SPE 86520

Method for Characterizing Secondary and Tertiary Reactions Using Short

Reservoir Cores
Murtaza Ziauddin, SPE, Matthew Gillard, SPE, Bruno Lecerf, SPE, Wayne Frenier, SPE, Schlumberger; and Iain
Archibald, Duncan Healey, ChevronTexaco

Copyright 2004, Society of Petroleum Engineers Inc.

This paper was prepared for presentation at the SPE International Symposium and Exhibition
on Formation Damage Control held in Lafayette, Louisiana, U.S.A., 1820 February 2004.
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Abstract
A new technique for characterizing secondary and tertiary
reactions during sandstone matrix stimulation treatments is
presented. In the new technique, traditional experiments on
short reservoir cores are supplemented with measurement of
the effluent element concentrations, batch reactor experiments
and geochemical simulations to predict the extent of secondary
and tertiary reactions in the reservoir treatment. Alternative
methods of characterizing secondary and tertiary reactions,
such as those using long core flow tests and laboratory radial
flow setups, are reviewed.
The new design technique is used in designing a treatment
for a well in the North Sea. Details of how this technique was
applied to the treatment design are presented. Post-treatment
data from the well showed a successful matrix treatment
design. The production from the well increased by 1,400%
immediately after the treatment. The 3-month stabilized
production gain was 650%.
Introduction
Recent studies on matrix stimulation have strongly
emphasized the importance of secondary and tertiary reactions
in determining the success of matrix stimulation treatments.1,2
However, the extent of these reactions under reservoir
conditions is difficult to quantify. Several factors make the
traditional acid response tests on short reservoir cores
inadequate for characterizing secondary and tertiary reactions.
First, secondary and tertiary reactions are slower than primary
reactions, and so much longer fluid residence times in the core
are required to observe these reactions. Second, linear flow
along the axis in cylindrical cores is not representative of
radial flow in a reservoir treatment. Third, cores used in the
core tests may not be representative of the entire
treatment interval.

Fig. 1 illustrates the limitations of traditional core flow

tests. Fig. 1a shows that a core plug is a small sample of the
area of interest. For formations in which the mineralogy
changes significantly in the pay zone interval, a single core
plug will not be representative of the entire treatment interval.
Fig. 1b shows an example of how a traditional core flow
test to evaluate two fluids on a short reservoir core can lead to
erroneous conclusions. Shown in the figure are permeability
profiles in a simulated reservoir treatment after injection of 50
gal/ft of acetic acid preflush followed by 100 gal/ft each of (i)
12/3 mud acid and (ii) an organic fluoboric acid. In both cases
the reservoir was undamaged prior to treatment. 12/3 mud acid
provides good stimulation near the wellbore, but causes
damage deeper in the reservoir. The organic fluoboric acid
achieves a lesser stimulation near the wellbore but also causes
lesser damage deeper in the reservoir than 12/3 mud acid. The
post-treatment skin for the organic fluoboric acid is -0.5,
compared to a skin of 2 for the 12/3 mud acid. The organic
fluoboric acid is, therefore, a better fluid for the reservoir
treatment. However, if these two fluids were evaluated with a
traditional core flow test, 12/3 mud acid would have been
erroneously selected because it provides better stimulation at
the length scale of the core (~4 in.). Therefore, core tests on
short cores by themselves are inadequate for fluid selection for
matrix treatments. For accurate evaluation of a proposed
stimulation design, it is necessary to account for the formation
damage caused by secondary and tertiary reactions, which are
typically not observed in tests on short cores.
Literature Review
The following is a brief review of the techniques suggested
in the literature to quantify secondary and tertiary reactions
and to overcome limitations of tests on short cores.
Experiments on Long Cores
Secondary and tertiary reactions are much slower than
primary reactions, and so much longer fluid residence times in
the core are required to observe these reactions. For typical
injection rates, temperatures below 250F, and typical clay
type and content, these reactions are not observed in cores
shorter than 6 in. Therefore, to observe these reactions much
longer cores of up to 3 ft in length have been suggested in the
literature3,4. This longer core length is also meant to simulate
the critical matrix near the wellbore. Secondary and tertiary
reactions can still occur beyond this depth in the reservoir, but

