Copyright 2000, Society of Petroleum Engineers Inc.

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Abstract
Conventional matrix acidizing in carbonate reservoirs uses
hydrochloric acid to remove formation damage and stimulate
well performance. Many experimental and theoretical studies
in carbonate acidizing have confirmed the existence of an
optimal acid injection rate at which major wormholes are
formed, and the benefit from stimulation is maximized. This
optimal rate depends on reservoir conditions, rock properties
and chemical reaction rate. At high reservoir temperature, the
optimal rate of hydrochloric acid is usually too high, and it
sometimes is beyond the maximum injection allowed (the rate
to avoid fracturing formation). In this case, weak acids, such
as acetic acid, are alternative fluids to stimulate the wells. In
our previous study, a theoretical model showed that under the
same condition, the optimal injection rate for weak acids is
relatively lower than the one for strong acids.
This paper presents an experimental study of the
wormholing process in carbonate acidizing with acetic acid.
Carbonate rock samples were acidized, and the effectiveness
of the process and the optimal injection rate were studied by
measuring the acid volume needed to propagate wormholes
through the cores and by making castings of the wormhole
structures after acidizing. The experimental results from this
study confirmed that the optimal injection rate of acetic acid is
lower than the optimal rate for hydrochloric acid. It also
showed from the castings that the radius of wormholes created
by acetic acid at the optimal rate is larger than that created by
hydrochloric acid at the optimal rate. We then demonstrate
how these results can be used to determine the optimal acid
system and injection schedule for field application.
Introduction
The success of conventional matrix acidizing in carbonate
reservoirs with hydrochloric acid is often limited due to rapid
acid spending at low injection rates to prevent fracturing the
formation rock. Previous studies
1~4
in carbonate acidizing
have demonstrated the existence of an optimal acid injection
rate at which major wormholes are formed, and the benefit
from stimulation is maximized. The injection of hydrochloric
acid into carbonate formations at low rates results in compact
dissolution, or face dissolution of the carbonate matrix near
wellbore, which consumes large volume of acid and stimulates
a short distance. These studies have also shown that the
acidizing process is most efficient (defined as the process that
will enhance near-wellbore permeability to the greatest depth
with the smallest volume of acid) when major wormholes
develop.
Different fluid systems such as chelating agents
5
(EDTA),
emulsified acids
6
and foamed acids
7
have been shown to
stimulate carbonate formations at lower injection rates. The
dissolution mechanism of chelating agents is different from
that of conventional acid. Their surface reaction rates depend
on appropriate pH value. The chelating agents, in general, are
more expensive than conventional acids. Emulsified acids and
foamed acids require appropriate surfactants to maintain their
stability. Compatibility with formation fluids is another
concern of their application.
Previous work
1
in our group has demonstrated that the
optimal injection rate for acetic acid is relatively lower than
the one for HCl for the same limestone rock. A method to
calculate the reaction rate of weak acid with carbonate
minerals was presented as follows
8
:
2 2 / m
acid weak
/ m
d
f acid weak
C K E r = (1)
The acid dissociation constant K
d
can be obtained from the
following equation
8
:
SPE 58715
Carbonate Matrix Acidizing with Acetic Acid
T. Huang, SPE, L. Ostensen, SPE, and A. D. Hill, SPE, The University of Texas at Austin
2 T. Huang, L. Ostensen, A. D. Hill SPE 58715
T A A
T
A
K log
d 3 2
1
10
+ = (2)
where A
1
, A
2
, and A
3
are constants.
And

=
RT
E
exp E E
f f 0
(3)
where E is activation energy (which is 1510
3
kcal/kg-mol.),
R is the gas constant (which is 1.987 kcal/kg-mol. K.),
reaction order m is 0.63, and
63 0
3 2
7
0
10 314 7
.
f
m
HAc mole kg
sec m
HAc mole kg
. E

= (4)
The optimal acid fluxes for HCl and acetic acid
(HAc) are:
( )
opt
Da
m
HCl
f
opt
N
RT
E
exp C E
u

