SPE 136217

Effect of Acid Spending on Etching and Acid Fracture Conductivity

M. Pournik, L. Li, B. Smith, and H.A. Nasr-El-Din, Texas A&M University, SPE

Copyright 2010, Society of Petroleum Engineers

This paper was prepared for presentation at the 2010 SPE Russian Oil & Gas Technical Conference and Exhibition held in Moscow, Russia, 26–28 October 2010.

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 prohi bited. 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
In acid fracturing, while the near wellbore area of the fracture receives fresh, unspent acid, sections of the fracture further
down the length receive partially spent acid due to reaction of acid. As a result, there is a distribution of acid concentration
along the fracture length. However, almost all experimental studies on acid fracture conductivity have been conducted with
fresh acid, which is representative of what occurs near the wellbore.
An experimental study was conducted to investigate the effect of spent acid on the resulting fracture conductivity in a
laboratory facility designed to perform acid fracture conductivity characterization. Gelled HCl acid systems with different
degrees of acid spending were used to etch fractured cores under identical treatment conditions, which were set to mimic field
conditions. Detailed etched surface characterization, fluid analysis, and conductivity measurements were performed on acid
etched fracture faces.
Experimental results clearly show that the amount of rock dissolved and actual etching pattern depend highly on acid
concentration. While there was less fracture face etching with more spent acid system, etching pattern also changed with acid
spending, which sometimes offset the additional etched volume of unspent acid. As a result, the retained conductivity was
generally higher for the more spent acid and the decline in conductivity with closure stress was more subtle with the spent acid
due to probably less weakening of the fracture face.
While there have been many developments in enhancing the etched length of acid fractured wells, a major reason for the
lack of long etched fractures is acid spending along the fracture. In order to understand the etched fracture profile, there is a
need to realize how the degree of acid spending limits etching and affects the resulting fracture conductivity. Based on the
newly discovered effect of acid spending on conductivity, acid etched length and conductivity can be predicted more
accurately and acid fracture treatments better designed.

Introduction
Acid fracturing is a well stimulation process in which acid dissolution along the face of the hydraulically induced fracture is
expected to create lasting conductivity after fracture closure. The success of treatment depends on acid etched fracture length
and retained fracture conductivity under closure stress. While reactive acid penetration distance is controlled by acid leak-off
rate, reaction rate, and fracture flow rate, fracture conductivity is influenced by etching pattern, volume of rock dissolved, rock
strength, and closure stress.
Acid reacts with fracture face as it flows along the fracture length, resulting in a distribution of acid concentration, which
in turn, creates a distribution of rock dissolution and fracture conductivity along the fracture length. In order to determine the
acid concentration profile, acid balance equation with appropriate boundary conditions, continuity and transport equations, and
a model of leak-off behavior must be solved simultaneously. Further complications such as temperature distribution along
fracture, viscous fingering of low-viscosity acid through a viscous pad, and the effect of acid on leak-off behavior can also be
considered (Ben-Naceur and Economides 1988; Lo and Dean 1989; Settari 1993). A simplified solution shows that acid
concentration profile is a function of leak-off Peclet number, which is the ratio of leak-off rate to effective diffusion. The
results indicate that at low Peclet numbers, diffusion controls acid propagation resulting in a large concentration distribution,
while at high Peclet numbers (greater than about 5), leak-off is the controlling factor and causes a rather flat concentration
profile (Nierode and Williams 1971; Williams and Nierode 1972; Schechter 1992). Based on typical field conditions and acid
systems used, Peclet numbers are usually less than 5 and hence conductivity distribution along the fracture length must be
considered. It is clear that in order to have a long etched fracture length, high acid concentration is needed to penetrate deep
into the fracture, which in turn depends on leak-off rate and effective diffusion coefficient.
2 SPE 136217

