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SPE 82268

Carbonate Matrix Acidizing Fluids at High Temperatures: Acetic Acid, Chelating Agents
or Long-Chained Carboxylic Acids?
Tianping Huang, SPE, Paul M. McElfresh, SPE, and Allen D. Gabrysch, SPE, Baker Oil Tools, Baker Hughes Inc.
Copyright 2003, Society of Petroleum Engineers Inc.
This paper was prepared for presentation at the SPE European Formation Damage
Conference to be held in The Hague, The Netherlands 13-14 May 2003.
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Abstract
Matrix acidizing of carbonate formations has been carried out
for many years using HCl acid in various strengths. However,
in some high temperature applications, HCl does not produce
acceptable stimulation results due to lack of penetration or
surface reactions. Organic acids, like formic acid and acetic
acid, were introduced to offer a slower reacting a thus deeper
stimulating acid. These retarded acids also had shortcomings due to solubility limitations of acetate or formate
salts. In recent years, several alternatives have been
developed, including aminocarboxylic acids and long-chained
carboxylic acids. These long-chained carboxylic acids offer
low corrosion rates, good dissolving power at high
temperature, high biodegradability, and easier and safer
to handle.
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 of the acid being used. In our
previous study, a theoretical model showed that under the
same conditions, the optimal injection rate for weaker acids is
lower than that for stronger acids. This paper presents a
comparison of the efficiency of stimulation in carbonate
acidizing of three different kinds of high temperature
stimulation fluids. A chelating agent, EDTA, acetic acid, and a
mixture of long-chained carboxylic acids were used to acidize
carbonate cores at high temperatures. The effectiveness of the
process and the optimal injection rate were studied by
measuring the acid volume needed to propagate wormholes
through 4-inch cores. The dendritic nature of the acid
penetration was also determined by making castings of the
wormhole structures after acidizing. The experimental results
from this study showed that the optimal injection rate of long-

chained carboxylic acids is lower than that for acetic acid and
the EDTA. This increase in efficiency then determines that a
deeper and more efficient stimulation per gallon of acid
mixture used is obtained with the long-chained
carboxylic acids.
Introduction
Matrix acidizing of carbonate formations has been carried out
for many years using hydrochloric acid acid in various
strengths. However, in some high temperature applications,
hydrochloric acid does not produce acceptable stimulation
results due to lack of penetration or surface reactions1,2. The
success of conventional matrix acidizing in carbonate
reservoirs with hydrochloric acid is often limited because the
optimal pumping rate would exceed the fracture gradient of
the formation3,4. The HCl-based acid fluids also pose problems
such as high corrosivity and sludging tendencies when the acid
contact crude oils, and the HCl sensitivity of some formations.
These problems are intensified by high temperature and high
pressure. Some corrosion problems may be alleviated by the
use of a corrosion inhibitor, but the adsorption of corrosion
inhibitors on the inside pipe surface may remove inhibitor and
reduce the protection to corrosion caused by the live acid on
the downhole tubulars. The adsorption of the inhibitors on the
rock may block the pore space, reducing water wettability and
therefore reduce the relative permeability to oil or gas16.
Organic acids, like formic acid and acetic acid, were
introduced to offer a slower reacting, and thus, deeper
stimulating acids. These retarded acids also had shortcomings due to solubility limitations of acetate or formate
salts at high acid concentrations17 and corrosion problems at
high temperatures12,13. In recent years, several alternatives
have been developed in high temperature applications,
including aminocarboxylic acids2,12 and long-chained
carboxylic acids(LCA)13,14 . Chelating agent-based fluids have
been investigated for high temperature matrix acidizing15.
Many experimental studies1~4 in carbonate acidizing
at lower temperatures have demonstrated the existence of an
optimal acid injection rate at which major wormholes are
formed, and the benefit from stimulation is maximized. These
studies have also shown that the acidizing process is most
efficient (defined as the process that will enhance nearwellbore permeability to the greatest depth with the smallest
volume of acid) when major wormholes develop. There is
some computer modeling to simulate the wormholing
process5~8. Theoretical models9,10 show this optimal rate

