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Wayne Frenier, SPE, Mark Brady, SPE, Salah Al-Harthy, SPE, Roberto Arangath, Keng Seng Chan, SPE,
Nicolas Flamant, SPE, and Mathew Samuel, SPE, Schlumberger
Summary
A revolutionary family of treating fluids designed for the stimulation of critical, hot, or exotic oil and gas wells has been developed through application of detailed chemical and engineering
studies.13 Formulations based on the hydroxethylaminocarboxylic acid (HACA) family of chelating agents have now been used
to successfully increase production of oil and gas from wells in
a variety of different formations. Included in the field test matrixes were new and producing wells drilled into carbonates
and sandstone formations. The temperatures of the wells treated
ranged from 230 to 370F (110 to 187C) bottomhole static temperature (BHST).
Because these formulations do not contain high concentrations
of corrosive mineral or organic acids (the formulations are less
acidic than carbonated beverages), very low corrosion rates of the
tubulars can be achieved by application of small amounts of special, inexpensive corrosion inhibitors. The mild fluids also are
highly retarded so that high-temperature carbonates can be stimulated and sensitive sandstone formations are not damaged. The
fluids have reduced health, safety, and environmental (HSE) footprints because:
(1) They are much less toxic to mammals as well as to aquatic
organisms than mineral acids or organic acids such as hydrochloric
(HCl), hydrofluoric (HF), or formic acid.
(2) The fluids are returned to the surface at pH values between
5 and 7, and they frequently can be added to normal well production fluids without neutralization.
(3) Because of much lower corrosion rates for corrosion resistant alloys (CRAs), lowered concentrations of Ni and Cr will be in
the well returns compared with conventional acids that also may
contain antimony (as a corrosion inhibitor).
Introduction
While mineral acids can be very effective stimulation fluids at low
temperatures, the use of HCl-based fluids at high temperatures
[generally defined as greater than 200F (93C)] can cause many
problems. The major concerns are damage to corrosion-resistant
tubular materials, toxicity of the fluids and inhibitors, too rapid attack
on the formation (carbonates), and massive damage to clays in sandstone formations. Alternative fluids based on the HACA family of
chelating agents can be formulated to alleviate these problems.
This paper will describe the scientific basis for using these
fluids in hot formations. We also describe a completely new family
of matrix stimulation fluids, based on HACA chemicals, that has a
unique ability to be tailored to specific formation conditions. Because of the high acid solubility of HACA chemicals, formulations
of low- as well as high-pH fluids have been produced. A major
application will be that of stimulating high-temperature carbonate
formations where mineral acids cannot be pumped fast enough to
produce wormholes unless these are retarded by the formation of
emulsions. In addition, this paper describes results from laboratory
tests and field treatments using chelating agent fluids for matrix
1
vKeq
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . (4)
1
1
1
+
+
K1 vkr vKeqK3
Damkhler numbers (low injection rates), the reactants are consumed at the core face, and little penetration (wormhole formation)
is achieved. The Damkhler number for a cylindrical wormhole
can be calculated using Eqs. 3 through 5. The Fredd and Fogler46
papers propose that the optimal Damkhler number is approximately 0.29 for a large number of solvents. Using this value and an
average wormhole diameter of 0.16 cm, the optimal flow rates for
Na3HEDTA fluids with pH of 12, 4, and 2.5 were calculated and
displayed as a function of temperature (Fig. 2).
To validate these predictions, coreflood tests with Indiana limestone were performed with various chelating agents and acid systems from 150 to 400F [65 to 204C]. All the HEDTA-based
fluids stimulated the cores; some produced as much as a 400-fold
increase in permeability.
The CT scans and inlet photographs of the wormholes for tests
run at 250F (121C) and 2 mL/min are shown in Fig. 3. Wormholes were observed to penetrate the entire length of the cores for
all pH values. The diameter of the wormhole formed with the
aggressive HEDTA pH 3.5 with formic acid fluid was much larger
than that formed with the other HEDTA fluids. This observation is
consistent with the weight loss of the core.
Several HEDTA formulations were tested at 350F (177C). In
addition, 10% acetic acid was used to stimulate the limestone core.
This acid was tested because it is currently one of the few materials
used at these high temperatures. A new procedure was used to
relate the laboratory core flow data to radial flow in a limestone
formation. The procedure relied on previous work performed by
Fredd and Fogler,16 who normalized the wormhole formation phenomenon with a single 3D surface. The kinetic and equilibrium
constants measured for HEDTA were incorporated into this model.