=
1
0
(5)
( )
opt Da
) / m (
HAc
/ m
d
f
opt
N
RT
E
exp C K E
u

=
1 2 2
0
(6)
The optimal Damkohler number is:
( )
( )
L k
r /
N
max
/
opt
Da
3 2 3
20
= (7)
The optimal Damkohler number is fixed for a given
formation and depends strongly on the largest pore size
naturally occurring.
From Equations (5) and (6), one can see the optimal acid
flux for HAc is lower than that for HCl for the same rock
system, because the surface reaction rate for HAc is slower
than that for HCl.
For 11.6% HAc and Indiana limestone which are used in
our experiments, we predict the optimal acid flux for this
system to be 0.017 cm/min by using equations above.
This paper presents an experimental study of wormholing
process in carbonate acidizing with acetic acid. One aim of the
study was to confirm the theoretical approach above. From the
experimental results, we discuss the efficiencies of a HCl acid
system and a weak acid system such as acetic acid in the field
applications. Then the wormhole size needed to overcome
formation damage is studied.
Experimental Procedures
Coreflood experiments were performed at room temperature
using the apparatus shown in Figure 1. Indiana limestone
cores of 1 inch diameter and 6 inches in length were used. The
cores had porosities around 16 percent and permeabilities of
4.8 to 14.5 md.
Experiments were performed by first vacuum saturating a
core with water and mounting it in a standard core-holder.
Confining pressures of 1500 psi were applied by a hand pump
to ensure that flow did not bypass the core. Fluid was injected
axially into the core at a constant rate using a syringe pump.
Water was first injected through the core at the desired flow
rate. The pressure drop across the length of the core was
monitored by a differential pressure transducer and recorded
by a computer. When the flow was stabilized (the pressure
drop was constant), acid injection was started. To avoid acid
contacting the pump, the acid was displaced by white oil. A
minimum system pressure of 1000 psi was maintained with a
back pressure regulator to keep carbon dioxide in solution.
The recorded pressure drop was used to calculate the
permeability as a function of fluid volume injected using
Darcy's law. The experiment was terminated when the
wormhole broke through the core as indicated by the pressure
drop being near zero. Then the core was removed from the
core-holder to dry in the oven. To determine the wormhole
structures in the acidized cores, Woods metal castings
9
were
made. The molten Woods metal at about 200 F and at
atmospheric pressure was injected into the acidized cores.
After the metal solidified, the Woods metal-filled cores were
placed in HCl acid to dissolve the remaining limestone and the
wormhole castings were kept. The castings were photographed
by a digital camera.
The acetic acid concentration used in the experiments was
1.96 N (11.6%) with a pH of 2 and a dissolving power on
limestone of 0.036 volume of limestone/volume of
acid
8
.
Results
Wormhole Formation with Acetic Acid. A group of
wormhole castings is shown in Figure 2. The pore volumes of
acid injection required for wormhole breakthrough at the end
of a core and the acid injection rates into the core are listed on
the top of the wormhole castings. From Figure 2, one can see
that the injection rate increases from left to right and the
wormhole radii at lower injection rates (first one and second
one) are larger than that of the third one which is at the
optimal injection rate. As injection rate continues to increase,
the wormhole radii are getting larger and small branches more
meandrous. Experiments exhibit a clear minimum acid
volume, illustrating the optimal acid injection rate for
wormhole propagation. The optimal acid injection rate for the
Indiana limestone with 11.6% acetic acid was 0.4 ml/min,
SPE 58715 Carbonate Matrix Acidizing With Acetic Acid 3
corresponding to an optimal acid flux of 0.078 cm/min. The
acid breakthrough volume was 3.9 pore volumes.
Comparing with our previous experimental results
3
with
3.4% HCl, which had an optimal acid injection rate of 1
ml/min, and a breakthrough pore volume of 1.6, the results
from this study confirmed that the optimal injection rate of
acetic acid is lower than the optimal rate for hydrochloric acid.
The acid breakthrough volume for acetic acid is also higher
than that for hydrochloric acid. Comparison of wormhole
castings between the two kinds of acids also showed that the
radius of the wormholes created by acetic acid at the optimal
rate are larger than that created by hydrochloric acid at the
optimal rate.
At low temperature as in our experiments, acetic acid
requires considerably more acid to propagate wormholes than
does HCl. At elevated temperature, the reaction rate is higher
and acetic acid will become more efficient, and may be the
preferred acid, as predicted by linear modeling work.
Experiments at high temperatures are needed to confirm this
supposition.
At low temperatures, HCl appears preferable to acetic
acid, unless large diameter wormholes are needed. The size
(radius) of wormhole needed to overcome the effects of
formation damage is investigated in the next section.
Wormhole radius needed to remove damage. To determine
the wormhole radius needed to overcome formation damage
effects, we can derive an approximate skin factor for a
damaged well with wormhole extending through the damaged
region. Consider a well with a damaged region having a
permeability k
s
extending to a radius r
s
, wormholes extend
through the damaged zone. Assuming radial Darcy flow
through the damaged matrix and linear tube flow through the
wormholes, the total flow rate is
( )

s
w s
wh
w
s
s
p h
r r
nr
r
r
ln
k
q

+ =
8
2
4
(8)
Comparing this rate with that obtained in an undamaged
well, and using the definition of the skin factor
10
, we find that
the skin factor is

