w’ m
. .
SPE 39418
Stimulation of Tight Carbonate Reservoirs Using Acid-in-Diesel Emulsions: Field
Application
H.A: A1-Anazi, SPE, H.A. Nasr-El-Din, SPE, and S.K. Mohamed, Saudi Arabian Oil Company (Saudi Aramco)
-right 1S9S,%iafy et Petroleum Enginaar$, Inc.
7hii papar was prepati fw praaantatlon at the 199S SPE IntematMal Sym~slum on
Forma~m Damage Mtrol haid h Lafayette, Louisiana, 1.9-19 February 19S3.
7hia -r was aelaotad for presentation by an SPE Program Cmmittae foltowing review of
information retained in an abatrad submitted ~ the author(s). Cw!enta of fha pepar, as
preaantd, hsvs not bean rav~wad by the *kty of Petroleum Englnaara end are subjast to
corraion ty the author(s). ~ material, as presented, tis not nacasaerfw rafleot any
poslfkm of the _ty of Patrobum Enginaara, tfs officers, w members. Papers pramtad at
SPE meetings are subject to publioatlon review @ Edfforial Committees oi the Society &
Petrtium Engineers. Ektronic rapr.xfuotlon, dlstribut~, or atoraga of any wrf of this paper
for sommercielpurpoaaa without the written cw$ant of Iha %iaty of Petroleum Enghwrs Is
pr~lbtiad. Permisslm to raprcduoe in print Is restrkted to an abstraof ef not more then 20J
wordq Illustratlari may not ba cqIiad. 7ha abstract must sontain mnsplcuous
acknowkrdgmentof whare snd by wh tha paper was presented. Write Librerien, SPE, P.O.
%X 83W3S, Richardew, 7X 7S0S3-3S3S,US.A, fax 01-972-9S2.9435.
Abstract
An oil producing well (WeI1-A) in a carbonate reservoir was
dead due to severe formation damage. The well was acidized
by regular 15 wt% HC1, but remained dead. A thorough
experimental study was conducted to evaluate using acid-in-
diesel emulsions, 70 vol% HC1 (15 wt%):30 vol% diesel, to
stimulate this well which had several tight zones.
Experimental results indicated that the acid-in-diesel
emulsion was a viscous and non-Newtonian fluid. The
thermal stability of the acid decreased as temperature was
increased. The stability of emulsified acid also decreased in
the presence of reservoir rock. The emulsified acid was found
to be compatible with native crude oil and acid additives,
except mutual solvents and demulsifiers. The reactivity of the
emulsified acid with reservoir reek was slower than that of
the 15 wt% HC1 by a factor of 45 at 24 ‘C. The reaction rate
of the emulsified acid increased as temperature was increased.
Coreflood results showed that the emulsified acid formed
deep wormholes in tight carbonate cores (< 50 red). At the
same acid volume and flow rate, the emulsified acid
penetrated deeper into the core compared to the regular acid
which caused face dissolution. Permeability ratio
(final/initial) of reservoir cores exponentially increased with
the acid injection rate. The size and number of the worrnholes
depended on the acid injection rate.
The acid-in-diesel was successfully applied in Well-A using
a coiled tubing unit, whereby the well productivity has been
increased by several orders of magnitude. After the treatment,
a flowmeter test indicated that the percentage production of
tight zones has increased by a factor of 2,
9
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Society of Petroleum Engineers
Introduction
Acidizing is used to remove wellbore damage or enhance
matrix permeability. The acid reacts within the rock’s pore
and, as a result, formation permeability near the wellbore will
be increased by removing damaging materials. Acids
commonly used to acidize carbonate reservoirs are
hydrwhloric, formic, and acetic acids. Recently, Fredd and
Fogler]’2 introduced ethylenediaminetetraacetic acid (EDTA)
to be used as an alternative fluid to acidize carbonate
formations.
The reaction rate of HCI acid with calcite is very fast.3’4In
conventional stimulation when 15 wtYo HCI is used at low
flow rates, the acid reacts with carbonate rocks and causes a
face dissolution or surface wash-out.5 This means that the
acid is spent on the formation surface and cannot penetrate
the damaged zone. to enhance the formation permeability.
Face dissolution leads to consumption of large volumes of
acid.2 One way to overcome this problem is to use acid-in-
diesel emulsions’ This emulsion consists of diesel
(continuous phase), HC1 acid (dispersed phase), and an
emulsifier. The role of using diesel is to act as a diffusion
barrier between the acid and the reek. 8-10Thus, the reaction
rate of the acid with carbonate rocks becomes slower. This
gives the acid the ability to penetrate deeper into the
formation by creating wormholes (i.e. channels with high
permeability) and enhances well productivity.l 1-14~
A regular acid 15 wt% HC1 was used to acidize a well in a
carbonate formation. However, the results were below
expectations. The objectives of this study were to: (1)
determine theological properties of acid-in-diesel emulsions,
(2) measure thermal stability of the emulsified acids at
reservoir temperature, (3) study emulsified acid propagation
into tight (e 50 md) carbonate reservoir cores, and (4) design
stimulation treatment using acid-in-diesel emulsions to
improve oil production from tight zones in carbonate
reservoirs in Saudi Arabia.
Experiment Studies
The acid-in-diesel emulsion was prepared according to the
acid formula given in Table 1. The volume ratio of HC1 (15
wt%) acid to diesel was 70:30. Diesel was mixed with the
,. .—-
I 2 H.A. AL-ANAZI, H.A. NASR-EL-DIN, S.K. MOHAMED
emulsifier (a cationic surfactant) into a Waring blender at a
medium speed, while a corrosion inhibitor, a chelating agent
(EDTA), and a reducing agent (sodium erythorbate) were
mixed with 15 wt% HCI acid in a separate beaker. The acid
was gently added to diesel in the blender. Then, the two
phases were mixed in the blender for 10 minutes at a high
speed.
The acid-in-diesel emulsion was evaluated for field
application. Experimental tests included rheology, thermal
