Copyright 2007, Society of Petroleum Engineers

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Chemistry held in Houston, Texas, U.S.A., 28 February2 March 2007.

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Abstract
The purpose of matrix treatments in carbonate reservoirs is to
increase connectivity of a formation with the wellbore in the
entire zone of interest. Successful matrix treatments depend on
the uniform distribution of the treating fluid over the entire
interval. When fluids are pumped into a well, they naturally
tend to flow into the zone with the highest permeability or
least damage. Field experiences showed that there is no
assurance of complete zone coverage without proper
diversion. Therefore, diversion is recommended in all
treatments, especially in extended reach and multi-lateral
wells.
Diversion techniques can be classified as mechanical or
chemical. Mechanical control of treating fluid placement can
be accomplished by coiled tubing with an inflatable packer, or
with conventional straddle packers or ball sealers. Although
mechanical techniques are very effective, they are more
expensive and time consuming than chemical techniques and
they are often not applicable or not effective in wells with
open-hole completion. More importantly, mechanical means
diverts treatment fluids from the wellbore; however, there is
no control once the fluid enters the formation. Chemical
diversion can be achieved through placing a viscous fluid,
foam or gel to lower the penetration of treatment fluid in the
created wormholes and their surrounding matrix, or a
particulate carrying fluid, which creates a filter cake on the
surface of the wormholes. This filter cake results in temporary
skin effect which alters the injection profile. Gelled and
foamed acids are also being used as a means of improving acid
placement by combining stimulation and diversion in one step.
Diversion is a critical step to ensure the success of matrix
acid treatments. Understanding how chemical diverters
interact with the formation rock and fluid is the key to
selecting the proper product for a specific treatment. It is the
intent of this paper to provide a technical overview of
mechanical and chemical diverters used in the oil industry.
The various mechanisms by which these chemicals to achieve
acid diversion, their application histories, and their limitations
are presented. This paper provides guidelines for production
engineers to optimize the fluid placement.

Introduction
Matrix acidizing in carbonates provides opportunity not only
to remove or by pass damage in the vicinity of the wellbore,
but to also improve the near-wellbore permeability by creating
large flow channels (wormholes) with the acid dissolution.
The chemistry of carbonate acidizing is much more straight
forward than sandstone acidizing. The simplicity results form
the fact that the rock is composed of calcite (CaCO
3
) and/or
dolomite (CaMg(CO
3
)
2
). Their reaction products are soluble
in the spent hydrochloric acid. However, the physics and
engineering aspects of the carbonate acidizing process is much
more complex.
1
This is because the rock structure is
significantly altered by the dissolution reaction, which
increases the permeability contrast between the treated and the
untreated zones.
Unless effectively diverted, the treated region eventually
becomes the sink for the acid and leaving other regions not
adequately acidized. Therefore, one of the most important
factors affecting the success or failure of a matrix acid
treatment is the correct downhole placement of the acid for
optimum zonal coverage.
2
Though over the years there have
been many products and techniques developed in the industry
for acid diversion, the preferred ones generally have to possess
the following characteristics:
1. Must not cause permanent damage to the formation.
2. The diverting agent must be compatible with the treating
fluids (overflush or displacement fluids) and formation
brines.
3. Must clean up rapidly and completely when the well is put
back on production.
4. The chemical and physical properties of the diverting agent
must sustain at the bottom hole treating temperature.

Understanding how each acid diversion technique works is the
first step towards the optimized carbonate acidizing design.
Two techniques can be applied to achieve acid diversion.
Mechanical diversion, including coiled tubing and utilizing
rate and pressure during pumping; and chemical diversion.
Combination of these techniques is often practiced for added
efficiency.
3


SPE 106444
Chemical Diversion Techniques Used for Carbonate Matrix Acidizing:
An Overview and Case Histories
Frank F. Chang and Xiangdong Qiu, Schlumberger, and Hisham A. Nasr-El-Din, Saudi Aramco
2 SPE 106444
The mechanical diverting technique uses zonal isolation
tools such as packers to control the point of fluid entry; or uses
ball sealers in the cased and perforated completion to
selectively block some perforations (undamaged or that
correspond to high permeability zones). The intention of
using these methods is to divert treatment fluid right from the
wellbore. It is also sometimes called external diversion.
Though effective, setting packers often requires multiple
stages of operations, which add time and cost to the
treatment.
4
In addition, placing isolation packers in open hole
completion is not an easy task and may not be effective,
especially if the hole is not gauged.
Originally introduced in 1956, ball sealers are small
spheres designed to seat in the perforations from the inside of
the casing, thereby diverting injected fluids to other
perforations.
5
These balls are normally made of nylon, hard
rubber, biodegradable materials such as collagen.
6-8
Ball
sealers are added to the treating fluids in stages to shut-off the
perforations that are taking the largest quantities of fluids.
Although they are widely used, several drawbacks limit this
technique from providing consistent diversion. In addition to
only applicable to cased and perforated wells, a sufficient rate
must be available to maintain a differential pressure across the
perforations to keep the balls in place. Their effectiveness is
also impacted by the roundness and smoothness of the
perforation holes and by the matching of the ball specific
gravities with the treating fluid. Finally, for naturally
degradable balls, e.g. biodegradable ball sealers, the timing of
the degradation can adversely affect the sealing efficiency.
4

