SPE 115926

Development and Field Application of a New, Highly Stable Emulsified Acid

Hisham A. Nasr-El-Din, SPE, Texas A&M University; Saad Al-Dirweesh, SPE, Saudi Aramco; and Mathew
Samuel, SPE, Schlumberger

Copyright 2008, Society of Petroleum Engineers

This paper was prepared for presentation at the 2008 SPE Annual Technical Conference and Exhibition held in Denver, Colorado, USA, 21–24 September 2008.

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 have not been
reviewed by the Society of Petroleum Engineers and are subject to correction by the author(s). The material does not necessarily reflect any position of the Society of Petroleum Engineers, its
officers, or members. Electronic reproduction, distribution, or storage of any part of this paper 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 SPE copyright.

Abstract
Acid-in-diesel emulsified acid has been used in the oilfield for many years. It is known that the emulsified acid should be
stable at ambient conditions for a long period of time. It should be stable also at downhole conditions for a period of time
long enough to pump the acid without encountering operational problems. Application of emulsified acid at higher
temperatures requires 20 to 30 gpt of a cationic emulsifier.
A thorough laboratory study was conducted to select an emulsifier that can be used at lower loadings, and meet the
stability criteria that are needed to stimulate oil and gas wells. Laboratory work included measuring stability, apparent
viscosity, and droplet size distribution as a function of emulsifier type and concentration, temperature, and additive type and
concentration.
A new emulsified acid was developed and used to acid fracture over ten wells in a deep gas reservoir in Saudi Arabia.
The formation is predominantly limestone and dolomite with streaks of anhydrite. Acid fracturing practices consist of
pumping 28 wt% emulsified acid (acid to diesel volume ratio = 70:30), a pad and in-situ gelled acid to create long conductive
fractures.
The new emulsified acid used a significantly lower amount (4 to 6 gpt) of the emulsifier, albeit it produced a stable
emulsion over a wide range of temperatures (from 75 to 275οF). The droplet size of emulsions produced from the new
emulsifier was much smaller and, as a result, the apparent viscosity of the acid-in-diesel emulsion was higher. Field data
showed greater reduction in the time needed to prepare the new emulsion in the field. The performance of wells stimulated
with the new emulsifier was significantly better than those stimulated with the old emulsifier.

Introduction
Hydrochloric acid is commonly used in matrix and acid fracturing treatments in carbonate reservoirs. However, application
of HCl acids in deep wells is a concern because this acid is very corrosive and its reaction rate with carbonate minerals is fast
at high temperatures. One way to address these issues is to emulsify the acid in a hydrocarbon phase, e.g., diesel (Crowe and
Miller, 1974; Bergstrom and Miller, 1975).
Diesel acts as a diffusion barrier between the acid and the rock (Hoefner and Fogler, 1985; Daccord et al., 1987; Peters and
Saxon, 1989). Thus, 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), which enhances well
performance (Williams and Nierode, 1972; Guidry et al., 1989; Navarrete et al. 1998a,b).
Depending on the droplet size of the dispersed phase, the emulsified acid can be categorized as micro (Hoefner and
Fogler, 1985) or macro-emulsion (Al-Anazi et al., 1998). The latter has larger droplet sizes and uses smaller amounts of
emulsifier. This study however will focus on macro-emulsions that were extensively used in the field (Al-Anazi et al., 1998;
Mohamed et al., 1999; Nasr-El-Din et al., 2000; Kasza et al., 2006).
Acid-in-diesel emulsion has several advantages besides its slow reaction rate with the rock. It has a relatively high
viscosity, which results in a better sweep efficiency that will improve acid distribution in heterogeneous reservoirs (Buijse
and van Domelen, 1998). Also, the live acid does not come in contact with well tubulars. Therefore, there is minimum
corrosion to well tubulars. As a result, the concentration of iron in the live acid reaching the formation will be low (Al-Anazi
et al., 1998). The presence of iron in the acid is a major concern because it will precipitate once the pH reaches around 2
(Taylor et al., 1999). Iron(III) can adversely interact with corrosion inhibitors, and cationic surfactants at high acid
concentrations (Al-Nakhli et al., 2008). It also enhances corrosion of well tubulars and aggravates the formation of acid-oil
sludges (Nasr-El-Din, 2000).
2 SPE 115926