Comparison of field data to simulation runs conducted by Novotny (1977) show that while plain HCl treatment can be well
predicted assuming infinite fracture conductivity along the entire fracture length, fracture conductivity distribution along the
fracture length must be considered to predict acid fracturing treatments with low leak-off acid solutions, like gelled acid
system. As it is believed that acid leak-off is the domintant factor limiting the length of etched fracture, leak-off control fluids
are used mainly in acid fracturing treatments to lengthen the etched fracture length. The difference in leak-off characteristics
results in short and highly conductive fractures with plain HCl, while a longer and lower conductivity fractures are created by
the low leak-off fluids. Leak-off tests on several gelled acids showed that there is loss of acid viscosity with spending,
resulting in development of more wormholes and leak-off down the fracture length. In order to overcome excessive leak-off
from acid spending, a gelled acid was designed that develops high viscosity with acid spending, resulting in much better leak-
off control (Crowe et al. 1989).
It has been shown that effective mass-transfer coefficient of hydrogen ion is affected by acid concentration. In addition,
common ion effect, which arises from acid spending, causes large reduction in effective mass-transfer coefficient of hydrogen
(Fig. 1), which in turn retards the acid/rock reaction rate and lengthens the fracture etched length (Ren and Xiong 1989; de
Rozieres et al. 1994; Mumallah 1997; Conway et al. 1999). The influence of the common ion effect becomes stronger as the
concentration of spent acid decreases. Calculations show acid penetration distance to be twice as long for acid solutions
containing common ions compared to acid solutions without common ions. Furthermore, if a constant fracture width is
assumed, fracture length calculation will be 15 to 25% smaller than that calculated with variable fracture width (Ren and
Xiong 1989). The combined effect of acid concentration and common ion effect suggests that reaction rate decreases and
fracture length increases with increasing amount of acid spending. A computational model of acid fracturing was used to
predict etched fracture length for fluids with various effective diffusion coefficients. The results clearly show that etched
fracture length increases with reduction in effective diffusion coefficient of fluid (Fig. 2) (de Rozieres et al. 1994).
The effect of acid concentration on reaction rate has been studied by several investigators, with the conclusion that reaction
rate is an increasing function of acid concentration up to bulk concentration of 12 wt% HCl and beyond this concentration, the
reaction rate becomes independent of acid concentration at the temperature of 1 oC (Nierode and Williams 1971; Lund et al.
1975). Similar results were obtained at a higher temperature of 200 oF and pressure of 5290 psi in an annular flow reactor with
increase in reaction rate up to the concentration of 15 wt% HCl (Mumallah 1991). A possible explanation for decline in
reaction rate of HCl with increasing concentrations above 15 wt% might be due to the presence of common ions generated
from spending of acid, hindering further reaction (Mumallah 1997).
A study was conducted on the effect of spent acid on acid fracturing operation. It was observed that spent acid is denser
than live acid and the density gradient between live and spent acid has significant effect on the reaction rate. As acid reacts
with carbonate rock, the solution becomes reach in calcium chloride, which makes the fluid near fracture face denser than the
main fluid stream. Consequently, gravitational force will influence the flow of boundary fluid layer more than the main stream
fluid, resulting in slower reaction rate as the boundary layer fluid will flow in the opposite direction to the main stream flow
(Mumallah 1991). Furthermore, it has been shown that leak-off rate is controlled by spent acid viscosity (Nierode and Kruk
1973).

Experimental studies
The experimental apparatus and procedure were designed to enable experiments to be conducted at conditions representing
field treatments more closely and accurately. Detailed information about the experimental apparatus and procedure can be
found in Pournik (2008). The experimental apparatus was designed to accommodate larger rock samples, higher injection
rates, and higher temperatures, while minimizing corrosion and mechanical failure. The core samples are placed inside a
modified API conductivity cell that has a body dimension of 10 in. × 3 ¼ in. × 8 in. with a 7¼ in. ×1¾ in. opening, allowing
the use of rock samples with up to 3 in. thickness. A pump with a maximum operating pressure of 2,200 psig and a maximum
flow rate of 1.04 L/min was used to allow injection at rates that scale appropriately to field conditions. Cylindrical ceramic
radiant heaters were wrapped around the flow line to heat the fluid before entering the cell so experiments could be conducted
at temperatures similar to field conditions. The heaters allow the fluid to be heated to approximately 300 oF. A back pressure
regulator is installed on the leak-off line to control the pressure drop across the core. This allows the leak-off flow rate to be
controlled at the desired rate to represent field conditions more accurately. Another back pressure regulator is installed on the
cell effluent line to maintain the cell pressure above 1,000 psi to keep CO2 in solution during the acidizing process.

