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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
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Wormhole Formation
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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.
References
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SPEJ. September 2000.
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11.
12.
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18.
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35
30
10%Na4EDTA
25
20
10%Acetic Acid
15
10%LCA
10
5
0
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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)