their influence on the final skin is generally assumed to

be minimal.
However, in practice, quantification of secondary and
tertiary reactions by experimentation with long cores is
problematic. Long reservoir cores are difficult to obtain, and
outcrop or synthetic cores often must be used instead. Cores
from outcrops with mineralogy similar to the reservoir are
seldom available, and therefore it is not possible to simulate
specific interactions between the various clays that can occur
in the reservoir treatment. In synthetic cores, it is not possible
to obtain the same clay sedimentation as in the reservoir even
if one matches the bulk mineralogy. Sedimentation affects the
reactive surface area and consequently the reaction rates.
Consequently, experiments with outcrop and synthetic cores
are only helpful in studying general reaction mechanisms and
are not useful in determining specific reactions that may occur
under reservoir treatment conditions. Experimental designs in
which multiple short reservoir cores are linked in series to
produce a long core have also been suggested.5,6 Although
these experiments are more representative than experiments
with synthetic and outcrop cores, they still do not adequately
represent the reservoir treatment as discussed below.
Experiments with Simulated Radial Flow
Linear flow along the axis in long cylindrical cores is not
representative of radial flow in a reservoir treatment. In radial
flow, the fluid velocity decreases as the fluid moves away
from the wellbore. Typically, the fluid velocity at about 3 ft in
the reservoir is only 10% of the velocity at the sandface,
whereas in linear flow the exit and entrance velocities are the
same. Entrainment, mobilization, and deposition of
precipitates depend strongly on the fluid velocity, and
therefore, are not represented well in a linear core flow test.
Furthermore, in typical core flow experiments, particulates are
produced with the effluent but are generally not collected and
quantified. Permeability damage will not be observed if
particulates do not accumulate in the core. Moreover, typical
core flow tests are conducted under constant flow rate
conditions and pressure spikes caused by any permeability
damage may dislodge some of the particulates that would
otherwise have stayed in the core. However, in a reservoir
treatment the increase in pressure would either divert the flow
to other zones or move the damage deeper in the reservoir.
Therefore, simple residence time corrections to linear core
flow tests are not adequate for predicting the location of
precipitates in the reservoir treatment.
Experimental setups using multiple cores have been
suggested in the literature. Kotlar and Hove7 suggest the use of
five linear reservoir cores to mimic radial flow. Calculated
volumes of fluid are withdrawn from the main fluid flow path
to reduce fluid velocities. This technique is more
representative of the field treatment than single linear core
flow tests. However, the experimental setup requires special
instrumentation and equipment that may not be available in
typical laboratories. Moreover, experimental costs can become
prohibitive if a large number of tests are required.
Scaleup to Reservoir Treatment
Cores used in the core tests may not be representative of
the entire treatment interval. Depending on the type, degree,

SPE 86520

and scale of reservoir heterogeneity, these differences can be

significant. If the length scale of the reservoir heterogeneities
is larger than the core dimensions, experimentation with a
single core can be misleading. To properly represent
heterogeneities in mineralogy in the treatment interval, tests
on several core samples are required, the cost of which can be
prohibitive. Proper representation of the heterogeneities in the
fabric of the formation, such as laminations, conglomerates,
shale lenses, or natural fractures is challenging, and the current
practice is to either ignore the effects of these heterogeneities
or account for them by some crude assumptions.
Damage caused by drilling, fines migration, or scale are
difficult to reproduce reliably in the laboratory. Therefore,
core tests, especially those that are used in ranking the
candidate stimulation fluids, are typically conducted on
undamaged cores. In many cases the damage consumes a large
fraction of the acid, and damage characteristics such as
composition and location are as important as reservoir
characteristics. If the core flow tests are conducted on
undamaged cores, the important interactions between the
dissolution products from damage and reservoir minerals
cannot be quantified. Consequently, traditional core tests alone
are not sufficient in evaluating proposed treatment designs.
Because of the limitations mentioned above, traditional
core flow tests on short cores only provide a first-level
screening for fluid compatibility with the reservoir. If the fluid
causes serious damage in the core test, the fluid is eliminated
from the candidate list. However, if the fluid does not cause
observable damage in the core, one cannot conclude that it
will not cause damage in the reservoir. Furthermore, even a
ranking of the proposed stimulation fluids is not possible with
traditional core tests because the ranking can be significantly
different in the reservoir treatment (Fig. 1b). Current
techniques suggested in the literature for quantifying the
impact of secondary and tertiary reactions do not provide
practical alternatives that can be used in routine treatment
design to overcome the limitations of traditional core
flow tests.
Description of the New Technique
In this paper we present a new technique for quantifying
the effect of secondary and tertiary reactions that circumvents
many of the problems described above. The new technique
uses tests on short reservoir cores in combination with simple
experiments with batch reactors and geochemical simulations.
The recommended procedure in the new technique is to
measure the element concentrations such as aluminum (Al)
and silicon (Si) in the effluent from the core, in addition to
measuring the permeability response during the core test. The
core flow test is then simulated with the geochemical
simulator and the mineral surface areas in the simulator are
calibrated to match the measured element concentrations. All
other kinetic and thermodynamic parameters are kept constant
during this calibration. The simulator computes a change in
core porosity for a given effluent element concentration. This
change in porosity and the measured permeability response
during the core test is used to calibrate the permeabilityporosity correlation in the simulator. Once the simulator is

SPE 86520

calibrated for the simulation of interest, then it is run in radial

flow mode to predict the reservoir treatment.
The calibration for mineral surface areas and permeabilityporosity relations in the geochemical simulator are required
because these parameters can vary significantly between
formations. However, if a reservoir core is not available, then
average values of these parameters from existing formations in
the database with similar geology and mineralogy can be used
to estimate the treatment outcome.
The use of the geochemical simulator in the new technique
eliminates the need for tests with long cores. This is because,
in the new technique, core tests are only required to calibrate
mineral surface areas and the permeability-porosity
relationship. Short reservoir cores are adequate and sometimes
even the preferred method of calibrating these parameters.
Typically, one core flow test is sufficient for calibration. If
desired, an additional core flow test at a different flow rate can
be included for validation. Previous techniques used cores to
calibrate the reaction kinetics, which necessitated the use of
long cores. In the new technique the reaction kinetics for the
individual minerals are obtained from batch reactor tests
(described below), which can be run for several hours and are
ideal for obtaining reaction kinetics for slow reactions.
In the new technique the scaleup to reservoir conditions of
radial flow is accomplished with a geochemical simulator.
Radial flow in the geochemical simulator is accounted for by
calculating the reduction in the fluid velocity in grid cells as
the fluids move away from the wellbore. An important aspect
of scaleup to radial flow conditions is the prediction of the
location and quantity of precipitates from secondary and
tertiary reactions in the reservoir. Since the reaction kinetics in
the new technique are obtained from batch reactor tests, which
are much more sensitive to these reactions than core flow
tests, an improved prediction is achieved with the
new technique.
The effects of heterogeneities in the treatment interval,
such as variation in mineralogy and permeability, can be
accounted for in the simulation if well logs such as gamma
ray, geochemical, or porosity logs are available. The extent of
the damage can be estimated from the damage skin from
NODAL* production system analysis and from production and
drilling logs. This information can be used to define initial
mineral profiles for reservoir and damage minerals prior to
simulation. If precise information about the damage and
reservoir mineralogy variation is not available, at least
sensitivity analysis on these variables can be performed.
Unlike with alternative design techniques, many treatment
scenarios can be simulated relatively easily on the computer to
optimize
the
treatment
design
and
examine
what-if scenarios.
The Geochemical Simulator
The geochemical simulator plays a crucial role in the
treatment design with the new technique. It is based on a
combination of equilibrium and kinetically controlled
reactions. Details of the geochemical simulator including its
validation have been presented previously,8 and only a brief
description is given here.
*