stability, compatibility, reactivity with reservoir rocks, and
coreflood experiments. The apparent viscosity of the acid-in-
diesel emulsion was measured as a function of shear rate at
various temperatures by using a Brookfield viscometer Model
DV-11. To conduct thermal stability tests, acid-in-diesel
emulsion was prepared in 100 ml graduated cylinder and
placed in an oil bath at 96 “C (reservoir temperature). The
volume of separated acid was monitored as a function of time.
A second test was conducted in the presence of a piece of
reservoir rock (22. 1 g in 40 cm3 emulsified acid) to simulate
acid/rock interactions in the reservoir. Temperature of the
acid-in-diesel emulsion was also recorded as a function of
time.
Compatibility of the acid-in-diesel emulsion with formation
brine, native oil, and regular 15 wt% HC1 acid mixed with
additives, such as corrosion inhibitors, chelating agents, and
reducing agents was examined. Formation brine was
synthesized according to the composition listed in Table 2.
The acid-in-diesel emulsion was mixed with each of the
previous fluids at a volume ratio of 1:1.
The acid-in-diesel emulsion was examined under an optical
microscope ~ikon Microphot EPI-FL3) using a phase
contrast technique and the drop size distribution of the
dispersed phase was determined.
The reaction rate (dissolving power) of the acid-in-diesel
emulsion was compared with that of a regular 15 wt~o HC1
acid at 24”C. Reservoir rocks were cut into cylindrical slices
of 1.5” diameter and 0.3” thickness. The rock slices were
placed in tested acids and their weight loss was monitored as
a function of time. More details on this method are given in
Ref. 13. The effect of temperature on the reaction rate of the
acid-in-diesel emulsion with reservoir rock was also
investigated using the above method.
Several coreflood experiments were performed on reservoir
cores at reservoir conditions (T = 96 ‘C and overburden
pressure = 2,500 psig). In each experiment, the core was first
saturated with the formation brine under vacuum. Either
brine or dead crude oil was injected until the core
I permeability became constant (+ 10%). Then, the acid was
injected and followed by the formation brine or oil as a
postflush. A new core sample was used in each experiment.
The effect of injection flow rate on acid propagation was
studied over the range of 0.5-12.0 cm3/min.
X-ray Powder Diffraction (XRD) analysis was used to
determine the mineralogy of reservoir cores. The
10
. ....”..
— ., —. ,.=—
SPE 39418
concentrations of key ions in the core effluent were measured.
Calcium, magnesium, and total iron ions were analyzed by
Induced Coupled Plasma Emission Spectrometry (ICP).
Chloride ion was measured by titration using a 0.1 N silver
nitrate solution. A few drops of potassium chromate were
added as an indicator. The concentration of hydrochloric acid
was measured by acid/base titration using a 0.1 N NaOH
solution.
Results and Discussion
Fig. 1 shows the apparent viscosity of the acid-in-diesel
emulsion as a function of shear rate at various temperatures.
The apparent viscosity decreased as the shear rate was
increased. This result indicates that the acid-in-diesel
emulsion is a non-Newtonian fluid (shear-thinning behavior).
This behavior is in agreement with the results obtained in
Refs. 6 and 15. The apparent viscosity (q) can be predicted
over the shear rate (Y) examined using the power-law model
given by the following equation:
q = k(~)n-l .............................................................(l)
Table 3 gives the power-law model parameters (n and k) at
various temperatures. This model gave good predictions
(straight lines shown in Fig. 1) for the apparent viscosity, The
model parameters are needed to calculate the pressure
required to pump this emulsion. The power-law index (n)
increased as the temperature was increased. As a result, the
emulsified acid approached Newtonian behavior at higher
temperatures. The apparent viscosity of the acid-in-diesel
emulsion could not be measured at temperatures > 45 “C
using this technique. This was most likely due to the shear
process which changed the droplet size distribution of the
emulsion.
The stability of the acid-in-diesel emulsion plays an
important role in field application. If the acid separated from
the emulsion before it reaches the formation, it will not b
retarded. Therefore, it is very important to make sure that the
emulsion reaches the formation without phase separation. The
acid-in-diesel emulsion was stable for more than 72 hours at
room temperature. However, emulsion stability decreased as
the temperature was increased. Fig. 2 depicts the volume of
the separated acid as a function of time at 96 “C. The
temperature of the acid-in-diesel emulsion was also
monitored during the test. The acid-in-diesel emulsion
temperature increased and reached the desired temperature
(96 “C) within 20 minutes.
The acid phase started to separate from the emulsion after
85 minutes. Then, the volume of acid separated gradually
increased until complete phase separation occurred after 219
minutes. In the presence of reservoir rock, the acid started to
separate after 21 minutes, and complete phase separation took
place after 58 minutes. During acid reaction with carbonate
rock, water is produced and the pH rises. Thus, this fast
separation was due to the rise in pH which affects the
 SPE 39418 STIMULATION OF TIGHT CARBONATE RESERVOIRS
concentration of the emulsifier (cationic surfactant) at the
acid/diesel interfaces These results indicate that a minimum
time of an hour is needed to soak the acid-in-diesel emulsion
into the formation to achieve complete acid/rock reaction. It
should be also noted that the emulsion should be stable for a
period of time long enough to inject the acid into the
formation. From the thermal stability tests, it was found that