In addition, computational fluid dynamics (CFD) simulations were
performed with a commercial simulator to investigate the effects
of the pressure and velocity fields on the wormhole density in
radial flow. Fig. 4 shows how the amount of flow going through
Fig. 2Projected optimal flow rates at specific core geometry for 20% Na3HEDTA at NDa=0.29.
November 2004 SPE Production & Facilities
191
chlorite, and illite) and a feldspar (albite). The initial reaction rates
were all below 0.5 mmol/kg/min. For comparison, 9/1-mud acid
has an initial rate on kaolinite at 150F (65C) of approximately 10
mmol/kg/min. See Fig. 8 for a rate curve for this reaction. Therefore, we would not expect this chelating agent to damage acid
sensitive clays. A study by Hartman et al.13 demonstrated the
deleterious effects of mineral acids on acid-sensitive clays at much
lower temperatures than those seen in tests.
To determine the effects of using different types of stimulation
agents (chelate, HCl, or mud acid) on an undamaged core, three
fluids were tested at 350F (177C). Results of coreflood tests
using Berea sandstone (bulk analysis in Table 2) are in Table 3
and Figs. 9 and 10. Each test included two stages of 2% KCl to
determine initial permeability, a treatment stage [10 pore volumes
(PV) of acid] followed by two stages of potassium chloride (KCl)
to determine retained permeability. Table 3 shows the permeability
values at the end of the initial two KCl stages, at the end of the acid
stage, and at the end of each retained-permeability KCl stage. The
percentage of returned permeability is based on the final KCl
stage. The graphs show metals (Al, Si, and Ca) in solution during
the coreflood tests run at 5 mL/min through the 1-in.-diameter by
6-in.-long (25150 mm) sandstone core.
The chelating fluid Na3HEDTA stimulated the Berea core better than HCl and 9% HCl with 1% HF (9/1-mud acid) at 10 PV.
From the data in Table 3 as well as the permeability vs. time traces,
it is clear that the HCl and mud acid fluids reduced the average
permeability of the cores during the treatment phase. This is expected based on the work of Bryant and Butler,21 who found
damage to a majority of cores exposed to HCl at 176F (80C).
Table 4 shows the total Al, Si, and Ca conversions at the end
of the experiment for the fluids investigated in the study. Conversions are based on Al and Si present in the aluminosilicates (i.e.,
all minerals excluding quartz) in the core. The wt% amorphous
silica reported in the table is the amorphous silica still present in
the core at the end of the experiment. It was estimated as follows.
First, an average Al/Si ratio in the aluminosilicates was calculated
using XRD data. The ratio was approximately 0.56. Second, the Al
and Si concentrations in the effluent were integrated to obtain the
total amount of Al and Si brought into solution. Third, the expected amount of Si in the effluent was estimated from the Al/Si
ratio in the virgin core and the produced amount of Al. It was
assumed that no Al compounds precipitated in the core. Fourth, the
missing Si in the effluent was assumed to precipitate as hydrated
silica (SiO2.2H2O). The wt% reported in Table 4 is based on this
composition of amorphous silica. This is an estimated value, but it
serves as a good indicator for the performance of each fluid.
The data support a model wherein the permeability of the HClor HF-treated cores improves because amorphous silica precipitated by these acids is removed by KCl. The solubility of silica
increased dramatically as the KCl displaced the acid. The concentration of Si in KCl is in agreement with literature22 values on
solubility of silica in aqueous fluids at high temperatures. However, in a reservoir treatment, a post-flush after the acid stage
would move the precipitates deeper into the reservoir. This may be
recorded as an improvement in injectivity during the treatment as
the precipitate bank would move away from the wellbore. However, when the well is put back on production, the precipitates
would flow back and damage the near-wellbore area. Shaughnessy
and Kline8 noted damage after treatment of wells using HCl but
not after chelant treatments. If the reservoir pressure is not high,
the damage may be permanent, as these precipitates may never be
produced back. Furthermore, during an actual treatment, the fluids
would initially go to the high-permeability zones. These zones will
be damaged first, before the fluid diverts itself to the lowpermeability zones in the well. If the treatment is continued, successively all zones will be damaged. After the well is put back on
production only certain zones may clean up, and after this happens,
the damage from other zones may prove difficult to remove. Thus,
the remaining damage may never be adequately removed. Therefore, although we see a net improvement in permeability with
the HCl/HF fluids, it may not be realized in practice because a
large pressure differential may be required to flow back the pre-
Fig. 4Flow distribution between the wormholes and the well face based on radial flow simulations performed with the CFD code.
192
Fig. 5Efficiency of stimulation (PVBT) vs. pump rate for four acids at 350F (177C).
