurs in a zone that contains anhydrite. The large
volume of this washout can act as a mixing container
for acid and spent acid flowing back from the formation. If unreacted acid remains in the washout zone
at the end of injection, then it will gradually mix
with spent acid flowing up the casing as the well is
flowed back.
As the spent acid flowed back from the well, it
was produced with seawater, the post-flush and the
pre-flush. The proportion of low sulfate water decreased and the proportion of seawater increased
with time Fig. 11.. At 2.7 h after flowback, when
the acid and spent acid production began, seawater

48

K.C. Taylor et al.r Journal of Petroleum Science and Engineering 28 (2000) 3353

Fig. 11. Matrix flowback composition.

already made up 30% of the total produced fluids.

By 4.1 h, nearly 90% of the total fluids produced
was seawater.
Finally, Fig. 11 shows the percentage of chloride
from spent acid in the flowback samples. These
values decrease from 25% to approximately 15%,
and show that a relatively constant amount of spent

acid was produced, although the amount of unreacted

acid was decreasing rapidly. This may mean that the
spent acid was produced from a different zone or
zones than the live acid.
Fig. 12 shows the concentrations of sulfate, magnesium and calcium in the fluid returns. The calcium
concentration is close to the expected value from the

Fig. 12. Flowback analysis matrix treatment.: sulfate, magnesium and calcium.

K.C. Taylor et al.r Journal of Petroleum Science and Engineering 28 (2000) 3353

amount of spent acid calculated in Fig. 11, for the

period 2.7 to 4 h. After that, the calcium concentration increases, indicating that a larger amount of
spent acid is being produced. However, a calcium
concentration of approximately 80,000 mgrl results
when 15 wt.% HCl completely reacts with limestone.
This shows that the spent acid flowing back from the
well was highly diluted. Magnesium concentration is
near 2200 mgrl, as compared to a value of 2000
mgrl in the seawater. Some magnesium is probably
present in the formation in the form of dolomite. A
large amount of sulfate is seen in the flowback
samples. The peak values of 5000 to 6000 mgrl are
similar to those observed in the flowback samples
before acid treatment. shown in Fig. 1. Sulfate
values fluctuate at 4 h and later, because precipitation of gypsum CaSO4 P 2H 2 O. occurred due to the
high calcium levels in these samples. Gypsum was
identified by XRD analysis as the major component
Table 6.. These results show that calcium sulfate
has a limited solubility in the flowback samples.
Once the solubility limit is exceeded, precipitation of
gypsum occurs.
The solubility of gypsum in seawater with a 3
wt.% chloride content. at 258C is 0.458 wt.%
Silcock, 1979.. This corresponds to a calcium con-

49

centration of 1060 mgrl and a sulfate concentration

of 2540 mgrl. The concentrations of calcium and
sulfate in the spent acid in Fig. 12 are both significantly higher than these values. The calcium concentration is approximately 7000 mgrl and the sulfate
concentration is approximately 4000 mgrl. Either
the samples are not at equilibrium with respect to
gypsum, or additives in the acid stimulation fluids
increase the solubility of gypsum in seawater. It is
known that partially hydrolyzed polyacrylamides and
polyacrylic acids are used as calcium scale inhibitors
Przybylinski, 1989.. The 10 wt.% in situ gelled acid
contained an acrylamide copolymer and may inhibit
gypsum precipitation.
Zirconium and aluminum concentrations in the
flowback samples are shown in Fig. 13. The concentrations of these metals were measured because they
are present in the in situ gelled acid that was injected
into the reservoir. Both zirconium and aluminum
were produced during the flowback time 2.7 to 4 h.
After 4 h, aluminum was present in the samples but
zirconium concentrations were below the detection
limit of 1 mgrl. From 2.7 to 4 h, a significant
amount of unspent acid flowed back from the well
Fig. 11., accounting for the produced zirconium.
After 4 h, the produced fluids contained only seawa-

Fig. 13. Flowback analysis matrix treatment.: zirconium and aluminum.

50

K.C. Taylor et al.r Journal of Petroleum Science and Engineering 28 (2000) 3353

ter and spent acid. These results indicate that zirconium may precipitate or adsorb in the formation.
Work is underway to determine the rate of propagation of zirconium and aluminum in the formation.

acetic acid reduced the treatment cost by more than

15%.