SPE 82268

depends on reservoir conditions, rock properties and chemical


reaction rate. In the previous study4,9, a theoretical model
showed that under the same condition, the optimal injection
rate for weaker acids is relatively lower than the one for
stronger acids.
This paper presents a comparison of the efficiency of
stimulation in carbonate acidizing of three different kinds of
high temperature stimulation fluids. A chelating agent,
Na4EDTA, acetic acid, and a mixture of LCAs were used to
acidize carbonate cores at high temperatures. The
effectiveness of the process and the optimal injection rate were
studied by measuring the acid volume needed to propagate
wormholes through 4-inch cores.
The LCA has been confirmed that it has very low
corrosion rate at high temperatures13,14. Corrosion tests show
that at 177C (350F) the corrosion rate caused by LCA is
0.00049 g/cm2 (0.001 lbs/ft2) on 22-Cr for 16 hours, which is
about 10% of the corrosion loss caused by acetic acid at the
same conditions. Frenier12 published corrosion tests showed
that corrosion rate caused by 20% Na3HEDTA is 0.00534
g/cm2 (0.0109 lbs/ft2) on 13-Cr at 177C (350F) for 6 hours.
The reaction of Na4EDTA and calcium carbonate is
different from regular acid reaction. This reaction does not
generate carbon dioxide. Na4EDTA with various ionization
reactions of carbonate system results in the overall reaction
as following:

temperature. 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 or the permeability was constant), acid injection
was started.
The experiment was terminated when the wormhole
broke through the core as indicated by the pressure drop being
near zero. Three reaction fluids were used to wormhole the
cores with different pumping rate: 10% LCA, 10% acetic acid
and 10% Na4EDTA. Each reaction fluid has shown the
optimal pumping rate (Figure 1), which means that at this
pumping rate the smallest volume of reaction fluids was
required to penetrate the cores. The cores acidized at optimal
pumping rates were selected to cast with Woods metal for
determining the wormhole structures. The molten Woods
metal at about 93C (200F) and at atmospheric pressure was
injected into the selected cores. After the metal solidified, the
Woods metal-filled cores were placed in 15% HCl acid to
dissolve the remaining limestone and the wormhole castings
were kept. The castings were photograghed by a
digital camera.

Na 4 EDTA + CaCO 3 Ca 2 EDTA + Na 2 CO3

Figure 2 to figure 4 show the wormholes at the core surface


with pumping rate increasing for 10% LCA, 10% acetic acid
and 10% Na4EDTA. From Figure 2 to Figure 4, one can see
that at lower injection rates either larger wormhole or multiwormhole generates; when injection rate increase to optimal
rate, single wormhole usually occurs; As injection rate
continues to increase past the optimal rate, multi-wormholes
are again generated.
Figure 1 shows the pore volumes of reaction fluids
injection required for wormhole breakthrough versus the
injection rate for the three reaction fluids at temperature 121C
(250F). Experiments exhibit a clear minimum reaction fluid
volume for all reaction fluids, illustrating the optimal acid
injection rate for wormhole propagation. The optimal injection
rate of LCA is the lowest rate among the three reaction fluids,
which confirms the theory4 that under same condition, the
optimal injection rate for weaker acid is relatively lower than
the one for stronger acids. The acid strength of acetic acid is
slightly strong than that of LCA, and the optimal fluid
injection rate of acetic acid is higher than that of LCA. Acid
volume required to penetrate the same distance of carbonate
formation for LCA at optimal injection rate is also the smallest
for the three reaction fluids. Nasr-El-Din18 described the
solubility of 10% Na4EDTA is much lower than that of 10%
acetic acid at 82C (180F). This may be the reason that the
fluid volume required to penetrate the carbonate cores for
Na4EDTA at optimal injection rate is higher than that for
acetic acid and the LCA. The experimental results from this
study showed that the optimal injection rate of LCA is lower
than that for acetic acid and the Na4EDTA. This increase in
efficiency then determines that a deeper and more efficient
stimulation per gallon of acid mixture used is obtained with
the LCA a mixture of the long-chained carboxylic acids.

Core Flow Test Procedures


All core flow experiments were performed at temperature
121C (250F). Indiana limestone cores of 2.54cm (1 inch)
diameter and 10.16cm (4 inches) in length were used. The
cores were cut from same rock which is 30.48 cm (1 ft) x
30.48 cm (1 ft) x 30.48 cm (1 ft). The cores had porosities
around 15 percent and permeability about 2 to 3md. X-ray
diffraction analysis indicates the Indiana limestone is
predominately calcite with a trace of quartz. Acid solubility
tests shown that the Indiana limestone is 99.01% soluble in
15%HCl and 98.86% soluble in 10%LCA. At room
temperature, the dissolving power of 10% LCA on calcium
carbonate is 53.86g/l (0.45 lb/gal.). For 10% acetic acid, the
dissolving power is 83.78g/l (0.70 lb/gal.). For acid strength,
at temperature of 25C (77F), pK a of acetic acid is 4.76,
which is slightly stronger than LCA, whose overall
average pK a is 4.89.
Experiments were performed by first vacuum
saturating a core with DI water and mounting it in a standard
core-holder. Confining pressures of 1700 psi were maintained
by an automatic air pump to ensure that flow did not bypass
the core. Back pressure of 700 psi was applied through a back
pressure regulator to prevent the liquid from vaporizing and to
keep carbon dioxide dissolved in solution. DI water was
pumped by a syringe pump through the core at 0.5ml/min
while the core was heating, and continued at the same rate for
at least one hour after the temperature reached 121C (250F)
to make the temperature of the core reach the desired