193
basis for the treatment and the best means of stimulating while
minimizing adverse precipitation reactions. A hydraulic fracture
was also considered but was left as a contingency option because
of the comparatively high cost, coupled with somewhat uncertain
economic potential in a relatively new and underdeveloped field.
The results of initial solubility tests conducted at 180F (82C)
indicated that the formation samples were dissolved 12 to 15% in
15% HCl, 27 to 38% in half-strength mud acid (HSMA), and 2 to
6% in HACA pH 4. The tests involving HSMA exhibited significant precipitation after the 1-hour solubility test at this low temperature. Further solubility tests were conducted in an autoclave at
370F (188C). The data showed a significant increase in formation solubility with the HACA pH 4 solutions with no reprecipitation evident. Because no suitable core plugs were available, a
geochemical simulator23 was used to predict the radial skin generated after treatment with a traditional mud acid treatment. Fig.
11a shows the detrimental impact of a 5% HCl preflush followed
by a 6/0.5-mud acid and is consistent with the precipitation of
amorphous silica. The use of organic mud acid systems (Fig. 11b)
showed a mild stimulation during the formic acid preflush and a
significant increase in skin when the formation was treated with a
6:0.5 formic/ HF system. The conclusion here was that an HFbased treatment constituted a high risk of damage. Organic acids
such as formic or acetic acid were considered less of a risk in terms
of formation damage, but still pose a problem in terms of difficulties inhibiting these acids for prolonged periods at 375F
(190C). On the basis of laboratory and simulation studies as well
as field experience relating to the use of HF systems in hightemperature wells, a chelating agent solution was thought to provide the least risk and the best option to at least remove the calcium, magnesium, and iron carbonate minerals without inducing
damage through clay degradation and precipitated byproducts.
Treatment Design. The interval [12,250 to 12,279 ft (3675 to
3684 m)] was treated through 238-in. (60-mm) tubing set with a
packer at 12,080 ft (3624 m). A preflush of 3% KCl brine with
mutual solvent and a strong water-wetting surfactant, nitrified with
N2 to 50% quality, was pumped. A clay-control additive was in-
was routed to the separator, allowing a significant savings in operating time (no need for neutralizing and pumping back to production facilities).
A 2.79-in. (71-mm) gauge cutter was run up to a 2.31-in.
(58-mm) nipple at 7,480 ft (2280 m) without finding any obstruction.
The post-treatment liquid rate was 2,528 B/D (402 m3/d)
with a water cut of 33.2%. The increase in oil production was 283
B/D (45 m3/d), indicating that the sandstone was not damaged. The
flow increased because of the removal of scale and possibly from
stimulation of the formation.
Fig. 9Metals during coreflood of Berea core with 9/1 mud acid,
350F (177C).
195
main reason for selecting the chelant is its enhanced reaction with
the limestone and limited reaction with the dolomite.
Treatment Design. The treatment was carefully designed with
the aid of a matrix stimulation design software package. The treatment consisted of using HACA pH 3, which was chosen for its
higher reaction rate than conventional chelants at this temperature
[230F (110C)], and the treatment was placed using coiled tubing.
A preflush of 10% mutual solvent mixed in water was used ahead
of the HACA solution to enhance injection. Water wetting of the
formation also will reduce surface tension during flowback. The
simulator predicted a radial penetration of 5 ft (1.5 m) of the
HACA into the critical matrix of the limestone. In addition, a
limited reaction of HACA with the dolomite layers was observed.
The simulator also predicted a skin evolution of 0 in the limestone
layer by the end of the treatment.
The average treating pressure and rate for the HACA treatment
was 1,200 psi (8280 kPa) and 0.35 bbl/min (0.056 m3/min). It was
observed that when the HACA reached the perforations, the pressure had declined by 400 psi (2760 kPa); therefore, the rate was
increased to ensure mechanical diversion across the zone. However, it was necessary to decrease the pumping rate because the
pressure was rebuilding as a result of pumping a lighter fluid into
the coiled tubing. After the well was displaced to diesel, the coiled
tubing was pulled 2,000 ft (600 m) above the perforated zone and
a lift was started with N2. As soon as the well was lifted with N2,
the coiled tubing was pulled out of hole.
Results. During treatment, a pressure drop was observed,
which demonstrates that the chelating agent did react with the
formation.
By stimulating the limestone and penetrating into the dolomite, we met the job objective. This was determined by production
on surface. It was estimated that if the dolomite streaks had been
stimulated and allowed to produce, the expected GOR could have
been 5000 ft3/bbl (880 m3/m3). With this kind of challenge, the
ideal stimulating fluid chosen for the job was the HACA, because
it has the feature of low reaction rate with the dolomite.