Several studies (de Rozieres et al., 1994; Conway et al., 1999; Kasza et al., 2006; Al-Mutairi et al., 2008a) examined the
reaction of emulsified acid with carbonate rocks. The rotating disk apparatus was extensively used and the results of these
studies indicated that the reaction of emulsified acid with carbonate rocks is slower than that of regular acids. Al-Mutairi et
al. (2008a) indicated that the size of the acid droplets affected the reaction rate. And this should be considered as an important
parameter in designing acid treatments. In a second study, Al-Mutairi et al. (2008b) examined the impact of the droplet size
on the rheologcial properties of acid-in-diesel emulsions.
Propagation of emulsified acid in reservoir cores was examined by monitoring the pressure drop across the cores, then
running CT scans before and after acid injection (Bazin and Abdulahad, 1999), examined the core plugs using optical
microscope (Lynn and Nasr-El-Din, 2001), and in some cases the cores were scanned during the whole acid injection period
(Siddiqui et al., 2006). These studies indicated the following: emulsified acid was injected into tight carbonate cores without
encountering any problems. The acid propagated through the core plugs in almost straight lines. The acid propagation rate in
the core plugs was very fast. The acid created narrow wormholes in the cores and did not cause wash-out on the injection
face of the core plugs. The acid enhanced core permeability by a factor that depended on the acid injection rate. The acid
created clean wormholes, but a residual diesel was noted in some areas of the cores. This residual can be removed by using
mutual solvents in the preflush and postflushes.
Emulsified acid has been successfully used in matrix acid treatments of oil wells, (Al-Anazi et al., 1998; Kasza et al., 2006)
seawater injectors (Mohamed et al., 1999), and wastewater disposal wells (Nasr-El-Din et al., 2000). It was also tested (Nierode
and Williams, 1971; Li et al., 1993; Navarrete et al., 1998a) and applied in acid fracturing treatments (Nasr-El-Din et al., 2001;
Bartko et al., 2003). Several authors reported positive results when emulsified acid was used in acid fracturing treatments.
Recently, Nasr-El-Din et al. (2008) found that field results obtained with emulsified acid was better than other acids used to
fracture deep gas wells. They also found that emulsified acid had minimum effect on rock softening, which was needed to
maintain high fracture conductivity for a long period of time.
Application of emulsified acid at high temperatures requires a stable emulsion to prevent corrosion of tubulars as well to
improve and sustain the retarded nature of the acid to create deeper wormholes in matrix acidizing application or longer etched
fractures in acid fracturing application. One of the key parameters in formulating emulsified acids is the type and concentration
of emulsifier used to create a stable emulsion. Two different emulsifiers were used earlier to maximize the stability of the
emulsified acid, one for low temperatures and the other for high temperatures. The objective of the present study is to select an
emulsifier that can be used at lower loadings and meet the stability criteria that are needed for oil and gas wells. In addition, the
corrosion rates of low-carbon steel tubing should be within the industry acceptable limits.