Mark of Schlumberger

Thermodynamic Data
Thermodynamic data for mineral and aqueous species in
the geochemical simulator were obtained from various
literature compilations. The main sources of the data were the
compilations prepared by Wagman et al.,9 and Shock and
Helgeson.10 For species for which no reliable data were
available, thermodynamic constants were estimated from
solubility and bond energy data. Most of the solubility data for
this purpose were obtained from Linke.11 Currently, the
geochemical database in the simulator contains data for more
than 1,000 aqueous species and more than 100 minerals. Data
on organic acids, chelating agents, and many precipitates
formed during sandstone acidizing are included. The validity
range for most of the data is up to 600F and 50,000 psi.
Batch Reactor Tests
In the new technique, reaction kinetic data for minerals are
obtained from batch reactor tests.8 Batch reactors are ideal for
determining reaction kinetics of slow precipitation reactions,
such as secondary and tertiary reactions, because they can be
conveniently run at long fluid residence times, and allow
accurate quantification of precipitates because the reactor is
closed. In the new technique, the geochemical simulator
mathematically combines the reaction kinetics of individual
minerals obtained from batch reactor tests and predicts the
results for a mixture of minerals. A thermodynamic model is
used to predict interactions between the dissolution products
from various minerals. The main advantage of this approach is
that once the reaction kinetics for a pure mineral with a fluid
are determined, they can be reused in all future treatments in
which the same mineral and fluid system are encountered.
More than 100 batch reactor tests were conducted to
determine the reaction kinetics of common sandstone minerals
(clays, feldspars, zeolites, carbonates) with common fluids
over a temperature range of 75 to 300F. In these tests the
reaction rates were monitored by analyzing the element
concentrations in the aqueous phase with an inductively
coupled plasma spectrometer (ICP). X-ray diffraction (XRD),
nuclear magnetic resonance spectrometer and scanning
electron microscope were used to examine the solid phase as
needed. In addition, to test the ability of the thermodynamic
model to predict the interactions between dissolution products
from various minerals, several batch reactor tests were also
conducted with mixtures of minerals. The data from the tests
were archived in a database for easy retrieval for
future treatments.
Fig. 2 shows a sample of data from batch reactor tests that
were used in determining the reaction kinetics in the
geochemical simulator. Shown in the figure are the evolution
of Al and Si concentrations in the aqueous phase during
dissolution of kaolinite clay with 9/1 mud acid and fluoboric
acid. Symbols in the figure are the measured concentrations,
while the solid lines are model predictions. To examine the
sensitivity of the batch reactor test to secondary and tertiary
reactions, two simulations were conducted. In the first
simulation the primary, secondary, and tertiary reactions were
included in the model, and in the second simulation only the
primary reaction of the clay was included. For the 9/1 mud
acid, the predictions with and without secondary and tertiary
reactions start deviating significantly after about 5 min of

reaction time, while for the fluoboric acid (a retarded acid)

significant deviations are observed after 25 min. These trends
are quite easily detected in batch reactor test. However, in a
short core test the typical fluid residence time is less than 5
min and contribution from secondary and tertiary reactions
would be difficult to observe (see below). Therefore, batch
reactor tests are much more sensitive to the kinetics of
secondary and tertiary reactions and more precisely determine
the kinetics of these reactions than tests on short cores.
Core Flow Tests
More than 50 cores from various formations were tested
under a wide range of conditions to validate the geochemical
simulator. The range of core lengths used in the test was from
1 to 36 in. The temperature range was from 75 to 300F.
Traditional fluids such as mud and organic mud acids, and
nontraditional fluids such as retarded acids and chelating
agents, were tested. The permeability response during the test
was measured and the effluent from the core was analyzed
with an ICP. For long cores (>1 ft) multiple pressure taps
along the cores were used to track the permeability fronts. The
data collected to date show that once the geochemical
simulator is calibrated with one core test, the results for other
tests on the cores from the same formation but for a different
set of input conditions (such as different core lengths, injection
rates, fluids, or temperatures) can be predicted accurately.
A sample of the core tests used in validation of the
geochemical simulator is shown in Fig. 3. These tests illustrate
the ability of the simulator to scale with respect to flow rate.
The data reported in the figure is from Hsi et al.12 Shown in
the figure are Al and Si concentrations in the effluent from the
core as a function of pore volumes of fluid injected. Symbols
in the figure are the measured concentrations, while the solid
lines are model predictions. Both cores shown in Fig. 3 are
from Kekiktuk formation and were acidized with 12/3 mud
acid but at different flow rates. The flow rate in the test shown
in Fig. 3a is approximately 3 times the flow rate for the test
shown in Fig. 3b. The same mineral surface areas were used
for all simulations shown in the figure. A good match between
measured and predicted (with 2 and 3 reactions) values is
obtained. This ability of the geochemical simulator to scale
with respect to flow rate, after calibration with a single flow
rate, is crucial for predicting results in radial flow in which the
fluid velocity constantly decreases as the fluids move away
from the wellbore.
To examine the sensitivity of the short core test to
secondary and tertiary reactions, a second set of simulations
were conducted for the cores shown in Fig. 3. In these
simulations the secondary and tertiary reactions were excluded
from the model. Fig. 3 compares the predictions with and
without secondary and tertiary reactions included in the
model. For both flow rates, the predictions of Al and Si
concentrations with and without secondary and tertiary
reactions are similar. This shows that Al and Si concentrations
from short core tests are insensitive to secondary and tertiary
reactions and cannot be used to obtain reliable kinetics for
these reactions.