Materials. Indiana limestone samples with an average permeability of 4 md were used in all experiments. The core samples
were cut into parallelepiped shape with the ends curved into half-circles to fit the API cell. The overall length of the cores was
approximately 7.1 in., with a width of 1.6 in. and a thickness of 3 in. The cores were covered on the sides with a silicone
rubber compound inside a mold of the API cell in order to secure a perfect fit of the core in the cell and to prevent any bypass
of the acid around the sides of the core samples. The fracture face was kept as smooth and flat as possible by ensuring straight
and smooth cut of the fracture face.
Gelled acid was used in all experiments and it was prepared with HCl acid (nearly 31.45 wt%), a corrosion inhibitor, and
an acid-soluble polymer. In order to prepare spent acid solutions, required amount of calcium chloride was added to prepare
spent acid solutions of 10, 5, and 1 wt% HCl from fresh, unspent 15 wt% HCl. The calcium chloride used was in the form of
small pellets with purity above 94%. Tap water (TDS = 500 mg/l) was used to dilute the acid to desired concentration. The
SPE 136217 3

corrosion inhibitor was used at 0.2 wt% and the polymer concentration was 1.5 wt%. The polymer was added to the solution
slowly with the addition taking about two hours. The solution was mixed using both a magnetic stirrer at the base of the fluid
tank and an impeller mixer which was situated in the middle of the fluid level. The mixing continued for about one hour after
the addition of polymer to ensure proper mixing and hydration of polymer in acid. About 150 ml sample of prepared acid
solution was taken for viscosity and fluid analysis. The fluid was mixed all the time until the acid injection was completed.
The total amount of acid prepared was 18 liters as the capacity of the tank was only about 20 liters and about 15 liters of acid
injected during the acidizing process.

Acid Etching Apparatus. The acid etching apparatus is shown in Fig. 3. Cores were placed in the cell and a fracture gap of
nearly 0.12 in. was kept between the two fracture faces using metallic shims. The cell was placed in vertical direction such
that fluid flowed upwards through the fracture to prevent gravity effects on the etching of the core faces. After ensuring that
the pistons were in place and the fracture width maintained at the desired value, a pre-flush of tap water was injected. After
achieving the desired cell pressure, leak-off rate, and temperature, acid injection was started. During acid injection,
temperature recordings were taken several times, leak-off volume, and leak-off differential pressures were monitored to ensure
appropriate leak-off rates. Finally, tap water was injected after acid injection time ended.

Analysis Techniques. The apparent viscosity of acid solutions was measured using a HPHT viscometer. All the measurements
were conducted at temperature of 28°C and atmospheric pressure as a function of shear rate in the range of 1 - 935 s-1.
Viscosity measurements were conducted on both fresh acid and fracture flow effluent samples. While fracture flow effluent
samples were taken at 3, 6, 9, 12, and 15 minutes from start of acid injection, leak-off effluent samples were taken each minute
for the whole duration of acid injection. Both fresh acid and effluent samples from both the fracture flow and leak-off direction
were analyzed for concentration of calcium ions, HCl concentration, and density. Calcium ion concentration was measured
using Perkin-Elmer atomic absorption. The concentration of HCl acid in effluent was measured by titration with a known
concentration of sodium hydroxide. The density was measured with a DMA-35N densimeter at 25oC.

Characterization of Fracture Surface. A profilometer was used to characterize the etched fracture faces after the acidizing
process. A profilometer is a precise vertical distance measurement device that can measure small surface variations in vertical
surface topography as a function of position on the surface. The vertical measurement is made using a laser displacement
sensor while the sample is moved along its length and width on a moving table. All the experiments used a 0.05 in.
measurement interval in the x and y directions. The resolution on the vertical measurement is 0.002 in., while in the horizontal
directions (both x and y direction), the transducer resolutions are 8 x 10-5 in (Malagon et al. 2008).