Experimental Studies
Materials
Hydrochloric acid was ACS grade, and its concentration was determined by titration using NaOH solutions. The acid was
diluted to the required concentrations using distilled water. Diesel, without additives, was used to prepare the emulsified acid.
It should be noted that commercial diesel with surface active species may impact emulsion stability. Lab testing using diesel
available to the field is strongly recommended.
The corrosion inhibitor and iron control agents were field chemicals and were used as received. It should be noted that the
emulsified acid systems can be prepared using both cationic (Al-Anazi et al., 1998) as well as anionic surfactants (Bazin and
Abdulahad, 1999). The presence of positive charges on the cationic surfactants will minimize loss of the emulsifier due to
adsorption on the surface of the rock, which will enhance propagation of the emulsified acid in carbonate formations.
The old emulsifier (E2) was cocoalkylamine acetate and was utilized at 20-30 gpt. Emulsified acid prepared using E2 had
good stability at high temperatures; however they partially broke at ambient conditions. These emulsions required remixing
and quality control in the field before use, which meant longer operation hours and higher cost. There was a need to come up
with a new emulsifier that can be used at a lower loading, and gives stability over a wider range of temperatures including
ambient conditions.
More than 10 different emulsifiers were tested. An emulsifier that was based on tallow amine acetate was very promising
and was studied in detail. Similar to the old emulsifier, the new one was cationic and had the same head group (amine
acetate). However it had different hydrophobic tail. The old emulsifier was made of coco (Table 1); whereas the new one
was made of beef tallow (Table 2). Beef tallow had a higher molecular weight (longer carbon chain with C12-C18) and
contained double bonds (unsaturation).

Experimental Procedure
Acid Preparation. Mix the required the required amount of the emulsifier into the diesel in a warring blender. Mix
separately water, acid and the required additives for the aqueous phase in a beaker equipped with a magnetic stirrer. Using a
syringe, drop the acid solution (acid + additives) into the diesel solution while stirring. Increase the mixing speed after
adding all acid solution into the diesel mixture for about 15-20 minutes. This should result in a stable emulsion. Tables 3
and 4 give the composition of emulsified acids using emulsifiers E2 (old) and E1 (new).

Stability and Characterization. Stability of emulsified acid was monitored at ambient conditions for several days. It was
also monitored at high temperature by placing the emulsion in a high temperature/high pressure see-through cell. The visual
SPE 115926 3

cell had a volume of 100 cm3. Nitrogen gas was connected to the instrument and the cell was heated electrically by a silicone
heater plates attached to the cell. More details on the procedure used for the visual cell were given by Al-Muntasheri et al.
(2008). Phase separation should not occur during the test period. The stability of emulsion was monitored using a
conductivity meter. If diesel is the external phase, then the conductivity should read near zero.
The apparent viscosity of emulsified acid was measured as a function of shear rate using a Chann 35 rotational viscometer
fitted with a Hastelloy bob/sleeve combinations. High temperature viscosity measurements were performed on HT/HP Grace
rheometer.
The size distribution of the dispersed phase in the emulsions was measured using a LIECA microscope and/or a Fritsch’s
Laser Particle Sizer and following the procedure of Al-Mutairi et al. (2008a,b).

Corrosion Testing. For corrosion experiments above 170°F, an autoclave, agitated and rated for operation at 5,000 psig at
400°F was used. For corrosion tests < 170°F, a hot water bath, equipped with temperature and water level control was
employed. Metal coupons were obtained from L-80, C-95 and P-110 (all low-carbon steel used in deep wells). Mill scale is
removed from low-carbon steel by tumbling/blasting with glass beads. Approximate dimensions were 1 in. x 1.75 in. with a
¼ in. diameter hole drilled in the upper part of the coupon. Surface area for coupons was approximately 25 cm2. The
coupons were cleaned ultrasonically in a suitable, oil-free solvent and rinsed in acetone, dried and weighed. The average
weight per unit area was determined.