3.5. Treatment ealuation

In the treatment design, alternate stages of regular

15% HCl acid and 10% in situ gelled HCl were
bullheaded. The objective of this staged process was
to provide effective acid diversion during the stimulation treatment. In situ gelled acid can be used to
stimulate carbonate reservoirs that have significant
permeability contrast. Basically, these acids consist
of an acid-soluble polymer, a pH buffer, a cross-linker and a breaker. The polymer in this system forms
a gel within a narrow pH range. As a result of gel
formation, the viscosity of the acid increases in situ
and acid diversion can be achieved. Ultimately, the
gelled acid will form wormholes evenly distributed
over the entire target zone. This gel will improve
acid placement and control acid fluid loss Yeager
and Shuchart, 1997; McGee et al., 1997..
When hydrochloric acid is injected into the formation, it has a pH of nearly zero. The pH of the acid
increases as the acid reacts with the carbonate rock.
At a pH value of approximately 2 to 4, the polymer
reacts with the cross-linker and forms a very viscous
gel. This reaction is reversible, but is dominant at
this pH range. The viscosity of the acid can reach
1000 cP Yeager and Shuchart, 1997. and is able to
divert unreacted acid further into the well bore. As
the acid continues its reaction, the pH will rise
further. At pH values greater than 4 to 5, the viscosity of the gel decreases as the polymer and cross-linker dissociate. A breaker is used in some types of
gelled acid to ensure a complete reversal of the
cross-linking process Yeager and Shuchart, 1997..
The reduced viscosity of the spent acid is designed
to improve its removal from the formation.
In the treatment design, maximum pumping rate
was to be achieved while holding pressure constant
below wellhead maximum pressure 17.2 MPa 2500
psi.. and formation fracture pressure. The significant
parameters to be evaluated are pumping rate and
volume of the injected fluids.
During the pre-flush stage, the pressure steadily
climbed to 15.9 MPa 2300 psi. Fig. 14.. During
this time, the average injection rate of 3.3 m3rmin
20.7 bpm. was maintained Fig. 15.. Upon switch-

Before the acid stimulation treatment, the injectivity index II. of the well was 0.12 m3rdayrkPa 5
bblrdayrpsi.. This value increased to 0.21 m3r
dayrkPa 9 bblrdayrpsi. after the treatment, an
increase of 75%. Flowmeter results could not be
obtained because of the large washout present directly below the casing shoe. However, it is likely
that a significant percentage of the flow into the
formation is into the region identified in the 1993
injection profile 2228 to 2256 m 7310 to 7400 ft...
The injectivity of the well may have declined as a
result of particulates carried into the well by the 5.6
million m3 35 million barrels. of seawater that have
been injected to June, 1999. These particulates contain significant amounts of acid-insoluble material.
This includes the iron carbide identified during the
pickle treatment and in previous sampling at the
seawater treatment plant. Other acid insoluble particulates include fine sand particles and clay minerals.
3.6. The importance of pickling the casing
Return samples from the pickle treatment contained up to 15,000 mgrl of iron III. and up to
1500 mgrl of suspended solids. The maximum practical amount of iron III. that can be complexed is
10,000 mgrl Taylor et al., 1999a.. This requires 12
kgrm3 of citric acid and 22 lrm3 of acetic acid Dill
and Smolarchuk, 1988.. At higher concentrations of
citric acid, precipitation of calcium citrate may occur. When the casing is pickled, a citric acid concentration of 2.4 kgrm3 in the main acid treatment is
sufficient to prevent precipitation of iron III. hydroxide in the near-wellbore region. The pickle treatment also prevents the injection of acid-insoluble
casing scale into the formation. The cost of the
pickle treatment itself was very small compared to
the chemical cost of the treatment. For a 37.9 m3
10,000 gal. matrix acid stimulation, using a pickle
treatment and reducing the amount of citric acid and

3.7. Acid diersion

K.C. Taylor et al.r Journal of Petroleum Science and Engineering 28 (2000) 3353

51

Fig. 14. Surface pressure and bottom hole pressure as a function of time.

ing to the acid, the rate was reduced to 1.4 m3rmin

8.8 bpm. to facilitate switching between the low
volume stages. The rate was then increased to 2.0
m3rmin 12.8 bpm, but was limited by the surface
pressure.

As the first stage of acid reached the formation,

the injection rate increased to maintain a constant
surface pressure. The rate increases from 2.0 to 3.3
m3rmin 12.8 to 21 bpm. while the treating pressure
remained constant. This indicates that as the acid

Fig. 15. Injection rate and cumulative injection as a function of time.