SPE 86520

Case Study
The case study presented here documents the use of the
new technique for a well in the North Sea. Additional case
studies using the new technique are presented in Ziauddin et
al.13 and Torres et al.14

Reservoir Description
The Galley Field is located wholly within UKCS Block
15/23a, approximately 145 km East-Northeast of Peterhead on
the Scottish mainland. The acreage is held under License with
Texaco North Sea UK Company (67.416%) as license holder
and partners being Summit UK Oil Limited (17.416%) and
ENI UK Limited (15.168%).
The Galley Field commenced production on 25 March
1998, and is currently producing from three oil accumulations;
two of which are Upper Jurassic Galley Sandstone Member
reservoirs and the other a Late Paleocene Cromarty sandstone
member reservoir. The Paleocene reservoir consists of two
main areas comprising Paleocene Forties turbidite stacked
channel and overbank reservoirs (Fig. 4). Reservoir properties
are depicted in Table 1. The subject well for this study, G5, is
situated in the Forties Channel. The Cromarty channel is a
narrow, sinuous channel of fine to very fine-grained, poorly
consolidated sandstone that is flanked by laterally extensive
overbank deposits. The pay zone height in the channel is about
48 ft and the temperature is about 162 F.
Well Description
Well G5 is an oil producer, completed horizontally with a
650-ft long openhole section. Fig. 5 shows the well log
marked with a channel sand near the heel of the well, followed
by a shale section and then by three main producing intervals
(marked as 1, 2, 3). It was intended to gravel pack this well,
but because of collapse of the shale section, only a quarter of
the wellbore length was packed. The remainder of the
wellbore length has only 100-m mesh screens with no gravel
behind it.
The production history for the well is shown in Fig. 6.
Initially the well produced without water. However, in March
2002, the water cut started increasing steadily. It reached a
level of 8% in May, after which the water cut suddenly
jumped to 20%. Oil production declined steadily from the
initial production rate of 7,000 BOPD. Even before the onset
of any water in March, the oil had declined by 50% in just 5
months of production and then by 72% when the water cut
jumped to 20%. The oil production had dropped to just 200
BOPD before the stimulation treatment was performed. This
decline from 7,000 to 200 BOPD was observed in just 1 year
of production. The wellhead pressure remained steady during
the decline.
Prior to the evaluation of G5 as a candidate for stimulation,
the well had produced about 1.1 MMbbl oil, 979 MMscf gas
and 31 Mbbl water. Stock tank original oil in place (STOOIP)
estimates for the whole Cromarty sandstone is approximately
3.7 MMbbl. G5 recoverable reserves are estimated at
approximately 1.6 to 1.9 MMbbl. It must be noted that G5 has
already produced nearly 30% of the estimated STOOIP, but
interestingly, the reservoir pressure has shown very little

SPE 86520

decline. A possible explanation could be that G5 is actually

draining a larger drainage area then originally calculated.
XRD data were obtained from a core sample from the
Cromarty Channel shown in Table 2. The analysis shows
about 20% aluminosilicates and about 3% carbonates.
Solubility test conducted on the core sample showed about 3%
solubility in hydrochloric acid (HCl) and about 27% solubility
in 12/3 mud acid. The high solubility in 12/3 mud acid was
assumed to be because of the dissolution of fine quartzitic
particles in addition to aluminosilicates.
Damage Identification and Characterization
Damage identification is critical to the success of the
stimulation treatment. Several potential damage mechanisms
were identified and evaluated. Fig. 6 shows that an increase in
water production correlates well with a decrease in oil
production. Therefore, several damage mechanisms related to
water production were investigated. These are (i) swelling clay
damage in the matrix near the wellbore, (ii) inorganic scale,
(iii) hydraulic production problems due to water holdup, and
(iv) fines migration. However, as the production had declined
rapidly even before water production, residual damage from
drilling and gravel pack placement were also investigated as
potential contributors to production loss.
Swelling Clay Damage
Damage due to clay swelling occurs when water reacts
with clays in the matrix, causing them to swell and block pore
throats, resulting in a loss of permeability. XRD analysis on
the core sample showed that the volume of swelling clays such
as smectite was small and it was concluded that this was not
the dominant damage mechanism.
Scale Formation
A review of the scaling potential of the well indicated that
both calcium carbonate (CaCO3) and barium sulfate (BaSO4)
scales were likely. Because of the limited data available, it was
not possible to precisely quantify volumes of each. However,
the volume of BaSO4 scale was expected to be small. The
volume of CaCO3 scale can potentially be large because of the
large pressure drop near the wellbore.
Water Holdup
NODAL analysis showed that with the current levels of
damage the well could produce steadily with 50% water cut at
an oil production rate near 1,500 BOPD. However, if the water
cut were to exceed 50% at this oil rate, it may impede
production. Therefore, it was important in the treatment design
to make sure that the watered-out zone was not stimulated
causing an increase in water cut.
Fines Migration
Several observations indicated that migration of fines was
the dominant damage mechanism. First, XRD analysis showed
presence of migratory clays (chlorite and illite) together with
silt and mobile quartzitic material. Second, a pump-in test with
diesel in July 2002 showed a temporary increase in injectivity.
This is the classic signature of fines migration problems. Fines
act as a check valve, with higher permeability in the injection