Results and Discussion

Laboratory Studies
The first set of experiments was conducted to assess the effect of various acid additives on the stability of emulsified acid
prepared using the new emulsifier E1. It is important to note that both emulsifiers have the same head group: amine acetate.
Laboratory results indicated that mutual solvent (ethyleneglycol monobutyl ether), will break emulsified acids. Therefore,
mutual solvent should not be used at high concentrations before or after pumping emulsified acid. The effect of other acid
additives depends on their ability to adsorb at the acid diesel interface. In general surface active species: corrosion inhibitors,
anti-sludge agents, may adversely affect the stability of emulsified acid. Non-surface active species, e.g., iron control agents,
had no significant effect of the stability of emulsified acid. It is strongly recommended to assess the stability of emulsified
acid using acid with all addivities as per field treatment. Emulsifier concentration can be adjusted to obtain the required
stability.
Emulsified acid made using E1 was found to be stable at high temperatures and ambient conditions. Unlike emulsifier E1,
the old emulsifier was stable at high temperatures, but broke in a few hours at room temperature. Emulsified acids prepared
in the field using the old emulsifier required long time to remix the acid before pumping. This problem was eliminated by
using the new emulsifier. The new emulsion system utilizes a single emulsifier over a wide range of temperatures.
Rheology: Rheological experiments of emulsified acid with various concentrations of HCl were conducted. Emulsified
acid made using the conventional emulsifiers requires 20 to 30 gal/1000 to make stable emulsions, Tables 3 and 4. The new
emulsifier requires only one forth the concentration of the emulsifier and hence the effect of emulsifier concentrations were
also examined (Figs. 1 to 3). The apparent viscosity of emulsified acid made using E1 was higher than that prepared with E2
(Figs. 1 to 4). The higher viscosity of E1 will help to some extent in retardation and diversion of this acid. The mean droplet
size of emulsified acid prepared by using 5 gpt E1 was found to be 35 μm, whereas that prepared using E2 at 20 gpt was 69
μm. The smaller droplet size of the emulsified acid prepared by E1 emulsifier had resulted in higher apparent viscosity. This
is in agreement with the results obtained by Al-Mutairi et al. (2008b) The breakdown tendency of emulsified acid was
studied by observing the changes in the viscosity of the emulsified acid when spent with CaCO3 (Table 5).
Effect of Acid to Diesel Ratio: The recommended volume ratio of acid to diesel is 70:30. Other ratios were tested (60,
70 and 80 vol% acid) and the apparent viscosity data are shown in Fig. 5. Emulsified acid that contained acid to diesel ratio
of 80:20 is very viscous and therefore is not recommended.
Effect of Corrosion Inhibitors: Tables 6 and 7 show the effect of a corrosion inhibitor (CI-A) and corrosion inhibitor
intensifier (Int-A) on the weight loss and pitting at two different temperatures. The type of inhibitor and its concentration
may increase or decrease the emulsion stability. The emulsion stability with the presence of some inhibitors was slightly
enhanced. It was noticed that some other inhibitors are incompatible with emulsified acid formulated with E1. Use of other
inhibitors will require stability and corrosion tests to determine emulsion stability before field application.

Field Application
The K-formation is located in the eastern province of Saudi Arabia. This formation belongs to the late Permian age and is
encountered at an average depth of approximately 11,500 ft. The K-formation is subdivided into four main zones, denoted A,
B, C, and D. Zones B and C are the two main intervals producing non-associated gas. A layer of anhydrite caps K-B
reservoir, whereas a layer of mudstone and anhydrite separates K-B and K-C reservoirs. A layer of anhydrite separates K- C
and D. Both K-C and K-B reservoirs appear to be well bounded and there are no indications that communication exists
between these two zones. Lithological studies have shown that the reservoir is composed of dolomite intermingled with
limestone and intermittent anhydrite stringers within the tighter section of the reservoir. The two reservoirs have varying pay
4 SPE 115926