52

K.C. Taylor et al.r Journal of Petroleum Science and Engineering 28 (2000) 3353

reached the formation, injectivity increased. As injection of the acid continued, the injection rate decreased until the post-flush reached the formation.
This shows that diversion was occurring during acid
injection. After 83 min, the injection rate increased
as the post-flush was injected into the formation.

work. The Chemistry Unit and Advanced Instruments Unit of Saudi Aramco provided valuable assistance with this work. The authors thank M. AlRamadhan, Dr. H.R. Rosser and G. Polkowski for
useful discussions.

4. Summary

References

Techniques were demonstrated to evaluate acid

stimulation treatments based on chemical analysis of
the return fluids. These techniques were used in Well
A to identify the source of formation damage, the
amount and type of scale on the casing, and the
efficiency of the acid treatment.
1. During flowback of the well before the pickle
treatment., 125 kg of calcium sulfate dissolved
from the near-wellbore area.
2. The pickle treatment was highly effective, dissolving an estimated 235 kg of iron from tubular
corrosion products.
3. The pickle fluid returns contained black suspended solids that were mostly iron carbide, Fe 3 C.
4. For the pickle treatment, the acid volume 0.29
galrft, 0.36 lrm. and the flowback time 4 h.
were sufficient.
5. The iron control chemical concentration can be
reduced for similar low temperature water injection wells that are pickled before acid stimulation.
Citric acid at 0.22 wt.% 20 lbr1000 gal of 15
wt.% HCl. is sufficient to keep 500 mgrl iron
III. in solution.
6. When it flowed back from the well, the injected
acid was diluted between 5 and 17 times based on
calculations using the chloride concentration as a
tracer.
7. The pH value of the flowback fluid is not an
adequate criterion to determine the flowback time.
The density of the aqueous phase should be used
instead.

Acknowledgements
The authors thank the Saudi Arabian Oil Company Saudi Aramco. for permission to publish this

Allaga, D.A., Wu, G., Sharma, M.M., Lake, L.W., 1992. Barium
and calcium sulfate precipitation and migration inside sandpacks. SPE Formation Evaluation, March.. pp. 7986.
Almond, S.W., Brady, J.L., Underdown, D.R., 1990. Return fluid
analysis from the Sadlerochit formation, Prudhoe Bay, AK:
FIeld study Part 1. SPE 18223, 63rd Ann. Tech. Conf.,
Houston, TX, USA.
Bayona, H.J., 1993. A review of well injectivity performance in
Saudi Arabias Ghawar field seawater injection program. SPE
25531, SPE Middle East Oil Tech, Conf., Manama, Bahrain.
Brown, J.S., Dubrevil, L.R., Schneider, R.D., 1979. Seawater
project in Saudi Arabia early experience of plant operation,
water quality and effect on injection well performance. SPE
7763, Middle East Oil Tech. Conf., Manama, Bahrain.
Carlberg, B.L., Matthews, R.R., 1973. Solubility of calcium sulfate in brine, SPE 4353, SPE Oilfield Chemistry Symp.,
Denver, CO, USA.
Chen, E.Y., Ahmed, T., 1998. Why internally coated piping is
used for the worlds largest seawater injection system. SPE
49211, SPE Annual Tech. Conf., New Orleans, LA, USA.
Coburn, S.K. Ed.., Corrosion Source Book. American Society for
Metals, Metals Park, OH, pp. 1213.
Cowan, J.C., Weintritt, D.J., 1976. Water-Formed Scale Deposits.
Gulf Publishing, Houston, TX, p. 68.
Cron, C.J., Payer, J.H., Staehle, R.W., 1971. Dissolution behavior
of Fe-Fe 3 structure as a function of pH, potential, and anion
an electron microscopic study. Corrosion 27, 1.
Crowe, C.W., 1985. Evaluation of agents for preventing precipitation of ferric hydroxide from spent treating acid. J. Pet.
Technol. 37 4., 691.
Dahlan, M.N., Nasr-El-Din, H.A., 2000. A new technique to
evaluate matrix acid treatments in carbonate reservoirs, SPE
58714, International Symposium on Formation Damage Control, Lafayette, LA.
Dill, W., Smolarchuk, P., 1988. Iron control in fracturing and
acidizing operations. J. Can. Pet. Technol. 27 3., 7578.
Dugstad, A., Hemmer, H., Seiersten, M., 2000. Effect of steel
microstructure upon corrosion rate and protective iron carbonate film formation. Paper 00024, Proceedings Corrosion 2000,
NACE, Houston, TX.
Gdanski, R.D., Peavy, M.A., 1986. Well return analysis causes
re-evaluation of HCl theories, SPE 14825, 7th SPE Symp. on
Formation Damage Control, Lafayette, LA, USA.
Ginest, N.H., Phillips, J.E., Al-Gamber, A.W.A., Wright, D.W.,
1993. Field evaluation of acid stimulation diverter materials
and placement methods in Arab-D injection wells with open-