the acid-in-diesel emulsion was stable for 85 minutes, which
was sufficient for field application of Well-A, as will b
discussed later.
The acid-in-diesel emulsion was examined under the
microscope and the drop size distribution of the dispersed
phase was determined using a phase contrast technique. Fig.
3 is a photomicrograph (x250) of the acid-in-diesel emulsion.
The average droplet size for the acid-in-diesel emulsion was
found to be 77 pm. When the acid-in-diesel emulsion was
mixed with each of 15 wt% HCI and oil, the average droplet
size decreased to 9.06 and 1.65 pm, respectively. This
decrease in the droplet size of the emulsified acid indicates
that a preflush of HC1 or hydrocarbon will improve the
infectivity of the emulsified acid, if the formation is severely
damaged. Droplet size could not be measured after mixing the
acid-in-diesel emulsion with the formation brine, where the
emulsion was broken due to change in the pH.
The acid-in-diesel emulsion was found to be compatible
with crude oil and acid additives which were initially mixed
with the HC1 acid, However, adding of mutual solvents or
demulsifiers to the acid-in-diesel emulsion broke the
emulsion instantaneously. Therefore, mutual solvents and/or
demulsifiers should not be added in the preflush, without
using a spacer.
Fig. 4 compares the weight loss of reservoir rocks by the
acid-in-diesel emulsion and 15 wt% HC1 at 24 “C. The 15
wtYo HCI dissolved 90 wt% of the reservoir rock after 6
I minutes. However, the weight loss obtained when the
reservoir rock slice was immersed in the acid-in-diesel
emulsion was 2 wt~o after the same period of time. This result
indicated that the reaction rate of the emulsified acid was
slower than that of the 15 wt% HC1 by a factor of 45.
Fig. 5 depicts the weight loss of reservoir rocks by the acid-
in-diesel emulsion at various temperatures ranged from 24 to
96 “C, The weight loss increased as the temperature was
increased, Therefore, the reaction rate of the acid-in-diesel
emulsion with reservoir rocks increased as the temperature
was increased. As mentioned earlier, the viscosity of the
emulsified acid decreased as the temperature was increased.
Accordingly, the decrease in the emulsified acid’s viscosity
enhanced the diffusion rate which exposed the rock surface to
the acid,
Coreflood experiments were conducted to determine acid
infectivity/propagation in reservoir cores at 96 ‘C. XRD
analysis indicated that the reservoir cores were calcite. Fig. 6
shows the calcium ion concentration in the core effluent for
two coreflood experiments where one pore volume (PV) of
11
USING ACID-IN-DIESEL EMULSIONS: FIELD APPLICATION 3
each 15 wt% HCI or acid-in-diesel emulsion was injected into
different cores at a flow rate of 0.5 cm3/min. Calcium ion
concentration reached a maximum value of 57,000 mgfl when
the 15 wt% HC1 acid was injected, then dropped to a constant
value of 16,300 mg/1 which was close to the calcium content
in the formation brine (Table 2). However, the calcium
concentration in the core effluent reached a maximum of
28,500 mg/1 when the acid-in-diesel emulsion was injected.
This value was 50% of the maximum calcium concentration
leached from the core by the regular acid. Also, it was noted
that the calcium concentration peak was delayed when the
acid-in-diesel emulsion was injected. This delay indicated
that the propagation of the acid-in-diesel emulsion in the core
was slower than that of the regular HCI acid.
Fig. 7 depicts the concentration of HCI acid in the core
effluent at a flow rate of 0.5 cm3/min, When the 15 W% HC1
acid was used, there was no HCI recovered in the core
effluent. In other words, the acid was totally spent on the
core. On the other hand, low HCI concentrations were
obtained in the core effluent in the case of the acid-in-diesel
emulsion. This result indicated that the acid-in-diesel
emulsion penetrated deeper into the formation than did
regular HCI acid.
Core permeability was determined before, ~, and after
acid injection, K, by using Darcy’s law for linear flow.
Permeability ratio, K,, was also calculated as a function of the
cumulative core effluent using the following equation:
K
K = — ...........................................................................(2)
K.
Fig. 8 displays the permeability ratio as a function of the
cumulative core effluent at a flow rate of 0.5 cm3/min. ‘fhe acid-
in-diwl emulsion increased the core (& = 7.2 md) permeability
by 9-fold, while the 15 W% HCI acid increased the permeability
of the core (& = 46,9 md) by a factor of 2. It was also observed
that the HC1acid formed shallow etching (face dissolution), while
the emulsified acid created dmp wormholes. This result
contirrned that the acid-in-diesel emulsion was more effective
than the regular acid in enhancing the matrix permeability which
led to higher productivity improvement.
Fig. 9 shows the calcium ion concentration in the core
effluent at injection flow rates of 0.5 and 3.0 cm3/min using
the acid-in-diesel emulsion at 96 ‘C. At an injection flow rate
of 3.0 cm3/min, calcium concentration reached a maximum
value of 39,000 mg/1 which was higher that that obtained at
0.5 cm3/min by 40%.
It was also noted that the number of wormholes was
directly proportional to the acid injection rate, At 0.5
cm3/min, a single wormhole was observed. The diameters at
the inlet and the outlet faces of the core were 2.8 and 0.94
mm, respectively. However, the wormhole diameter in the
inlet and the outlet faces of the core increased to 3.4 and 1.9
mm, respectively, at an injection flow rate of 3.0 cm3/min. It
was also noted that 9 other small diameters wormholes were
4 H.A. AL-ANAZI, H.A. NASR-EL-DIN, S.K. MOHAMED
formed on the inlet face of the core, but they did not break
through the core.
At a higher flow rate of 3.0 cm3/min, the maximum HCI
concentration in the core effluent was higher than that