thickness, on average, from 120 ft in the K-B to 200 ft in the K-C. The reservoir temperature in K-B is 260°F whereas in the
K-C formation the temperature is 275°F.
Stimulation efforts in the K-reservoirs are needed to remove drilling mud filter cake and enhance reservoir permeability.
Both matrix and fracture acidizing treatments are conducted regularly in this field. Regular hydrochloric acid at 28wt% has
been used to stimulate gas wells in this formation. However, 28 wt% HCl is very corrosive, especially at the high
temperatures encountered in these deep, sour gas reservoirs. There is a need for acid formulations that have the same rock
dissolution power, but are less corrosive. One of these acid formulations is the acid-in-diesel emulsion. This acid system
consists of diesel (continuous phase), HCl acid (dispersed phase) and an emulsifier.
The new acid-in-oil emulsion systems with 6 gal/1,000 gal emulsifier concentration was used in acid fracturing
application in the Khuff reservoir described previously. A pilot campaign of 4 wells was undertaken to evaluate the
effectiveness of the new acid-in-oil emulsion. Zone B of the Khuff formation was acid fractured in all 4 wells. It should be
noted that the only change from previous treatments and the 4 well pilot campaigns was the reduction in emulsifier
concentration during the mixing of acid-in-diesel emulsion systems. The rest of the fluid system as well as the total acid
volume used in the pilot campaign were exactly the same as used in previous treatments.
Fig. 6 provides a comparison of field mixing times to prepare a 500 bbl tank of acid-in-diesel emulsion systems. On
average a reduction of 25% was observed in the time taken to mix the fluid on location. This reduction is a substantial
benefit to field operations as it reduced the fluid preparation time and cost.
Fig. 7 is a comparison of actual initial production rate to expect initial production rate of wells treated with the old acid-
in-diesel emulsion and the new emulsion tested in the 4 well campaigns. With the old emulsion system an average of 63%
increase in rate was observed when comparing actual to expected production. In the 4-well pilot campaign an average of
97% increase in rate was observed when comparing actual to expected production. As pointed out earlier there were no
changes made to the treatment methodology or the acid volumes used in the acid fracturing treatments. As such, the positive
production response indicated that the new acid-in-diesel emulsion system provided better stimulation compared to the old
emulsion system. The new emulsified acid had smaller droplet size and higher viscosity, which means slower reaction rate
and deeper acid penetration. Since the success of the 4 well campaign, the new acid-in-oil system has been fully deployed for
all matrix and acid fracturing applications.

Conclusions
A new and highly stable emulsion was developed and used in acid fracturing treatments of deep gas wells. Based on the
results obtained in this study, the following conclusions can be drawn:

1. The new emulsified acid used a significantly lower amount of the emulsifier, albeit it produced a stable emulsion
over a wide range of temperatures.
2. The droplet size of emulsions produced from the new emulsifier was much smaller and, as a result, the apparent
viscosity of the acid-in-diesel emulsion was higher.
3. Field data showed greater reduction in the time needed to prepare the new emulsion in the field. The new emulsion
did not require remixing before the treatment
4. The performance of wells stimulated with the new emulsifier was significantly better than those stimulated with the
old emulsifier.

Acknowledgments
The authors would like to thank Saudi Aramco and Schlumberger for the permission to present and publish this paper.
Thanks are also to Kartina Abdul Kassim, Sai Aung Zaw Min (of Middle East and Asia Client Support Laboratory), Laura
Schafer and Brett Cardwell (of Sugar Land Product Center) for the laboratory data. The authors would like to thank Keng
Seng Cham, Ramanathan Venkateshwaran and Shrihari Kelkar of Schlumberger for useful discussions.

References
Al-Anazi, H.A., Nasr-El-Din, H.A. and Mohamed, S.K.: Stimulation of Tight Carbonate Reservoirs Using Acid-in-
Diesel Emulsions - Field Application, paper SPE 39418 presented at the 1998 SPE Int. Symposium on Formation
Damage Control, Lafayette, LA, 18-19 February.
Al-Muntasheri, G.A., Nasr-El-Din, H.A., Peters, J.A., and Zitha, P.L.J.: Thermal Decomposition and Hydrolysis of
Polyacrylamide Co-tert-butyl Acrylate, European Polymer Journal 44(4) (2008) 1225-1237.
Al-Mutairi, S.H., Nasr-El-Din, H.A., and Hill, A.D.: Effect of Droplet Size on the Reaction Kinetics of Emulsified Acid
with Calcite, paper SPE 112454 presented at the 2008a SPE International Symposium and Exhibition on Formation
Damage Control held in Lafayette, LA, 13-15 February.
Al-Mutairi, S.H., Hill, A.D. and Nasr-El-Din, H.A.: Effect of Droplet Size and Acid Volume Fraction on the Rheological
Properties and Stability of Emulsified Acid, paper SPE 107741, accepted for publication, SPEPO, 2008b.
SPE 115926 5