Fracture Conductivity. The fracture conductivity was measured by flowing nitrogen gas between the two acid-etched
fracture faces, recording the absolute pressure at the mid-point of the fracture, and the pressure drop across the fracture. The
cell was placed in a horizontal direction with horizontal flow of nitrogen gas through the fracture as shown in Fig. 4. The
conductivity cell was placed in a load frame which provided the application of different closure stresses. The closure stress
was applied in increments of about 500 psi, starting from nearly no load to 2,000 psi, and then in increments of about 1,000 psi
from 2,000 psi to 4,000 psi, changing the load after approximately 45 minutes. Nitrogen flow was resumed after placing the
first desired load on the cell. The pressure drop across the length of the fracture faces (one inch from each end of core,
therefore 5.25 inches in total length) and absolute pressure at the center of the fracture face were measured during the
experiment. After 45 minutes, these pressure readings were recorded at six different flow rates after the pressure stabilized at
each flow rate. The flow rate ranged from about 5 to 25 liters/min with flow measured using a mass flow meter. Forcheimer’s
equation for turbulent gas flow through a porous medium was used to calculate the fracture conductivity from flow rate and
differential pressure measurements (Pursell et al. 1988).

Results and Discussion

A set of four experiments were conducted using different degree of spent acids (Table 1) in order to determine the effect of
acid spending on acid fracturing process, which included the effect on dissolved volume, fracture etching pattern, effluent
concentration, and fracture conductivity. Indiana limestone samples were used with a fixed 0.12 in. fracture width. All the acid
etching steps were conducted at an injection rate of 1 L/min with injection time of 15 minutes, fluid temperature of around
150oF, and a backpressure of 1,000 psi. Based on the fracture dimension and injection rate, the shear rate in the fracture was
about 300 s-1 for non-Newtonian fluids (with power law index, n of about 0.6) based on methodology of Navarrete et al.
(1998). The leak-off flux was fixed at nearly 0.0035 ft/min, however there were some variations between experiments as
shown in Table 1.

Apparent Viscosity of Fresh Acids. Viscosity measurements were conducted on prepared acid solutions in addition to acid
concentration and density measurements. Acid concentration and density for all of experiments are given in Table 2, while
viscosities of all acid systems are shown in Fig. 5. The acid concentrations clearly show that acid solutions were prepared
correctly in terms of HCl concentration. The apparent viscosity can be described using the power-law model, and the constants
n and K are given for the 4 different acids in Table 3. The results cleary show that as acid spends, acid solution becomes
4 SPE 136217

denser and acid viscosity increases. It is interesting to note that viscosities of spent acids become more similar as acid spending
increases.

Apparent Viscosity of Effluent Acids. Viscosity of fracture flow effluent samples collected about every 3 minutes was
measured and the percent change relative to the original acid are shown for all the acids in Fig. 6 for two different collection
times. While fresh 15 wt% HCl showed the greatest amount of viscosity change in effluent, the most spend acid of 1 wt%
spent HCl had the least viscosity change in effluent compared to the original injected acid. The results clear show there is less
viscosity change of effluent with increasing degree of acid spending, which is consistent with lower reaction rate of spent
acids. It is interesting to also note that there is no significant change in viscosity with time, which indicates similar reaction
rate at different times and also steady-state process.