Paccaloni and coworkers
9
have developed a method of
using the maximum pressure differential and injection rates
(MAPDIR) to force the acid into low permeability zones. This
technique involves pumping the treatment fluids at the highest
possible rate without fracturing. Results show that the
MAPDIR technique allows fast total skin reduction in terms of
pumping time, but at the expense of large acid volumes
injected into the layer with lower damage. Furthermore, it
does not allow treating the low-permeability layer fully.
Nonetheless, the MAPDIR is a physically sound technique. It
is always practiced when a chemical diverter is used.
Coiled tubing has become a widely accepted and routinely
prescribed tool for well services and workover operations.
Coiled tubing offers several advantages over the conventional
bull heading treatments during a matrix acid stimulation.
Performing acid treatment through coiled tubing avoids
exposing the wellhead or completion tubular to direct contact
with corrosive fluids. Spotting the treatment fluid with coiled
tubing will ensure the delivery of the treatment fluid against
the target sections. When combined with chemicals
diverters
10
and MAPDIR technique, coiled tubing provides
much better chance for success in acid coverage. The
drawback of the coiled tubing is that the tubing diameter is
much smaller than that of the drill pipe or production tubing
used for bull heading treatments. Therefore, the injection rate
is limited in situations when sustained high rate and pressure
are required. In addition, when treating long horizontal wells,
extending coil tubing to the toe of the well requires tractors or
vibrators,
11-13
significantly increasing the complexity of the
treatment execution.

The fundamental difference between a chemical and a
mechanical diversion is that a chemical diverting agent
achieves diversion by increasing flow resistance insides the
created channels, whereas a mechanical diversion process
controls the fluid entry point at the wellbore. Hence the
chemical diverting agents can be considered as an internal
diverting agent as opposed to the external mechanical
diversion. It is the intent of the authors that by reviewing the
application histories of various chemical diverting agents, an
overview of the commonly used products can be provided so
that more angles can be considered by the engineers when
designing the acidizing jobs in carbonate reservoirs.

Chemical Diverting Agents
Foam, viscous gels, and particulates are commonly used
diverting agents during matrix acidizing of carbonates. These
materials reduce the fluid penetration rate in the created
wormholes by increasing effective viscosity or allow plugging
of the wormholes with finely sized solids.

Foam
Foam is a dispersion of a gas in a liquid with gas being the
non-continuous phase and liquid is the continuous phase. Its
stability is largely affected by the nature of the fluid that it
contacts. Foams have been used for acid diversion since the
1960s.
14
The acid itself can be foamed with the addition of
gas and a suitable surfactant, or, more commonly, foam can be
injected in alternating slugs with acid. Due to its profile
control capability, foam has also been used in improved oil
recovery (IOR) processes
15
and in sealing leakage in gas
storage reservoirs.
16
Foam can be generated by injecting a
surfactant solution into a porous medium and followed by gas
injection. Or it can be created by co-mingled injection of a
gas and a surfactant solution.
17
The mixing energy provided
by forcing the two phases through the porous medium is the
dominant foam generation mechanism.
18
As it flows through
the porous medium, additional foam is generated. Its
resistance to movement through the rock matrix increases until
the pressure required for further flow exceeds the pressure
required to break down other sections of the formation.
14

There are many advantages of foam diversion. Foam
blocking contains no solid material that could damage the
formation permeability. Foam expansion, while flowing well
back, helps clean well at lower reservoir pressure. Case
history
19
showed when treating many openhole water injection
wells completed in Arab-D formation in Saudi Arabia the
injection pressure gradually rose throughout the treatment
giving a positive indication of diversion. The post stimulation
injectivity increased from 26 to 112 BWPD/psi with improved
water injection distribution profile.