Al-Nakhli, A., Nasr-El-Din, H.A., and Al-Baiyat, A.A.: Interactions of Iron and Viscoelastic Surfactants: A New
Formation Damage Mechanism, paper SPE 112465 presented at the 2008 SPE International Symposium and Exhibition
on Formation Damage Control held in Lafayette, LA, Feb. 13-15.
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.
Bazin, B. and Abdulahad, G.: Experimental Investigation of Some Properties of Emulsified Acid Systems for
Stimulation of Carbonate Formations, paper SPE 53237 presented at the 1999 SPE Middle East Oil Show held in
Bahrain, 20-23 February.
Bergstrom, J.M. and Miller, B.D.: Results of Acid-in-Oil Emulsion Stimulations of Carbonate Formations, paper SPE
5648 presented at the 1975 SPE Annual Fall Meeting held in Dallas, TX, September 28-October 1.
Buijse, M.A. and van Domelen, M.S.: Novel Application of Emulsified Acids to Matrix Stimulation of Heterogeneous
Formations, paper SPE 39583 presented at the 1998 International Symposium on Formation Damage Control held in
Lafayette, LA, 18-19 February.
Conway, M.W., Asadi, M., Penny, G., and Chang, F.F.: A Comparative Study of Straight/Gelled/Emulsified
Hydrochloric Acid Diffusivity Coefficient Using Diaphragm Cell and Rotating Disk, paper SPE 56532 presented at the
1999 SPE Annual Technical Conference and Exhibition, Houston, TX, 3-6 October.
Crowe, C.W. and Miller, B.D.: New, Low-Viscosity Acid-in-Oil Emulsions Provide High Degree of Retardation at High
Temperature, paper SPE 4937 presented at the 1974 SPE Rocky Mountain Regional Meeting held in Billings, MT, 15-17
May.
Daccord, G., Touboul, E., and Lenormand, R.: Carbonate Acidizing: A Quantitative Study of the Wormholing
Phenomenon, paper SPE 16887 presented at the 1987 SPE Annual Technical Conference and Exhibition held in Dallas,
TX, 27-30 September.
de Rozieres, J. Chang, F.F. and Sullivan, R.B.: Measuring Diffusion Coefficients in Acid Fracturing Fluids and Their
Application to Gelled and Emulsified Acids, paper SPE 28552 presented at the 1994 Annual SPE Conference held in
New Orleans, LA, 25-28 September.
Guidry, G.S., Ruiz, G.A. and Saxon, A.: SXE/N2 Matrix Acidizing, paper SPE 17951 presented at the 1989 SPE Middle
East Oil Technical Conference and Exhibition held in Manama, Bahrain, 11-14 March.