Material Balance and Effluent Analysis. Effluent samples from both the leak-off and fracture flow direction were collected
and analyzed for calcium and HCl concentration. Using the concentration and volume of each sample with molecular weight
of desired species, the amount of calcium and HCl in moles were calculated and summed to define the total amount of calcium
and HCl acid present for both the leak-off and fracture flow effluent, which is summarized in Table 4 and Table 5,
respectively. The amount of calcium and HCl in moles that were injected into the cell, both in the leak-off and fracture flow
direction are also shown in Table 4 and Table 5, respectively. Concentration profiles of calcium and HCl at different times
during the acid injection process are shown in Fig. 7 and Fig. 8, respectively. The solid and dashed lines represent the inlet
concentrations, which does not change with injection time. HCl concentration cleary shows that there is greater amount of acid
spending and reaction in the leak-off direction compared to the fracture flow, as the leak-off effluent HCl concentration is
almost half of the injected amount, while the fracture flow effluent HCl concentration has only reduced by less than 5% from
inflow concentration (see Fig. 8). In addition, there is a general trend of increasing reaction rate as shown by an increase in
amount of change in HCl concentration from inflow as the acid becomes less spent and more highly concentrated as expected.
While calcium concentration in the fracture flow direction also shows similar trend with increasing reaction rate with less
spent acid as shown by increasing amount of change in calcium production, there is anomaly in the leak-off direction as there
is lower calcium concentration in the effluent than the inlet (see Table 4 with numbers in red font). Lower calcium
concentration in the leak-off effluent indicates possible entrapment of calcium within the pore spaces. The calcium is most
probably trapped inside the polymer within the pore spaces as there is evidence of polymer residue on the fracture face.

Etching Pattern. Scanning of the etched fracture faces with the profilometer provides 3D images of the etching pattern. The
etched profiles of one fracture face obtained from the profilometer are shown in Fig. 9. In addition, photographs of both
fracture faces of all experiments are also shown in Fig. 10. There is a clear difference in etching pattern among the different
spent acids, with the trend of decrease in etching extent as the acid becomes more spent. Furthermore, there is greater degree
of roughness and number of asperities developed as acid spending increases. It is also interesting to note that there is also a
general pattern of more etching toward the outlet of the fracture as acid spends, while most of the etching for unspent acid
occurs near the inlet of fracture. The results concur with our understanding of reduced reaction rate and longer etched lengths
with more spent acids.

Etched Width. Based on the etching pattern analysis, the etched fracture surface volume was calculated from the difference in
surface volume between the before and after acidizing samples. From the etched surface volume, the etched surface width was
calculated using the cross-sectional area of the fracture. The etched surface width values for all the acids and both faces of the
fracture are shown in Fig. 11. There were similar etched widths on both fracture faces etched with the same acid, however the
differences among the two fracture faces increased with more acid spending. Fresh, unspent acid generated about twice as
much etching as other spent acid systems. There is a general trend of decreasing etched width with increasing degree of acid
spending, which is expected from reduced effective diffusion coefficient and acid reaction rate as acid spends.
Etched fracture width was also determined from effluent concentration of HCl as shown in Fig. 12 with the use of density
and volume of collected samples. The calculations were based on amount of HCl consumed, accounting for both the leak-off
and fracture flow, separately. As the effluent fracture flow sample was taken every 3 minutes, it was assumed that the
concentration was the same for each 3 minute interval in calcuting the etched width. As a large volume of acid is injected into
the fracture, even a small error in measurement of effluent concentrations can result in large miscalculation of etched width.
The etched widths based on effluent concentration might be more appropriate for comparison purposes. While the surface
pattern analysis for determination of etched fracture volume accounts for mainly surface etching, the effluent concentration
method takes into account both the surface and leak-off etching. While etched width based on leak-off effluent shows similar
values to surface profilometer data, the fracture flow etching shows much higher values, which is mainly due to the high
volume throughput. It is interesting that the general trend, except for the 1 wt% spent acid, is more similar etched widths
between fracture flow and leak-off flow as acid is spend more, which is expected based on lower reaction rate of spent acid.
The etched widths based on effluent concentration also generally agree with the trend of decreasing etching with more spent
acid as was the case from surface profile data.
SPE 136217 5

Fracture Conductivity. Conductivity measurements after the acidizing for all experiments are shown in Fig. 13. It is
interesting that the most spent acid generates highest conductivity values at almost all closure stress levels, while the fresh,
unspent acid of highest acid concentration results in the lowest etched conductivity at almost all closure stresses. Furthermore,
while the spent acid solutions only show a sharp decline in conductivity at the closure stress of 1,000 psi, fresh acid shows a
rather steeper decline in conductivity over the entire tested closure stress interval. As a result, spent acids retain conductivity at
high values much more than the fresh acid. The results suggest that the spent acid systems weaken the fracture face to a lesser
degree than the fresh, unspent acid, resulting in better retainment of conductivity with increasing closure stress. While the
fresh, unspent acid dissolved larger volume of fracture face, the etching pattern was not as conductive as etching generated by
spent acids, which dissolved less fracture face.