direction compared to the production direction. The injectivity

increases as fines are washed off from the screens and out of
pore throats temporarily. Third, the production decline
correlated with an increase in water production. Water
production can destabilize fines and cause them to migrate.
Furthermore, the unconsolidated nature of the formation and
prior experience in the area supported the hypothesis that this
was the dominant damage mechanism.
Residual Drilling and Completion Damage
The reservoir was drilled with a water-based mud and
CaCO3 as bridging agent. The drilling-induced damage was
suspected to be caused by (i) invasion of filtrate, (ii) invasion
of CaCO3, polymer, starch, and drilled solids, and (iii) filtercake plugging of screen and sandface. Initially this damage
can go unnoticed in a horizontal well. However, it leads to
localized production areas, which over time can cause early
water breakthrough and accelerate fines migration.
The well could also have been damaged significantly
during the gravel-packing process. Only a quarter of the
wellbore length was packed with gravel because of the
collapse of the shale section. It is expected that the filter cake
and mud removal in the remainder of the well was extremely
poor. By restoring the productivity along the length of the
wellbore, it was believed that the drawdown on the wateredout section could be reduced. This would lower the water cut
and increase oil production.
Production Logging
The PLT* Production Logging Tool was run just before
the main stimulation treatment. The data were interpreted in
real time and were used to guide the treatment design. The
PLT results showed that there was no production (water or oil)
from the channel section of the well. In the remaining section
of the wellbore, the top 50% was producing with a water cut
of 50%, while the bottom 50% was producing dry oil but at a
low production rate.
Treatment Design
The objective of the treatment design was to remove
damage caused by (i) migration of clays, silts, and small
quartzitic particles, (ii) inorganic scale, and (iii) drilling. The
fluids selected for damage removal were (i) a chelating agent,
(ii) acetic acid, and (iii) 9/1 organic mud acid (OMA). A
chelating agent was selected to remove CaCO3 scale as well as
BaSO4 scale (if any). Acetic acid was selected to provide
additional removal of CaCO3 scale as well as serve as a
preflush for the mud acid to remove carbonates present in the
matrix. A 9/1 OMA was selected to remove fines migration
and drilling-induced damage. A mud acid formulated with
HCl, such as 12/3 and 9/1, was not selected because prior core
flow tests with these acids had resulted in core
deconsolidation. The deconsolidation was believed to occur
because of the dissolution of the quartz cement. A 9/1 OMA is
only slightly weaker then 9/1 formulated with HCl. However,
no deconsolidation was observed with it and it was decided to
use the OMA instead of an HCl-based mud acid. The use of a
fines stabilization agent, such as fluoboric acid, was thought to
be beneficial for the treatment. The dominant damage

mechanism was believed to be fines migration and the

stabilization of fines near the wellbore would help extend the
life of the treatment. However, the stabilization agent was not
registered in the region and it could not be used.
Several fluid placement options were evaluated for the
treatment. After an economic analysis, a coiled tubing with a
jetting tool was selected as the preferred method of placing the
fluids. The cost of the placement with coiled tubing was high.
However, the benefits of using a jetting tool to clean the
screens and nitrogen lift to improve flow from the well
outweighed the additional cost.
The planned sequence of treatment fluids was as follows.
In the first phase of the treatment the chelating agent was to be
jetted along the entire wellbore. This would increase the flow
rate from the well and improve the accuracy of measurement
with the PLT tool, which was to be run next. After the
interpretation of PLT results in real time, the viscoelastic
diverter was to be injected in the zones producing
predominantly water (as identified from the PLT data). This
was to be followed by the second phase of the treatment, in
which the main oil-bearing zones were to be treated for fines
migration and residual drilling damage. Acetic acid was to be
used as a preflush, followed by the main stimulation stage
with 9/1 OMA and a brine postflush. The viscoelastic diverter
was to be pumped after stimulation of each zone. The above
sequence of preflush, main stage and postflush was to be
repeated for all oil-bearing zones.
Estimation of Damage Caused by Secondary and Tertiary
Reactions
The steps taken to estimate the damage caused by
secondary and tertiary reactions for the G5 stimulation
treatment are as follows.
(1) Core flow test with measurement of element
concentrations and permeability
The core plug from the Cromarty formation with
dimensions 3.73 x 6 cm was vacuum-saturated with simulated
formation brine. The sample was then loaded into a highpressure, high-temperature core cell for testing at reservoir
conditions. The core was cleaned by alternately flooding with
Isopar oil and simulated formation brine at 3 cm3/min
through its pore space. The sample was judged clean when the
effluent for the core was clear.
The core was then heated to the reservoir temperature.
Prefiltered test fluids were pumped through the core at 3
cm3/min. The backpressure was maintained at 1,000 psig to
keep any generated carbon dioxide in solution. Monitoring of
the flow rate and differential pressure across the core was
carried out every 30 s by a computerized data acquisition unit.
The data were stored and used to generate a plot of
permeability versus volume of fluid pumped.
All effluent leaving the core flooding apparatus was
collected using 10 mL plastic tubes. This enabled the
technician to observe the effluent and establish whether fines
were being produced during each stage of the testing
sequence. The samples were then filtered and diluted with

Isopar is a registered trademark of ExxonMobil Corp.