Hoefner, M.L. and Fogler, H.S.: Effective Matrix Acidizing in Carbonates Using Microemulsions, Chem. Eng. Prog. 37
(May 1985) 40.
Kasza, P., Dziadkiewicz, M. and Czupski, M.: From Laboratory Research to Successful Practice: A Case Study of
Carbonate Formation Emulsified Acid Treatments, paper SPE 98261 presented at the 2006 International Symposium on
Formation Damage Control held in Lafayette, LA, 15-17 February.
Li, Y. Sullivan, R.B., de Rozieres, J., Gaz, G.L., and Hinkel, J.J.: An Overview of Current Acid Fracturing Technology
with Recent Implications for Emulsified Acids, paper SPE 26581 presented at the 1993 Annual SPE Technical
Conference and Exhibition, Houston, TX, 3-6 October.
Lynn, J.D. and Nasr-El-Din, H.A.: A Core-Based Comparison 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.
Mohamed, S.K., Nasr-El-Din, H.A. and Al-Furaidan, Y.A.: Acid Stimulation of Power Water Injectors and Saltwater
Disposal Wells in a Carbonate Reservoir in Saudi Arabia: Laboratory Testing and Field Results, paper SPE 56533
presented at the 1999 SPE Annual Technical Meeting, Houston, TX, 3-6 October.
Nasr-El-Din, H.A., Al-Anazi, H.A. and Mohamed, S.K.: Stimulation of Water Disposal Wells Using Acid-in-Diesel
Emulsions - Case Histories, SPEPF 15(3) (2000) 176-182.
Nasr-El-Din, H.A., Al-Driweesh, S.M., Chesson, J.B., and Metcalf, A.S.: Fracture Acidizing: What Role Does
Formation Softening Play in Production Response?, SPEPO 23(2) (2008) 184-191.
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
Technical Meeting, New Orleans, LA, 30 September 3 October.
6 SPE 115926

Nasr-El-Din, H.A.: Surfactants Used in Acid Stimulation, In Surfactant, Fundamental and Applications in the Petroleum
Industry, L.L. Schramm (Editor), Chapter 9, Cambridge University, 2000.
Navarrete, R.C., Miller, M.J. and Gordon, J.E.: Laboratory and Theoretical Studies for Optimization of Acid Fracture
Stimulation, paper SPE 39776 presented at the 1998a SPE Permian Basin Oil and Gas Recovery Conference, Midland,
TX, 23-26 March.
Navarrete, R.C., Holms, B.A., McConnell, S.B. and Linton, D.E.: Emulsified Acid Enhances Well Production in High
Temperature Carbonate Formations, paper SPE 50612 presented at 1998b SPE European Petroleum Conference held in
The Hague, The Netherlands, 20-22 October.
Nierode, D.E. and Williams, B.B.: Characteristics of Acid Reaction in Limestone Formations, SPEJ 11 (1971) 406-418.
Peters, F.W. and Saxon, A.: Nitrified Emulsion Provides Dramatic Improvements in Live Acid Penetration, paper SPE
19496 presented at the 1989 SPE Asia-Pacific Conference held in Sydney, Australia, 13-15 September.
Siddiqui, S., Nasr-El-Din, H.A., and Khamees, A.: Wormhole Initiation and Propagation of Emulsified Acid in
Carbonate Cores Using Computerized Tomography, J. Petroleum Science Engineering 54 (2006) 93-111.
Taylor, K.C., Nasr-El-Din, H.A. and Al-Alawi, M.: Systematic Study of Iron Control Chemicals Used During Well
Stimulation, SPEJ 4 (1999) 19-24.
Williams, B.B. and Nierode, D.E.: Design of Acid Fracturing Treatments, JPT 24 (July 1972) 849.
SPE 115926 7

Table 1: Composition of Coco (used in E2).

Number of Percentage Number of

Carbon Atoms Composition Double Bonds
Lauric 12 44 0
Myristic 14 17 0
Palmitic 16 8 0
Caprylic 8 8 0
Others 23

Table 2: Composition of Tallow (used in E1).

Number of Percentage Number of

Carbon Atoms Composition Double Bonds
Oleic 18 47 1
Stearic 18 14 0
Palmitic 16 26 0
Others 13

Table 3: Composition of emulsified acid using emulsifier E2.

Oil-Based Additives Quantity Unit

Diesel 280 gal/1000
Emulsifier E2 25 gal/1000
Water-Based Additives
Fresh water 262 gal/1000
32% HCl 414 gal/1000
Corrosion Inhibitor (CI-A) 8 gal/1000
Chelating agent 25 gal/1000
Iron Control additive 10 gal/1000

Table 4: Composition of emulsified acid using emulsifier E1.