obtained at 0.5 cm3/min as illustrated in Fig. 10. Another set
of coreflood experiments was performed on different reservoir
cores, but the flow rate was changed in the range of 0.5-12.0
cm3/min. Fig. 11 shows the permeability ratio as a function of
injection flow rate. For brine saturated cores, the final core
permeability exponentially increased with the acid injection
rate. For instance, the final permeability improved by more
than 600-fold at 12 cm3/min, The same-trend was observed in
the case of oil saturated cores. Also, increasing the flow rate
increased the number of wormholes which enhanced the core
permeability (Fig. 12).
The above results indicated that increasing the flow rate
will increase the convective mass transfer which leads to
faster propagation of the emulsified acid in the core. Higher
flow rates resulted in deeper penetration than that performed
at lower rates. Therefore, it is rmommended to inject the
acid-in-diesel emulsion at the highest possible injection flow
rate, below fracture pressure, to achieve better permeability
enhancement,
Field Application
Well-A was drilled in a carbonate reservoir as an open hole
oil producer in May of 1973. The formation is divided into
four main zones; 1, 2 (A&B), 3 (A&B), and 4. The depth of
each zone is given in Table 4. Zone 2 is the main productive
zone, while fines 3 and 4 are tight carbonate zones. The
second workover operations were completed in February of
1995 to isolate a high permeability interval at the top of Zone
2B which increased water production. Following the
workover, a total of 50 ft were perforated in Zones 2B and
3(A&B). The perforated intervals were acidized with 3,000
gallons of 15 wt~o HC1 using a coiled tubing (CT) unit.
However, the well did not sustain flow to the gas-oil
separation plant, In July of 1995, 15 ft interval of perforations
was added in Zone 2A. Nevertheless, these additional
perforations did not liven the well which remained dead.
After different diagnostic work, it was decided to stimulate
Zones 2A and 3 (A&B) using an emulsified acid, while
isolating the perforated interval of Zone 2B by a temporary
plugging gel. The acid-in-diesel emulsion was selected to
improve the permeability of the formation, The treatment
consisted of three main stages. Table 5 lists the composition
of fluids used in the treatment. All fluids were prepared in a
low-sulfate content water with a total dissolved solids of
2,800 mg/1. In the first stage, the temporary gel was used to
isolate Zone 2B at 6,627-6,710 ft interval which is producing
water and oil simultaneously. The hydrostatic head in the
coiled tubing was adjusted to avoid gel movement, while
waiting for the gel to set. The well was shut in for a period of
2 hours which was needed for the gel to set. The perforated
12
SPE 39418
interval below the gel plug was acidized in the second stage
by pumping 15 bbls of 15 wt% HCI, 69 bbls of acid-in-diesel
emulsion followed by 12 bbls of gelled acid, while
reciprocating the CT across the interval (6,710-6,818 ft). The
gelled acid was used for better acid diversion. It was injected
into the bottom zone to minimize the downward movement of
the gel plug, while acidizing the interval above the gel plug.
However, the upward movement of the gel was mitigated by
pumping diesel down in the CT-tubing annulus to control the
differential pressure across the plug, while acidizing the
intervals below. In the third stage, the interval above the gel
plug was acidized with 8 bbls of 15 wt% HC1 acid followed by
36 bbls of emulsified acid. The acid was displaced with diesel
and the CT was reciprocated through the interval (6,627-
6,710 ft) isolated by the gel plug while pumping diesel to
clean out the temporary gel. Table 6 gives pumping stages of
Well-A. Nitrogen lift was used to clean up the well, while
flowing to the flare pit. After 2 hours from the backflow, the
well flowed at a wellhead pressure of 360 psi without nitrogen
lift. Fifteen acid return samples were collected during flowing
back the well over a period of 4.2 hours. The acid returns
were analyzed for key ions.
Treatment Evaluation
The treatment using the emulsified acid was very successful
where the well productivity has been increased by several
orders of magnitude. Flowmeter tests were performed befo~
and after the treatment. The results indicated significant
increase in oil production from the stimulated intervals,
especially Zone 3 which in general has low permeability.
After the treatment, the flowmeter test showed that the
percentage production of ~ne 3 (A&B) has increased from
14 to 29Y0.
It is interesting to highlight the low concentration of the
total iron present in the acid returns of Well-A. Fig 13
displays the total iron concentration in the acid returns as a
function of time. The total iron concentration reached a high
value of 237 mg/1 after 1.8 hours from the backflow. Then, it
gradually dropped until it reached a constant value of less
than 1 mg/1 after 4.2 hours. The source of iron is the acid
(regular and gelled) reaction with the coiled tubing, mixing
tanks, and corrosion products. However, this value is much
less than that produced after conventional stimulation.lG For
example, the total iron concentration measured in the acid
returns of Well-B (an oil producer) which was acidized by
regular HC1 acid (15 wtYo)reached up to 6,000 mg/1 as shown
in Fig. 14. The iron produced by regular acid is much greater
than that resulted after stimulation using emulsified acid. In
the case of using the emulsified acid only, diesel is in contact
with tubing/casing and the acid is the dispersed phase which
has less interaction with tubing/casing surfaces. Therefore,
the acid-in-diesel emulsion minimized corrosion and
potential for forming acid/oil sludge.
Fig. 15 represents the calcium ion concentration in the acid