Conclusions
The impact of acid spending on acid fracturing process was examined. Based on the results obtained, the following
conclusions can be drawn:

1. Acid spending influences the degree of etching and the etching pattern due to differences in chemical and physical
properties of acid systems. While unspent acid generated the greatest amount of etching, more conductive etching patterns
were created by the spent acid systems.
2. The majority of experiments showed significant differences in conductivity among the different degree of spent acid. Under
the experimental conditions, the most spent acid of 1 wt% gelled HCl generated the highest conductivity at almost all closure
stresses, while the unspent acid of 15 wt% gelled HCl had the lowest retained conductivity and also the sharpest decline in
conductivity over the whole closure stress interval.
3. Furthermore, effluent analysis on both the leak-off and fracture flow showed that there was greater etching and reaction in
the leak-off direction compared to the fracture flow direction. Effluent concentration and viscosity measurements confirmed
reduction in reaction and etching as acid became more spent.
4. Calcium effluent concentrations in the leak-off direction also indicated possible entrapment of certain amount of calcium in
the pore spaces, which was most likely contained within the polymer system.

Acknowledgements
We would also like to thank Dr. A.D. Hill for lending fracture conductivity setup that was used in this study. Also we would
like to express our gratitude to Schlumberger for providing us with chemicals.

References
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Conway, M.W., Asadi, M., Penny, G.S., and Chang, F. 1999. A Comparative Study of Straight/Gelled/Emulsified Hydrochloric Acid
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and Exhibition, Houston, TX, 3-6 October.

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Engineering 4 (2): 215-220. SPE-16883-PA

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6 SPE 136217

Novotny, E.J. 1977. Prediction of Stimulation from Acid Fracturing Treatments Using Finite Fracture Conductivity. JPT 29 (9): 1186-1194.
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SPE 136217 7

TABLE 1—SUMMARY OF EXPERIMENTAL CONDITIONS.

Fresh Acid Viscosity at
Case Calcium Concentration, wt% Leak-off Flux, ft/min
300 s-1, cp
15 wt% Fresh HCl 0 0.0035 22.92
10 wt% Spent HCl 7.62 0.0060 31.20
5 wt% Spent HCl 15.23 0.0052 43.57
1 wt% Spent HCl 21.33 0.0030 48.13

TABLE 2—PROPERTIES OF INJECTED ACIDS.

15 wt% Fresh 10 wt% Spent 5 wt% Spent 1 wt% Spent
HCl HCl HCl HCl

Density,a g/cm3 1.07 1.11 1.16 1.18

HCl Concentration, wt% 15.57 9.57 4.94 1.12
a. measured at 25ºC.

TABLE 3—POWER-LAW CONSTANTS AS A FUNCTION OF ACID SPENDING.

Acid System n K, g/(cm s2-n)
15 wt% Fresh HCl 0.703 131.38
10 wt% Spent HCl 0.663 226.28
5 wt% Spent HCl 0.641 362.39
1 wt% Spent HCl 0.668 352.87

TABLE 4—CALCIUM MATERIAL BALANCE IN BOTH LEAK-OFF AND FRACTURE FLOW.

Leak-off, moles Fracture, moles
Acid System Inlet Outlet Inlet Outlet
15 wt% Fresh HCl 2 74 106 201
10 wt% Spent HCl 693 545 25,595 26,321
5 wt% Spent HCl 934 713 39,800 41,975
1 wt% Spent HCl 704 482 51,251 51,717

TABLE 5—HCL MATERIAL BALANCE IN BOTH LEAK-OFF AND FRACTURE FLOW.