SPE 86520

nitric acid to prevent further precipitation. The samples were

then analyzed with ICP to measure the concentration of Al and
Si in the samples.
(2) Calibration of the Geochemical Simulator
Experimental data from the core flow test were used to
regress mineral surface areas and the parameters in the
permeability-porosity correlation in the geochemical model.
All other reaction kinetic parameters obtained from batch
reactor experiments were kept constant. Final regression-fitted
results from the geochemical model and comparisons with the
measured values are shown in Fig. 7. Symbols in the figure
are measured concentrations, while the solid lines are the
results from the geochemical simulator. No deconsolidation of
the cores was observed during the test. The figures show that
the treatment fluids were compatible with the native
mineralogy and provide an increase in permeability at least at
the core length scale.
(3) Scaleup to Reservoir Conditions
The reservoir treatment was simulated in the geochemical
simulator to see if it would provide a net increase in
permeability on the reservoir scale. Fig. 8 shows the skin
evolution during the treatment as predicted from the
geochemical simulator. The damage was assumed to be only
due to fines migration in the simulation. The skin declines
steadily with injection of 9/1 OMA. Fig. 9 shows the profile
of amorphous silica precipitate after injection of the designed
volume of 9/1 OMA. Amorphous silica is formed from
secondary and tertiary reactions, and is an indicator of the
extent of these reactions. The figure shows that the total
volume of amorphous silica is small. These results show that
the increase in permeability due to the dissolution of
aluminosilicates is more dominant than the decrease in
permeability due to precipitation of amorphous silica.
Therefore, a steady decline in skin is observed with continued
injection of 9/1 OMA.
A clay stabilization agent, such as fluoboric acid, could not
be used because it was not registered in the region. However,
it was still useful to predict the results to see if it would
provide a favorable stimulation if it were allowed. Fig. 9
shows the skin evolution with half of the volume of the 9/1
OMA substituted with fluoboric acid (thus keeping the total
fluid volume the same as before). The treatment skin after the
required shut-in with the fluoboric acid is still only slightly
larger than with 9/1 OMA alone. As treatments in offshore
wells are expensive, this small increase in skin may be
acceptable if it would increase the life of the
treatment significantly.
Treatment Execution
The treatment was executed as planned except that it was
not possible to flow back the well at the design rates. The
planned flowback rate would have recovered all the treatment
fluids in a couple of hours. However, because of operational
problems the flowback took about 24 hr. The additional
residence time of fluids in the well caused further precipitation
from secondary and tertiary reactions near the wellbore. The
geochemical simulator was used again to estimate the quantity

SPE 86520

of amorphous silica precipitated because of this delay in

flowback. Fig. 9 shows the amorphous silica profile at the end
of the flowback period. The total quantity of amorphous silica
is still small, and therefore the delayed flowback was thought
to have minimal impact on the final treatment.
Treatment Results
The stimulation treatment increased the production from
approximately 200 to 3,000 BOPD immediately after the
treatment. This represents an increase of more than 1,400%.
The water cut after the treatment was 45%, which is a small
increase over the water cut prior to the treatment. The PLT just
before the main treatment had showed that the water was
being produced with the oil and not from an isolated zone.
Therefore, it was not possible to stimulate the oil production
alone. Three weeks after the treatment, the production rate was
about 2,500 BOPD. Currently, 3 months have elapsed since
the treatment and the well is producing steadily at 1,500
BOPD. This represents an increase of 650% over the
prestimulation rates.
The production increase after the treatment was much
larger than what is typically achieved after removal of fines
migration damage. This is consistent with Fig. 8, which
shows a small improvement in skin after the treatment, if fines
migration is assumed to be the only damage. It is, therefore,
possible that the dominant damage is due to CaCO3 scale or
residual drilling and completion fluids and not due to fines
migration. A flowback analysis or post-treatment PLT log
was not available to test this hypothesis. The presence of
significant quantities of Ca+2 in the flowback would have
suggested the presence of CaCO3 (either from scale or drilling
fluids). A PLT after the treatment would have identified zones
contributing to the additional production. If the zones
producing with a high water cut, were contributing to
additional production, then damage due to CaCO3 scale would
have been more likely. However, if the zones that were
originally producing dry oil or no fluids at all were stimulated,
then damage due to CaCO3 scale would have been less likely.
Furthermore, due to equipment failure, no pressure data was
recorded during the treatment. Therefore, it was not possible
to determine during which stage in the treatment the greatest
gain in injectivity was achieved.
To estimate the improvement due to the injection of acetic
acid and 9/1 OMA, the production rates after the first phase of
the treatment were compared to the production rate
immediately after flowback. The first phase of the treatment
involved jetting of a chelating agent along the entire wellbore.
As 9/1 OMA or acetic acid were not used in the first phase of
the treatment, the improvement in production after the first
phase can be assumed to be due to mechanical cleaning and
the removal of inorganic scale by the chelant. The total
production rate after this phase of the treatment was 1,000
BOPD, with a water cut of about 40%. A comparison of this
production rate, with the production rate of 3,000 BOPD, after
the treatment with acetic acid and 9/1 OMA, suggests that at
least an increase in production by 2,000 BOPD can be
attributed to these fluids. However, as bottomhole pressure
was not recorded during the treatment, it was not possible to
determine if either the 9/1 OMA or acetic acid provided the
most stimulation during the second phase of the treatment. If