SPE $9418 STIMULATION OF TIGHT CARBONATE RESERVOIRS
returns of Well-A. Calcium ion concentration reached a
maximum value of 48,432 mg/1 after 2 hours. This increase in
the calcium concentration was the result of the acid reaction
with the formation rock (calcite), Calcium concentration
gradually decreased and reached 18,603 mg/1 in the last
sample. Fig. 16 shows the magnesium ion concentration in
the acid returns as a function of time, Magnesium
concentration started at 513 mg/1 due to the dilution by
mixing water which had a low magnesium ion content (58
mg/1). After 1.8 hours, it slowly increased until it reached an
average value of 1,700 mg/1. Magnesium concentration
became almost constant in the acid return samples after 3.5
hours. The concentration of magnesium ion in the last sample
(1,685 mg/1) was close to that in the formation water (1,560
mg/1),
Conclusions
1. Acid-in-diesel emulsion was a viscous non-Newtonian
fluid (shear-thinning behavior).
2. Acid-in-diesel emulsion was stable for more than 72
hours at 24 ‘C.
3. Stability of acid-in-diesel emulsion decreased as the
temperature was increased.
4. Acid-in-diesel emulsion was compatible with native
crude oil and acid additives, but mutual solvents and
demulsifiers broke the emulsion.
5. The reaction rate of the acid-in-diesel emulsion with
reservoir rocks at 24 “C was slower than that of the 15 wt70
HC1by a factor of 45.
6. The reaction rate of the acid-in-diesel emulsion
increased as the temperature was increased.
7. Corefloed experiments indicated that the acid-in-diesel
emulsion created wormholes in tight carbonate zones (< 50
red).
8. Number and size of wormholes were found to be
functions of the injection flow rate of the acid.
9. At the same acid volume and flow rate, acid-in-diesel
emulsion penetrated deeper through reservoir cores than the
15 wt% HCI.
10. Emulsified acid improved the core permeability by 9-
fold, while 15 wt% HCI increased the permeability by a factor
of 2 only at a low (0.5 cm3/min) injection rate.
11. Acid-in-diesel emulsion was successfully applied in the
field with a substantial increase in oil production.
12. Emulsified acid reduced corrosion of well tubing and
casing compared to that of a regular acid.
Acknowledgments
The authors would like to thank the Ministry of Petroleum
and Mineral Resources for permission to publish this paper.
We also acknowledge M.A. A1-Jawfi, A.A. Bin-Hassan, T.A.
A1-Shafei, J.A. Saleem, A.A. Hawsawi, and S,A. A1-Zaki for
conducting lab and field work. The authors would like to
thank the Chemistry Unit for performing chemical analyses of
13
—- ——-
USING ACID-IN-DIESEL EMULSIONS: FIELD APPLICATION 5
the core effluent and the acid returns and the Advanced
Instruments Unit for conducting XRD analysis.
Nomenclature
consistency factor, cp.sn-’
injected fluid permeability, md
initial permeability, md
permeability ratio, dimensionless
power-law index, dimensionless
shear rate, s-l
apparent viscosity, cp
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6 H.A. AL-ANAZI,H.A. NASR-EL-DIN, S.K. MOHAMED SPE 39418