Leak-off, moles Fracture, moles
Acid System Inlet Outlet Inlet Outlet
15 wt% Fresh HCl 1,087 640 69,702 66,920
10 wt% Spent HCl 1,176 618 43,440 42,828
5 wt% Spent HCl 550 362 23,453 23,084
1 wt% Spent HCl 75 38 5,435 4,733
8 SPE 136217

Fig. 1— Effect of acid spending on effective diffusion cofficient for 15 wt% HCl (Conway et al., 1999).

Fig. 2— Effect of effective diffusion cofficient on etched conductivity and acid penetration (de Rozières et al., 1994).
SPE 136217 9

API Back Pressure

Conductivity Cell Regulators

Heater

Brine Acid Leak-off Spent

Acid Acid
Flowmeter

High pressure Data

pump Acquisition

Fig. 3— A schematic diagram of the acid etching process.

Fig. 4— A schematic diagram of the fracture conductivity setup.

10 SPE 136217

1,000
15% Fresh
10% Spent
5% Spent
1% Spent
Viscosity, mPa.s

100

10
1 10 100 1000

Shear Rate, s-1

Fig. 5— Viscosity of original acids with different degrees of spending.

70.0

60.0

50.0
% Change in Viscosity

40.0

30.0

20.0

10.0

0.0 After 12 minutes

15% Fresh
10% Spent After 6 minutes
5% Spent
1% Spent

Fig. 6— Change in viscosity at 300 s-1 of fracture flow effluent for all experiments at two different collection times.
SPE 136217 11

160,000
15% Fresh -
Fracture

1% Spent Inflow 15% Fresh -

140,000
Leak-off

10% Spent -
Fracture
120,000
10% Spent -
Leak-off
5% Spent Inflow
5% Spent -
Calcium Concentration, mg/l

100,000 Fracture

5% Spent -
Leak-off

80,000 1% Spent -
Fracture
10% Spent Inflow
1% Spent -
Leak-off
60,000

40,000

20,000

15% Fresh Inflow

0
0 2 4 6 8 10 12 14 16 18
Time, minute

Fig. 7— Calcium concentration profile for both leak-off and fracture flow for all experiments.

18
15% Fresh -
Fracture
15% Fresh Inflow
16 15% Fresh -
Leak-off

10% Spent -
Fracture
14
10% Spent -
Leak-off

12 5% Spent -
HCl Concentration, wt%

Fracture

10% Spent Inflow 5% Spent -

10 Leak-off

1% Spent -
Fracture
8
1% Spent -
Leak-off

6 5% Spent Inflow

1% Spent Inflow
2

0
0 2 4 6 8 10 12 14 16 18
Time, minute

Fig. 8— HCl concentration profile for both leak-off and fracture flow for all experiments.
12 SPE 136217

Depth, in.
15 % Fresh HCl 10 % Spent HCl

5 % Spent HCl 1 % Spent HCl

Fig. 9— 3-D etched profiles after acidizing process for one face of all experiments.

Flow direction

15 % Fresh HCl

10 % Spent HCl

5 % Spent HCl

1 % Spent HCl

Fig. 10— Photos of etched fracture faces for both acids of all experiments.
SPE 136217 13

0.018

0.016

0.014

0.012
Etched Fracture Width, in.

0.010

0.008

0.006

0.004

0.002

Face B
0.000

Face A
15% Fresh HCl
10% Spent HCl
5% Spent HCl
1% Spent HCl

Fig. 11— Etched fracture width from surface profile for both fracture faces of experiments.

0.300

0.250
Etched Fracture Width, in.

0.200

0.150

0.100

0.050
Surface
Fracture

0.000
Leak-off

15% Fresh HCl

10% Spent HCl
5% Spent HCl
1% Spent HCl

Fig. 12— Total etched fracture width from HCl effluent in leak-off and fracture flow direction in addition to surface profilometer values.
14 SPE 136217

100,000
15% Fresh HCl

10% Spent HCl

5% Spent HCl

1% Spent HCl

10,000
Conductivity, md-ft

1,000

100

10
0 1000 2000 3000 4000 5000 6000
Closure Stress, psi

Fig. 13— Fracture conductivity for all the experiments.