Oil-Based Additives Quantity Unit

Diesel 300 gal/1000
Emulsifier E1 5 gal/1000
Water-Based Additives
Fresh water 262 gal/1000
32% HCl 424 gal/1000
Corrosion Inhibitor (CI-A) 8 gal/1000
Chelating agent 25 gal/1000
Iron Control additive 10 gal/1000
8 SPE 115926

Table 5: Apparent viscosity of emulsified acid (with E1) before and after spending.

Reading on Chann 35 Viscosity (cp) at

Fluid 300 rpm 200 rpm 100 rpm n' k' 100 s-1 170 s-1 Remarks
100 75 46 0.7067 0.01368 173 148 at 80 oF
Before 50 39 25 0.6321 0.01135 100 82 at 150 oF
3 2 1 1 0.00006 3 3 Added CaCO3
35 27 18 0.6031 0.00949 73 59 72 hrs at 150 oF
37 26 15 0.8188 0.00249 52 47 At 80 oF
After 25 18 12 0.6591 0.00464 46 39 at 150 oF
3 2 1 1 0.00006 3 3 added CaCO3

Table 6: Corrosion data of the low temperature formulation of the emulsified acid (with E1)

0.4 vol% CI-A and 1 vol% Int-A; 175oF, 8 hours, 1,500 psi

Metallurgy Corrosion Rate (lb/ft2) Pitting Index

L-80 0.0079 0
P-110 0.004 0
C-95 0.0054 0

a. CI-A denotes corrosion inhibitor A

b. Int-A denotes intensifier A

Table 7: Corrosion data of the high temperature formulation of the emulsified acid (with E1)

0.8 vol% CI-A and 1.5 vol% Int-A; 250oF, 8 hours, 1,500 psi
Metallurgy Corrosion Rate (lb/ft2) Pitting Index
L-80 0.0417 1
P-110 0.0454 1
C-95 0.0358 0

a. CI-A denotes corrosion inhibitor A

b. Int-A denotes intensifier A
SPE 115926 9

200

175 15% HCl

Viscosity at 170 s-1 (cp)

20% HCl
150
28% HCl
125

100

75

50

25

0
50 100 150 200 250 300 350 400
Temperature (F)

Fig. 1. Effect of temperature on the viscosity of emulsified acid (with 4 gal of E1/1000 gal of emulsified acid)

350
15% HCl
300
Viscosity at 170 s-1 (cp)

20% HCl
250 28% HCl
200

150

100

50

0
50 100 150 200 250 300 350 400
Tem perature (F)

Fig. 2. Effect of temperature on the viscosity of emulsified acid (with 5 gal of E1/1000 gal of emulsified acid)

250

15% HCl
Viscosity at 170 s-1 (cp)

200
20% HCl
28% HCl
150

100

50

0
50 100 150 200 250 300 350 400
Tem perature (F)

Fig. 3. Effect of temperature on the viscosity of emulsified acid (with 6 gal of E1/1000 gal of emulsified acid)
10 SPE 115926

175
15% HCl
150

Viscosity at 170 s-1 (cp)

20% HCl
125
28% HCl
100

75

50

25

0
50 100 150 200
Temperature (F)

Fig. 4: Effect of temperature on the viscosity of emulsified acid (with 20 gal of E2/1000 gal of emulsified acid)

400 200

350 175
Viscosity at 170 s-1 (cp)

300 70:30 60:40 150

Temperature (F)
250 80:20 Temp (F) 125

200 100
150 75
100 50

50 25

0 0
0 10 20 30 40 50 60
Tim e (m in)

Fig. 5: Viscosity of emulsified acid (with E1) with various acid to diesel ratios at 170 oF.
SPE 115926 11

300

250

200
Time, Minutes

150

100

50

0
E2 Emulsified Acid E1 Emulsified Acid

Fig. 6: Time to mix 500 bbl in the field

250%
Actual Rate/Expected Rate

200%

150%

100%

50%

0%
Old System New System

Fig. 7: Ratio of actual to expected production rates