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14. Buijse, M.A., “Understanding Wormholing Mechanisms Can
Improve Acid Treatments in Carbonate Formations,” paper SPE
38166 presented at the SPE European Formation Damage
Conference heId in The Hague, The Netherlands, June 2-3,
1997.
15. Krawietz, T.E., and Rael, E.L., “Horizontal Well Acidizing of a
Carbonate Formation: A Case History of Llsbume Treatments,
Prudhoe Bay, Alaska,” SPEPE (November 1996), 238-243.
16. Smith, C.F., Crowe, C.W., and Nolan III, T.J., “Sadary
Deposition of Iron Compounds FoI1owing Acidizing Treatments;
Jfl(September 1969), 1121-28.

Table 1. Formula of the acid-in-diesel emulsion. Table 2. Chemical composition of the formation brine’.
Component Quantity/l ,000 gals
15 wt% HCI 700 gals
Diesel 300 gals
EmuIsitier 20 gals
Corrosion Inhibitor 7.5 gals
Chelating Agent 50 lbs HCO~ 440
Reducing Agent 10 lbs so4- 303
TDs 117,701
a pH = 6.8

Table 3. Power-1aw parameters (n & k) for the Table 4. Depth of producin zonw in WeII-A.
acid-in-diesel emulsion.
Temperature,‘C n k, CP.Sn-’
24.0 0.62 344,0 ~
35.0 0.64 290.3 IAI 6,575-6,626 I
45.0 0.68 240.0