( )
( )
w
s
w s s
w
s
wh
w
s
w s
r
r
ln
r r k
r
r
ln nr
r
r
ln r r k
s
+

=
16
16
4
(9)
where k is the undamaged permeability and n is the
wormhole density (number of wormholes per unite length of
wellbore).
From our previous studies
11
, a typical wormhole density is
12 wormholes per foot of wellbore. For a 6 inches diameter
wellbore, a damaged zone extending 6 inches beyond the
wellbore, an undamaged permeability of 50 md, and damaged
permeability of 5 md, the relationship between skin factor and
wormhole radius is given in Fig. 3. This shows that
wormholes of about 0.1 mm radius are large enough to give an
overall skin factor of zero. At room temperature, HCl creates
wormholes significantly larger than this, so the larger
wormholes created by acetic acid are not needed.
Conclusions
1. The optimal injection flux of acetic acid is lower than that
of HCl for the same reservoir conditions.
2. Larger wormholes are created by acetic acid at the
optimal flux than that by hydrochloric acid at the optimal
rate.
3. Wormholes of 0.1 mm radius are sufficient to give a skin
factor of zero if they extend through the damaged zone.
4. While acetic acid may have benefit over HCl at elevated
temperature, at low temperature HCl is the preferred acid.
Nomenclature
A
1,2,3
= constants
C
weakacid
= acid concentration of weak acid
C
HCl
= acid concentration of HCl
= activation energy
E
f
= reaction rate constant
k = permeability of the rock matrix
k
s
= permeability of damaged area
K
d
= acid dissociation constant
h = formation thickness
L = average pore length
m = reaction order
n = wormhole density
(N
Da
)
opt
= optimal Damkohler number
p
s
= pressure drop
q = production rate
r = reaction rate
R = gas constant
r
max
= maximum pore radius
r
s
= formation damage radius
r
w
= radius of the wellbore
r
wh
= radius of the wormhole
s = skin factor
T = temperature
u
opt
= optimal acid flux
= acid viscosity
References
1. T. Huang, A. D. Hill, and R. S. Schechter: Reaction Rate and
Fluid Loss: The Keys to Wormhole Initiation and Propagation in
Carbonate Acidizing, SPE 37312 J. Production & Facilities in
press.
2. C. N. Fredd and H. S. Fogler: Alternative Stimulation Fluids
and Their Impact on Carbonate Acidizing, SPE 31074
presented at the SPE Formation Damage Control Symposium
held in Lafayette, Louisiana, 14-15 February, 1996.
4 T. Huang, L. Ostensen, A. D. Hill SPE 58715
3. Y. Wang, A. D. Hill, and R. S. Schechter: The Optimum
Injection Rate for Matrix Acidizing of Carbonate Formations,
SPE 26578 presented at the 1993 SPE Annual Technical
Conference and Exhibition, Houston, 3-6 October, 1993.
4. C. N. Fredd and H. S. Fogler: The Influence of Equilibrium
Reactions on the Kinetics of Calcite Dissolution in Acetic Acid
Solutions, Chem. Eng. Sci., 53 (22), 3863-3874 (October
1998).
5. C. N. Fredd and H. S. Fogler: Chelating Agents as Effective
Matrix Stimulation Fluids for Carbonate Formations, SPE
37212 presented at the 1997 SPE International Symposium on
Oilfield Chemistry held in Houston, Texas, 18-21 February
1997.
6. B. Bazin, and G. Abdulahud: Experimental Investigation of
Some Properties of Emulsified Acid Systems for Stimulation of
Carbonate Formations, SPE 53237 presented at the 1999 SPE
Middle East Oil Show held in Bahrain, 20-23 February 1999.
7. M. G. Bernardiner, K. E.Thompson, and H. S. Fogler: Effect of
Foams Used During Carbonate Acidizing, SPEPE (Jan. 1992)
350-356.
8. R. S. Schechter: Oil Well Stimulation, Prentice-Hall, New York
City (1992).
9. M. L. Hoefner and H. S. Fogler: Pore Evolution and Channel
Formation During Flow and Reaction in Porous Media, AIChE
J. ( January 1988) 34, No. 1, 45-54.
10. M. J. Economides, A. D. Hill and C. Ehlig-Economides:
Petroleum Production Systems, Prentice Hall PTR, New Jersey
1994.
11. T. Huang, D. Zhu, and A. D. Hill: Prediction of Wormhole
Population Density in Carbonate Matrix Acidizing, SPE 54723
presented at the 1999 SPE European Formation Damage
Conference held in The Hague, 31 May-01 June, 1999.
SPE 58715 Carbonate Matrix Acidizing With Acetic Acid 5
Figure 1 Schematic diagram of coreflood apparatus.
Control Panel
Pump
Transducer
C
O
R
E
Water/Acid
source
Acid/water
Waste
Confining
Pressure
Computer
6 T. Huang, L. Ostensen, A. D. Hill SPE 58715
Q=0.15ml/min Q=0.20ml/min Q=0.40ml/min Q=0.75ml/min Q=2.0ml/min Q=6ml/min
k=10 md k=13 md k=14.5 md k=7.5 md k= 11.8 md k= 11.5 md
PVBT= 15.0 PVBT= 4.5 PVBT= 3.9 PVBT= 5.9 PVBT= 9.7 PVBT= 21.9
Figure 2 Wormhole castings formed during the dissolution of limestone by 11.6% HAc.
-2
0
2
4
6
8
10
12
0 0.005 0.01 0.015 0.02 0.025 0.03
wormhole radius (cm)
S
k
i
n

f
a
c
t
o
r
Figure 3 Influence of wormhole radius on damaged well skin factor.