Results and Discussion

Wormhole Formation

SPE 82268

Figure 5 shows the wormhole castings with Woods


metal for the three reaction fluids at their optimal injection
rates at temperature 121C (250F). The number of wormhole
branches of LCA created at the optimal injection rate is less
than that created by acetic acid and Na4EDTA at their optimal
injection rates. The radius of wormhole created by the LCA at
the optimal injection rate is smaller than that created by acetic
acid and Na4EDTA at their optimal injection rate. Previous
study4 shows that wormholes of about 0.1 mm radius are large
enough to give an overall skin factor of zero. The radius of
wormhole created by the LCA at the optimal injection rate is
significantly larger than this, so the larger wormholes created
by acetic acid and Na4EDTA are not needed. The smaller
wormhole makes the LCA more efficient for
deeper penetration.

Corrosion Tests
In addition to the static corrosion tests performed on the LCA
and acetic acid, the following dynamic flow procedure has
shown a different perspective of corrosion tests in regard to
the LCA and acetic acid at 121C (250F).
A 1000ml of acid with 2%CI (corrosion inhibitor)
and 5% NH4Cl was loaded into a Hastalloy accumulator and
was heated to desired temperature. Two layers of 400 mesh
stainless steel screen (3.81 cm (1.5 inch) in diameter) similar
metallurgy to that used in conventional sand control screens
were on each end of a 15.24cm (6 inch) long sand pack, and
loaded into another Hastalloy tube. After the screens and sand
pack were heated to the desired temperature, the acid fluid was
pumped from the bottom up through the screen and sand pack
at 10ml/min until all the acid fluid flowed through the screens.
The screens were then examined for corrosion.
Figure 6 shows the screens after pumping 10% LCA
at 121C (250F). There is no detectable damage to the
screens as a result of the acid flow tests at the high
temperature. Figure 7 shows the two screens after pumping
10% acetic acid at 121C (250F). The acetic acid showed
high reactivity on the screens, a situation that is not obvious
from the static corrosion results.
Conclusions
1. The optimal injection rate of the LCA is lower than
that of acetic acid and EDTA for the same
reservoir conditions.
2. Smaller wormhole is created by the LCA at the
optimal injection rate than that by acetic acid and
EDTA at the optimal rates.
3. Corrosion tests demonstrate that the LCA is much
less corrosive than acetic acid at high temperatures.
4. Need more experimental and theoretical studies on
reaction rate of Na4EDTA with carbonate to provide
more information to predict the optimal pumping rate
for this application.

Acknowledgments
The authors would like to thank Jim Treadway and
Bob Uresti for their assistance with this paper. Additionally,
authors thank the management of Baker Oil Tools, Baker
Hughes Inc. for their support and permission to publish
this paper.
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SPE 82268

Comparison of LCA, Acetic acid, Na4EDTA wormholing at 121C


(250F)

35

Breakthrough Pore Volume

30

10%Na4EDTA
25

20

10%Acetic Acid
15

10%LCA
10

5
0

Pumping Rate (ml/min)


Figure 1. Pore volumes of reaction fluids breakthrough a core vs. pumping rates at 121C (250F).

pumping rate increases


Figure 2. Wormholes at the core surface for 10%LCA pumping through the cores at121C (250F).

SPE 82268

pumping rate increases


Figure 3. Wormholes at the core surface for 10%acetic acid pumping through the cores at 121C (250F).

pumping rate increases


Figure 4. Wormholes at the core surface for 10%Na4EDTA pumping through the cores at 121C (250F).

SPE 82268

H LCA; E Na4EDTA; A Acetic acid


Figure 5. Wormhole castings with Woods metal for the three reaction fluids at the optimal fluid injection rates at 121C (250F).

SPE 82268

Figure 6. 400mesh screens after pumping1000ml 10%LCA at 10ml/min and 121C (250F).

Figure 7. 400mesh screens after pumping1000ml 10% acetic acid at 10ml/min and 121C (250F)