such data was available, the geochemical simulator could have

been used to estimate the contributions of the various
damage mechanisms.
Conclusions
This paper presents a new technique for quantifying the
extent of secondary and tertiary reactions during sandstone
acidizing treatments. The new technique uses one or two short
reservoir cores (1 to 6 in.) to determine the type, quantity, and
location of precipitates in the reservoir. Previous techniques
required the use of long cores (1 to 3 ft) or elaborate radial
flow setups for such determination. Long reservoir cores are
difficult to obtain and the cost of radial flow experiments can
be prohibitive. The use of short reservoir cores by the new
technique makes it more accessible for routine
treatment design.
In the new technique, core tests on short cores are used to
determine surface areas of minerals and the porositypermeability relationship for the formation. This information
is then mathematically combined with previously archived
reaction kinetics of secondary and tertiary reactions of the
individual minerals to determine precipitation under reservoir
treatment conditions.
The presented case study shows that successful matrix
stimulation treatments can be designed for complex reservoirs
using the new technique. One core flow test with a short
reservoir core combined with geochemical simulations was
adequate in estimating the damage caused by secondary and
tertiary reactions. The new technique showed that for this
particular case the damage due to secondary and tertiary
reactions would not be significant. The new technique was
also helpful in estimating the damage caused by secondary and
tertiary reactions due to a delay in flowback because of
operational problems during the treatment. It was not possible
to identify the dominant damage mechanism conclusively, as
limited data was available for analysis due to budget
constraints and operational problems during the treatment.
However, even with the limited data, the sensitivity analysis
with the new technique did provide additional insight into
likely damage mechanisms for the well. The treatment
designed with the new technique resulted in a successful
matrix treatment.

Acknowledgments
The authors thank Schlumberger, ChevronTexaco and their
partners ENI UK Ltd and Summit UK Oil Ltd, in the Galley
license for their permission to publish the paper. The authors
would also like to thank Justin Thomas for his invaluable
reservoir performance and economics analysis, Martin Taylor
and Liz Morris for help with core flow tests, and Richard
Warren for his interpretation of the real-time production
logging data.
References
1. Gdanski, R. SPE 37214 Kinetics of the Secondary
Reaction of HF on Alumino-Silicates in SPE
International Symposium on Oilfield Chemistry,
1997. Houston.

SPE 86520

2.

3.

4.

5.

6.
7.

8.

9.

Gdanski, R.D. SPE 31076 Kinetics of Tertiary

Reaction of HF on Alumino-Silicates in International
Symposium on Formation Damage Control, 1996.
Lafayette.
Fambrough, J.D. and D.P. Newhouse. SPE 26186 A
Comparison of Short-Core and Long-Core Acid Flow
Testing for Matrix Acidizing Design in SPE Gas
Technology Symposium, 1993. Calgary, Canada.
Gdanski, R.D. SPE 30100 Fractional Pore Volume
Acidizing Flow Experiments in SPE European
Formation Damage Symposium, 1995. The Hague.
Wehunt, C.D., et al. SPE 25211 Laboratory
Acidization of an Eolian Sandstone at 380F in SPE
International Symposium on Oilfied Chemistry, 1993.
New Orleans, LA.
Gdanski, R.D., AlCl3 Retards HF Acid for More
Effective Stimulation. OGJ, 1985: p. 111-115.
Kotlar, H. and A. Hove. Acid Stimulation Studies in
Simulated Radial Flow Conditions: Laboratory
Results Compared with Field Data in SPE
International Symposium on Formation Damage,
2000. Lafayette, LA.
Hartman, R.L., et al. SPE 82267 Acid Sensitive
Aluminosilicates: Dissolution Kinetics and Fluid
Selection for Matrix Stimulation Treatments in SPE
European Formation Damage Conference, 2003. The
Hague, The Netherlands.
Wagman, D.D., et al., The NBS Tables of Chemical
Thermodynamic Properties. Selected Values for

10.

11.

12.

13.

14.

Inorganic and C1 and C2 Organic Substances in SI

Units" Supplement No. 2. J. Phys. and Chem. Ref.
Data. 1982. 11: p. 2-392.
Shock, E.L. and H.C. Helgeson, Calculation of the
Thermodynamic and Transport Properties of
Aqueous Species at High Pressures and
Temperatures: Correlation Algorithms for Ionic
Species and Equation of State Predictions to 5 kb and
1000 C. Geochim. Cosmochim. Acta, 1988. 52: p.
2009-2036.
Linke, F., Solubilities of Inorganic and MetalOrganic Compounds. fourth ed. Vol. 2. 1965,
Washington, D. C.: American Chemical Society.
1914.
Hsi, C.D., S.L. Bryant, and R.D. Neira. SPE 25212
Experimental Validation of Sandstone Acidization
Models in SPE International Symposium on Oilfield
Chemistry, 1993. New Orleans.
Ziauddin, M., et al. SPE 78314 The Use of a Virtual
Chemistry Laboratory for the Design of Matrix
Stimulation Treatments in the Heidrun Field in SPE
13th European Petroleum Conference, 2002.
Aberdeen, Scotland.
Torres, C., et al. Application of a Unique Clay
Stabilizing Acid in the Gulf of Thailand in PetroMin
Deepwater
Technology,
2003.
Kuala
Lumpur, Malaysia.