Table 5. Flu 1scomposition used in stimulation of WeII-A.

Additives Quantity/l ,000 gals
15 wt% HC1 700 gals
Diesel 300 gals
Emulsifier 20 gals
F Corrosion Inhibitor 7.5 gals
15 wt% HC1 Acid Corrosion Inhibitor 7.5 gals
Reducing Agent 5 lbs
Iron Chelating Agent 50 lbs
HzS Scavenger 2 gals
Friction Reducer 2 gals
Anti-Sludge Agent 5 gals
Surfactant 1 gals
Gelled Acid Corrosion Inhibitor 4 gals
Inhibitor Aid 10 gals
Surfactant 2 gals
Iron Control Agent 10 lbs
Fluid-Loss Additive 3 lbs
Acid Gelling Agent 20 lbs
Temporary Gel Gelling Agent 500 lbs
Suspending Agent 30 Ibs
Stabilizer 15 Ibs
Breaker 4 Ibs
Soda Ash 50 lbs/10 bbls water

14
 SPE59418 STIMULATION OF TIGHT CARBONATE RESERVOIRS USING ACID-IN-DIESEL EMULSIONS: FIELD APPLICATION
7

500 100
Temperature,“C

1 1 1 r ! I
50 ~
1 235 10 20 30 50
Shear Rate, 1/s
Fig. I-Apparent viscosity of acid-in-diesel emulsion as a
Fig. 2-Thermal stability of acid-in-diesel emulsion at 96 “C.
function of shear rate at various temperatures.