Viscous Diverter
A viscous gel diverter uses its high viscosity or visco-elastic
property to slow down the fluid penetration rate in the existing
wormholes so that the acid following the diverter can have
better chance to contact the rock in which wormholes have not
formed. The viscous gels use either a polymer solution or a
viscoelastic surfactant (VES).
20-22
Polymer diverters leave
residues after the gels break, potentially negating the
stimulation by damaging the matrix or the surface the
SPE 105931 3
wormholes, especially if the volume is designed incorrectly.
Surfactant-based gel is claimed to be non-damaging, however,
the potential of gel not breaking or forming the emulsion with
the reservoir oil are drawbacks of this material.
Polymer-based systems have been used previously for
blocking zones to help the gel plug reach the desired stiffness
and the required isolation between intervals. One of Polymer-
based systems Polymer Gel Diverter (PGD) has been used on
field for many wells injection. The overall injection was more
than 40% and the skin was reduced from +1 to 2.5.
23

Another Polymer based Associative Polymer Technology
(APT) also has been tested in field. Based on treatment-
pressure response, the treatment using several stages of APT
and acid appeared to divert the acid into sections of lower
permeability. Oil production increased by 34% and the water
cut decreased from 21 to 17%. Laboratory and field tests have
shown that APT can divert acid from predominantly water-
saturated zones to predominantly oil-saturated zones in
carbonate formations.
24

In addition to use alternating stages of acid/diverter, many
polymer and VES systems can be prepared in acid. Increasing
the viscosity of the acid causes elevated treating pressure
when the acid reaches the formation. There high injection
pressure thereby drives the acid into the lower permeability
zones. This idea is similar to the MAPDIR concept.
However, a much higher injection pressure is required than
MAPDIR using straight acid in order to squeeze a more
viscous acid into the lower permeability zones. The other
drawback is the potential of damaging the lower permeability
zones if the gelled acid is not efficiently broken.
An improved technology of using viscosity control
mechanism for acid diversion is an in-situ gelled acid. The
major advantage of an in-situ gelled acid over conventional
stimulation treatments is that less number of stages is required
to achieve diversion since the acid provides the stimulation
and diversion at the same time. An in-situ gelled acid uses
unique polymer or surfactant chemistry to produce an acid
system that has very low viscosity before reacting with the
carbonate rocks. In-situ gelled acid has been shown to
improve acid placement in carbonate reservoirs.
10,25
The
difference between an in-situ gelled acid and external gelled
acid is that the external gelled acids or diverting gels are
already activated on the surface. Thus, when they reach the
formation face, the viscosity is the same against the high
permeability and the low permeability rock. The proportion of
fluid entering each zone is simply determined by the
permeability contrast following the Darcys law. The in situ
gelled acid offers the benefit of increasing viscosity inside the
formation, therefore, when acid first enters the high
permeability zone and generates wormholes, its viscosity
becomes higher than the acid still in the wellbore. This
creates an injectivity contrast, which provides extra resistance
in the already treated high permeability region or in the
wormholes, in turn it helps alleviate the severity of the
permeability contrast. The result is that the acid has a better
chance to enter the low permeability un-treated zone.
The polymer-based in-situ gelled acid is prepared by
gelling the HCl acid with a polymer and adding into the
system a crosslinker.
26-28
When the acid spends upon
dissolving carbonate, the increase in pH causes the crosslinker
to activate and the gelled acid becomes crosslinked. This
crosslinked gel temporarily blocks the wormholes being
created and diverts acid elsewhere. Further increase in the pH
value by complete spending of the acid causes the crosslink to
break, the in-situ gelled acid hence breaks down to nearly
water-like viscosity to assist easy flow back. Since the system
contains polymers, even though the bulk fluid viscosity is
dramatically reduced, there is still polymer residue,
29,30
which
can potentially plug the face of the wormholes.
Viscoelastic Surfactants (VES) have been used in the
industry for several stimulation applications. Due to the
ability of surfactant monomer to associate and form certain
structures under cretin conditions, it can increase the apparent
viscosity and elastic properties of the treating fluids. A VES
based in-situ gelled acid system can be prepared by adding a
surfactant in the acid.
13,31
Under the live acid state, the
micellar structure does not cause the acid to form an elastic
gel. As the acid spends in the formation, the pH increases and
reaction products, CaCl
2
and MgCl
2
, force the surfactant
molecules to form rod-like micelles, which increase the
viscosity and elasticity of the solution. The gel breaks when
hydrocarbons contact the fluid during flow back. The
surfactant leaves no residue on the wormhole surfaces and
requires very low cleanup pressures. Due to its ease of clean
up, the VES-based gelled can have a prolonged viscosity
buildup without having to break back until the hydrocarbons
flowback. This prolonged viscosity buildup provides
additional benefit of sustained diversion. When reservoir fluid
does not naturally break the VES based in-situ gel, a post flush
of mutual solvent (ethyleneglycol monobutlyether) is
recommended to ensure the breaking of the gel.
One of field use of VES produced an average 1,600% OPD
more than conventionally treated wells. In a second oil field,
oil production increased by 4 to 5 folds. Also, several dead
wells are now naturally producing up to 7,500% OPD after
VES treatments. Since the volume of VES acid treatment is
used less than polymer based acid, this makes VES acid
operationally attractive to offshore environments. All the
wells cleaned-up faster than wells treated with polymer
systems.
13
Although the VES based in-situ gelled acid has
demonstrated its merits. Thorough lab testing is required to
ensure the applicability to specific fields. The rheological
properties of viscoelastic surfactant are a complex function of
its type, concentration, pH, additives, salinity, temperature,
shear rate and mixing procedure.
32,33
A study showed the
effect of acid additives and contaminants (mainly Fe
3+
) on the
rheological properties of VES over a wide range of parameters
(i.e. pH, temperature, and shear rate). It is observed that
temperature, pH, shear conditions and acid additives have a
profound influence on the apparent viscosity of the surfactant-
acid system.