SPE 86520

Table 1. Reservoir and Well Properties

Reservoir Properties
Porosity
2831%
Permeability
40100 mD
Residual water saturation
25%
Reservoir pressure
2,666 psi
Reservoir temperature
162F
Well Properties
API gravity
49.1
Gas/oil ratio
1,032 scf/bbl
Reserves for G5
2.1 MMbbl

Table 2. Mineralogy from X-ray Diffraction

Whole Rock Analysis

Albite
K-feldspar
Quartz
Illite-smectite
Calcite
Clay Analysis
Mixed-layer illite-smectite
Chlorite

6%
10%
77%
4%
3%
97%
3%

10

SPE 86520

(a) Core Sample

(b) Permeability Profile and Skin Values

k / k0

300F
Kaolinite 10%
Calcite 3%
Quartz 87%
Porosity 20%

12/3 Mud Acid

Final Skin = 2

Wellbore

Pay Zone

4 inch core

Organic Fluoboric Acid

Final Skin = -0.5

2
1
0
0

Critical matrix (3ft)

1
2
3
Distance from center of wellbore (ft)

Core Plug
(1-6 in)

Fig. 1. (a) Core plugs are only a small sample of the area of interest. (b) Permeability profiles after treatment of an undamaged reservoir with 12/3 mud
acid and an organic fluoboric acid

Kaolinite in Fluoboric Acid (65C)

Kaolinite in 9/1 Mud Acid (65C)

0.6

0.6

Al, Si without 2 & 3 Rxns

Al with 2 & 3 Rxns

Conc (mol/kg)

Conc (mol/kg)

Al with 2 & 3 Rxns

0.4
Al measured
Al,
. Si without 2 & 3 Rxns
0.2

Si measured
Si with 2 and 3 Rxns

0.4
Al measured
.
0.2

Si measured
Si with 2 & 3 Rxns

0
0

100

Time (min)

200

300

100

Time (min)

200

300

Fig. 2. Data from batch reactor experiments used in determining the dissolution rate of kaolinite in 9/1 mud acid and fluoboric acid. The model
predictions are shown with and without secondary and tertiary reactions included in the model.

Core Flow Test on Kekiktuk Core (Alaska)

Core Flow Test on Kekiktuk Core (Alaska)

0.2

0.2
Si without 2 & 3 Rxns

(a)

Core Length 3 in
Acid Flux 0.03 cm/sec
Data from SPE 25212, Run 9

(b)

0.16
Core Length 3 in
Acid Flux 0.0099 cm/sec
Data from SPE 25212, Run 7

0.12

Si measured
0.08
Al without 2 & 3 Rxns

0.04

Al with 2 & 3 Rxns

Al measured

Concentration (mol/liter)

Concentration (mol/liter)

Si with 2 & 3 Rxns

0.16

Si without 2 & 3 Rxns

0.12
Si with 2 & 3 Rxns
Si measured
0.08

Al without 2 & 3 Rxns

Al with 2 & 3 Rxns
Al measured

0.04

0
0

10

20

30
40
Pore Volume

50

60

10

20

30
40
Pore Volume

50

60

Fig. 3. Core tests used in the validation of the geochemical model. The model predictions are shown with and without secondary and tertiary reactions
included in the model

SPE 86520

11

Fig. 4 . Overview of the Galley field.

Fig. 5. Log section of the G5 well.

G5 Production
800
OIL

6000

700

WHP
Oil

WATER

Water

600

5000

500

4000

400

3000

300

2000
1000

200
WHP

100

Date

Fig. 6. G5 production history.

Water BPD

7000

17 Da t
-N e
07 ov-0
-D
1
e
27 c-0
-D 1
e
16 c-0
-J 1
a
05 n-0
-F 2
e
25 b- 0
-F 2
e
17 b- 0
-M 2
a
06 r- 0
-A 2
p
26 r-0
-A 2
16 pr-0
-M 2
a
05 y- 0
-J 2
u
25 n-0
-J 2
un
15 -02
-J
04 u l- 0
-A 2
ug
-0
2

BOPD and WHP (psi)

8000

12

SPE 86520

Effluent Concentrations

Permeability
0.06

200

(b)

Concentration (mol/kg)

Permeability (mD)

(a)

150

100

50
Acetic Acid

9/1 OMA

Brine

Acetic Acid

9/1 OMA

0.04

Brine

Si

Al

0.02
K

0
0

10
15
20
Pore Volumes Injected

25

10
15
20
Pore Volumes Injected

25

Fig. 7. Data from the core flow test used in calibration of the geochemical simulator. Symbols depict measured values, while solid lines depict model
results.

Skin Evolution
250
Without Fines
With Fines Stabilization
Stabilization Treatment
Treatment

Skin

200
150
100

HAc 10%
30 gal/ft

50
Brine

0
0

25

(1) 9/1 OMA 40 gal/ft

or
(2) 9/1 OMA 20gal/ft
Fluoboric Acid 20

50
75
Volume (gal/ft)

100

Brine

125

Fig. 8. Skin evolution for reservoir treatment with OMA and a combination of OMA and fluoboric acid.

Amorphous Silica (End of Treatment)

1

Mineral Vol(%)

Critical Matrix
Amorphous Silica Due to
Delay In Flow back

0.75

Amorphous Silica at the

End of Treatment w ith OMA

0.5
0.25

0
0

1
2
3
4
5
Distance from Center of Wellbore (ft)

Fig. 9. Amorphous silica profile in the reservoir at the end of the OMA treatment and after delay in flowback