The HACA stimulation treatment had increased the oil production from 0 to 600 bbl/d (96 m3/d) with a GOR of only 1500 to
1700 ft3/bbl (264 to 299 m3/m3).
Conclusions
1. Laboratory tests and simulations have shown that HACA chelating agents can be used to stimulate carbonate and sandstone
formations at high temperatures. Because of reduced reaction
rates and corrosion rates, these fluids can be used to successfully
stimulate high-temperature hydrocarbon formations, where
strong mineral acids could damage the well tubulars and the
producing formations.
2. During field tests in sandstone and carbonate formations with
BHST to >365F (185C), fluids based on these chelating agents
196
14. Kung, M.S.: Flow and Reaction of Weak Acids in Carbonate Porous
Media, MS dissertation, U. of Michigan, Ann Arbor, Michigan (1998).
15. Lund, K. and Fogler, H.S.: AcidizationII. Dissolution of Calcite in
Hydrochloric Acid, Chem. Eng. Sci. (1975) 30, 825.
16. Fredd, C.N. and Fogler, H.S.: Optimum Conditions for Wormhole
Formation in Carbonate Porous Media: Influence of Transport and
Reaction, SPEJ (September 1999) 196.
17. Gdanski, R.D. and Shuchart, C.E.: Advanced Sandstone-Acidizing
Designs With Improved Radial Models, SPEPF (November 1998)
272.
18. Thomas, R.L., Crowe, C.W., and Simpson, B.E.: Effect of Chemical
Treatment Upon Formation Clays Is Revealed by Improved SEM Technique, paper SPE 6007 presented at the 1976 SPE Annual Technical
Conference and Exhibition, New Orleans, 36 October.
19. Van Domelen, M.S. and Jennings, A.R., Jr.: Alternate Acid Blends for
HT/HP Applications, paper SPE 30419 presented at the 1995 SPE
Offshore Europe Conference, Aberdeen, 58 September.
20. Shuchart, C.E.: Chemical Study of Organic-HF Blends Leads to Improved Fluids, paper SPE 37281 presented at the 1997 SPE International Symposium on Oilfield Chemistry, Houston, 1821 February.
21. Bryant, S.L. and Butler, D.C.: Formation Damage From Acid Treatments, SPEPE (November 1990) 455.
22. Iler, R.K.: The Chemistry of Silica, John Wiley and Sons, New York
City (1979) 76.
23. Ziauddin, M. et al.: The Use of a Virtual Chemistry Laboratory for
Design of Matrix Stimulation Treatment in the Heidrun Field, paper
SPE 78314 presented at the 2002 SPE European Petroleum Conference,
Aberdeen, 2931 October.
Wayne W. Frenier has recently retired from Schlumberger after
more than 30 years of research and development activities in
the energy industry. His most recent assignment was as a
Schlumberger Advisor in product development in Sugar Land,
Texas. He is the author of 23 U.S. patents, two books, and nu-
Fig. 11Geochemical simulator output showing the radial skin developed during (a) 5% HCl followed by a 6:0.5 mud acid
treatment, and (b) a 9% formic acid preflush followed by a 6:0.5 organic mud acid (6% formic acid: 0.5% hydrofluoric acid).
November 2004 SPE Production & Facilities
197
Fig. 12Treatment pressure responses during stimulation of a high-temperature sandstone with a chelating agent solution.
merous technical articles. Frenier holds an MS degree in chemistry from the U. of Chicago. Mark Brady is a Geomarket Technical Engineer for Schlumberger in the Arabian Gulf area,
where he is responsible for introduction of new technology and
development of stimulation services. He also has been responsible for research and development activities involving drilling
and stimulation services in North America and Europe. He is the
author of four U.S. patents and numerous technical articles.
Brady holds a PhD degree in chemistry from The Queens U.,
Belfast, U.K. Salah Al Harthy is currently an operations manager
for Schlumberger in Oman and is responsible for stimulation
services in the Arabian Gulf region. He has extensive experience with implementation of numerous well services, including
Fig. 13pH vs. time plot for returns from Test Well 2.
198
held technical and engineering posts with Schlumberger, introducing and developing new well-servicing products. He is
the author of numerous technical papers. Chan holds a PhD
degree in chemical engineering from the U. of Florida. Nicolas
Flamant is a Senior Solutions Engineer in Schlumbergers Sugar
Land engineering center, where he is responsible for developing engineering models to support stimulation services. He is
the author of several technical papers. Flamant holds an MSc
degree from the Ecole Natl. Superieure des Mines de Nancy,
Parc de Saurupt, France. Mathew Samuel is an MEA client sup-
199