Particulate Diverters
Bridging agents or particulate diverters is a common chemical
diverting technique used in carbonate formation. Particulate
diverting agents are fine particles that form a relatively low-
permeability filter-cake on the face. The pressure drop through
this filter cake increases the flow resistance and diverting the
acid to other part of the formation.
4 SPE 106444
There has been report of the injection of soap solutions
could react with calcium chloride (CaCl
2
) to form water-
insoluble, but oil-soluble, calcium soaps.
4
The precipitate
acted as a diverting agent for hydrochloric acid (HCl). The
generation of solid precipitates in the formation was not, of
course, desirable, because they could cause permanent
damage. Thus, in the late 1930s, more sophisticated systems
were used. Other systems utilized cellophane flakes suspended
in a water gel with a biocide, later gels were replaced by oil-
external emulsions. Oil-soluble naphthalenes, crushed
limestone, sodium tetraborate, oyster shells, gilsonite, perilite,
paraformaldehyde and chicken feed were used as diverters
with mixed success. These compounds were replaced
progressively by rock salt, which is partially soluble in the
acid, but inexpensive and easy to handle. A major
improvement of diversion techniques were brought about by
completely soluble materials, including wax-polymer blends
and hydrocarbon resins in production wells and rock salt and
benzoic acid in water-injection wells.

Benzoic acid flakes have one distinct advantage as a
diverting agent: they are soluble in both water and oil.
However, they can be used in low temperature reservoirs.
Several researchers have found that mixing benzoic acid and
rock salt in a 50/50 blend provided a very effective diverting
material. The rock salt is soluble in spent acid and some
formation fluids, and its dissolution simplifies the rate of
solubility of the remaining benzoic acid. The size of diverter
stage usually depends upon the size of the interval being
treated. A common stage size is 1,000 gallons of carrier fluid.
This stage will usually contain 1-2 lbs of sized diverting agent
per gallon for diverting treatments over long intervals.
34

Naphthalenes were first used as a blocking material in
1954. Oil-soluble naphthalenes were thought to be ideal
diverters because they sublime above 175F.
4
In 1956
Gilsonite was used as an oil-soluble diverting agent.
4
The
primary advantage of these materials is their good clean-up
characteristics and that they can be used over a broad
temperature range.
35
However, most oil-soluble resins are not
useful for acidizing in carbonates because the resin particles
are not able to bridge the large flow spaces created by the
reaction of the injected acid with the reservoir rocks.
Recently solid organic acids such as lactic acid flakes have
been used as a particulate diverting agent.
36
This type of
material hydrolyzes to release acid after the acidizing
treatment under reservoir temperature. However, hydrolysis
reaction requires sufficient water to ensure full conversion of
the solids into acid. Otherwise, the solids remain and
formation damage can be expected.
Though the particulates are soluble in water or
hydrocarbons, their removal requires exposure to the flowing
stream when the well is put back on production. Otherwise,
severe formation can occur to negate the stimulation results.

Conclusions
Effective diversion of reactive acid is necessary for efficient
matrix acidizing in carbonates. Diversion in carbonates is
more difficult than in sandstones because of the ability of acid
to significantly increase the permeability in carbonates as it
reacts in the pore spaces and flow channels of matrix.
Although mechanical techniques are very effective, they
are more expensive and time consuming than chemical
techniques and they are often not applicable nor effective in
open-holes.
The best diverting technique for a specific field is not
necessarily the best for other fields. It is crucial to understand
the geological characteristics and the petrographical properties
of the reservoir when designing the acidizing treatment by
incorporating the fit-for purpose diverting techniques.
The properly designed diversion should retain effective
blocking of fluid into the high permeability zone throughout
the treatment, but the diverting agent is rapidly and completely
removed during flow back.

Acknowledgments
The authors would like to thank Saudi Aramco and
Schlumberger for the permission to present and publish this
paper. The authors would also like to thank Abdullah S.
Sultan for many useful discussions.

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