K.C. Taylor et al.r Journal of Petroleum Science and Engineering 28 (2000) 3353
hole completions. SPE 25412, SPE Middle East Tech. Conf.,
Manama, Bahrain.
Gougler, P.D. Jr., Hendrick, J.E., Coulter, A.W., 1985. Field
investigation identifies source and magnitude of iron problems, SPE 13812, SPE Production Operations Symp., Oklahoma City, OK, USA.
Kaesche, H., 1985. Metallic Corrosion. National Association of
Corrosion Engineers, Houston, TX, p. 7.
Lee, W., Lewandowski, Z., Nielsen, P.H., Hamilton, W.A., 1995.
Role of sulfate-reducing bacteria in corrosion of mild steel: a
review. Biofouling 8, 165194.
Little, B.J., Ray, R.I., Pope, R.K., 2000. The relationship between
corrosion and the biological sulfur cycle. Paper 00394, Proceedings Corrosion 2000, NACE, Houston, TX.
Loewen, K., Chan, K.S., Fraser, M., Leuty, B., 1990. A well
stimulation acid tube clean methodology. CIMrSPE 90-47,
Petroleum Society of CIMrSPE International Tech. Meeting,
June 10 to 13, Calgary, Canada, Preprints, vol. 1.
McGee, J., Buijse, M.A., Pongratz, R., 1997. Method for effective
fluid diversion when performing a matrix acid stimulation in
carbonate formations, SPE 37736, Middle East Oil Show,
Bahrain, 1518 March.
Mohamed, S.K., Nasr-El-Din, H.A., Al-Furaidan, Y.A., 1999.
Acid stimulation of power water injectors and saltwater disposal wells in a carbonate reservoir in Saudi Arabia: laboratory testing and field results. SPE 56533, SPE Annual Technical Meeting, Houston, TX. pp. 36.
Nasr-El-Din, H.A., Rosser, H.R., Hopkins, J.A., 1996. Stimulation
of injection water supply wells in central Arabia. SPE 36181,
7th ADIPEC, Abu Dhabi, UAE. pp. 1316.
Nasr-El-Din, H.A., Al-Anazi, H.A., Mohamed, S.K., 1999. Stimulation of water disposal wells using acid-in-diesel emulsion:

53

case histories, SPE 50739, SPE International Symposium on

Oilfield Chemistry, Houston, TX, USA.
Patton, C.C., 1993. Corrosion control in water injection systems.
Mater. Perform. 32 8., 4649.
Przybylinski, J.L., 1989. Adsorption and desorption characteristics
of mineral scale inhibitors as related to the design of squeeze
treatments, SPE 18486, SPE International Symposium on Oilfield Chemistry, Houston, TX, USA.
Shuchart, C.E., 1995. HF acidizing returns analyses provide understanding of HF reactions, SPE 30099, SPE European Formation Damage Control, The Hague, The Netherlands.
Silcock, H.L. Ed.., Solubilities of Inorganic and Organic Compounds vol. 3 Pergamon, New York, USA, pp. 754755.
Simon, D.E., Anderson, M.S., 1990. Stability of clay minerals in
acid, SPE 19422, SPE Formation Damage Control Symposium, Lafayette, LA, USA. .
Smith, C.F., Crowe, C.W., Nolan, T.J. III, 1969. Secondary
deposition of iron compounds following acidizing treatments.
J. Pet. Technol., 1121, September.
Taylor, K.C., Nasr-El-Din, H.A., 1999. A systematic study of iron
control chemicals part 2, SPE 50772, SPE International Symposium on Oilfield Chemistry, Houston, TX, USA.
Taylor, K.C., Nasr-El-Din, H.A., Al-Alawi, M.J., 1999a. Systematic study of iron control chemicals used during well stimulation. SPE J. 4 1., 1924.
Taylor, K.C., Nasr-El-Din, H.A., Al-Alawi, M.J., 1999b. Field
test measures amount and type of iron in spent acids, SPE
50780, SPE International Symp. on Oilfield Chemistry, Houston, TX, USA.
Yeager, V., Shuchart, C., 1997. In situ gels improve formation
acidizing. Oil Gas J., 70, Jan. 20.