100
T= 240c

80 -
@
F
# 60 -
3
~40-

Acid-in-disel emulsion
o
0 1 234 5 67
Time, min

Fig. 3-Photomicrograph (x250) of acid-in-diesel emulsion. Fig. 4-Weight loss of reservoir rocks by acid-i~diesel
emtision and 15 wt% HC1 acid at 24 ‘C.

15
 H.A. AL-ANAZI, H.A. NASR-EL-DIN, S.K. MOHAMED SPE 39418
8

Acid-in-diesel

80 -
L

9doc 1; 50,000 -
■
emukion
# •l 15 wt% HCI
.8
s
# 60 - g 40,000 -
Q
3 :
0 30,W -
g 40 - u
E
“~ 20,000 -
24°c a

o
0 10 20 30 40 50 60 70
Time, min Cumulative Core Effluent, PV
Fig. 5-Weight loss of reservoir rocks by acid-in-diesel Fig. 6-Calcium ion concentration in the core effluent at a
emulsion at various temperatures. flow rate of OS cm3/min and 96 “C.

0.35
■ Acid-in-diwel 14~
$ 0.3 - emukion
T Acid-in-did
B ❑ 15 wt% HCI
~- 0.25 - emdsion
0
.=
$~ 0.2 -
c }
& ().15 -

8
G
x
c
0.1 “

0.05 -
) n
IY 15 wt% HCI

0 16 14
4~ 6 8 10 14 “4 6 8 10 12
Cumulative Core Effluent, PV Cumuhtive Core Effluent, PV
Fig. 7-HC1 acid concentration in the core effluent at a flow Fig. 8-Permeability ratio as a function of the cumulative
rate of 0.5 cm3/min and % ‘C. core effluent at a flow rate of 0.5 cm3/min and 96 “C.

45,000 0.5
Flow Ratq cmshfn Flow Rate, ans/ndn I
9 40,000 - m ■ 0s
•1 3.0

I I I ! I ! I
10,OOO‘
4 6 8 10 12 14 16 18
Cumulative Core Effluent, PV Cumulative Core Effluent PV
Fig. 9-Calcium ion concentration in the core effluent at Fig. 10-HCI acid concentration in the core effluent at
different flow rak using acid-in-diesel emubion. different flow rates using acid-in-diesel emdsion.

16
 —.. —A.. .

SPE 39418 STIMULATION OF TIGHT CARBONATE RESERVOIRS USING ACID-IN-DIESELEMULSIONS:FIELDAPPLICATION 9

e ■ Brine saturated cor~

•l Oil saturatedcores
El 600 /

Injection
na~ 0.5 3.0 6.0
cm3/min

o
0 2 4 6 8 10 12 14 Fig. 12-Photo of the inlet face of core plugs treated with
~ection F1OWRate, cm3/min acid-in-diesel emukion (1 PV) at different injection
Fig. 11-FinaI permeability ratio as a function of acid rates.
~ection flow rate at 96 “C.

I Well-A (Oil Producer) -Start production

Acfd-in-Diesei Emtision of aqueous phase
\ 1.7s’ m

Well-B (Oil Producer

15 wt% HCl Acid
1.75” cm

.~
L 2 3 4 5 “o 0.5 1. . 3
Time, hour Tim%hour
Fig. 13-ToM iron concentration in the acid returns of Fig. 14-Total iron concentration in the acid returns of
Well-A (an oil producer) after stimulation using Well-B (an oil producer) after stimulation using
acid-in-d]esel e-mulsion by 1.75” CTU. 15 wt% HCI by 1.75” CTU.

2 3 4 5 2 3 4 5
Time, hour Time, hour
Fig. 15-Calcium ion concentration in the acid returns of Fig. 16-Magnesium ion concentration in the acid returns of
Well-A. Well-A.

17