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A Contemporary Approach

to Matrix Acidizing
G.R. Coulter, SPE, Coulter Energy Intl. and A.R. Jennings, Jr., SPE, Enhanced Well Stimulation Inc.
Summary
This paper presents an updated look at the many variables asso-
ciated with successful matrix acidizing. Damage types and forma-
tion characteristics significant when considering formation dam-
age and damage removal are presented. Emphasis is placed on
knowledge of formation mineralogy and temperature. The require-
ment for and the function of the many acid additives are dis-
cussed. General information and guidelines for matrix stimulation
of carbonates and sandstones are provided.
Introduction
The oil and gas industry has been acidizing oil and/or gas bearing
formations since the 1890s.
1
The primary acid used in the early
days was hydrochloric acid. It is interesting to note that hydro-
chloric acid is still the primary acid used today for oil and gas
well damage removal and stimulation. Since the early days, vari-
ous other acid types have been developed along with additives to
help make acidizing more effective. Acid types in use today in-
clude inorganic ͑hydrochloric and hydrochloric/hydrofluoric acid
blends͒, organic ͑formic and acetic acids͒ and mixtures of
inorganic-organic acids. Other acids such as citric, sulfamic, chlo-
roacetic, EDTA ͑ethylene diamine tetracetic acid͒, NTA ͑nitrilo
triacetic acid͒, erythorbic acid, and benzoic acid may be used in
acidizing systems for specific purposes, such as pH control, iron
sequestering, diverting, etc. In addition to these, many other addi-
tives are often used in acid treatments. These include corrosion
inhibitors, surfactants, alcohols, friction reducers, fluid loss con-
trol additives, diverting agents, acid reaction rate retarders, anti-
sludging agents, suspending agents, mutual solvents, and carbon
dioxide and nitrogen gases. Determining the acid type, concentra-
tion, additives required and their concentrations for various tem-
perature and mineralogical environments can be very perplexing
to the practicing engineer. The objective of this paper is to discuss
the important factors in selecting the correct acid for the proper
well situation. General information is presented and points out the
need to know formation mineralogy and as much about the type of
formation damage existing as possible. It is always best to con-
duct laboratory tests on core and fluid samples from the well and
interval of interest prior to conducting any damage removal treat-
ment.
A number of prior authors have contributed greatly to the in-
dustry’s understanding of matrix acidizing and damage removal.
Many of these are referenced at the end of this paper. One of the
widely referenced papers was presented by McLeod in 1984.
2
This work made an excellent contribution to the industry. With
the many new theories, additives and acid blends in use today,
there is a need to update some of the acid selection criteria from
earlier work. Additionally, the amount of interval now being
treated in many horizontal wells invites a review of the industry’s
treating and diverting methods, as well as additives and acid
types.
A premise of this paper is that the wellbore tubulars have been
thoroughly cleaned with solvent and acid or with other efficient
cleanout methods prior to the acidizing treatment. Pumping acids
and other fluids down the wellbore prior to obtaining knowledge
of the wellbore condition is discouraged. Even new tubing can
have significant amounts of mill scale as well as pipe dope, etc.
which can be detrimental to a matrix acidizing treatment. Older
producing ͑or injection͒ wells may have deposits which may only
be partially dissolved by the reactive acid and may act to divert
the acid away from portions of the producing interval where it is
most needed. Circulation of such deposits out of the well may
provide information pertinent to the acidizing treatment ͑that is,
confirm the need of organic solvents with the acid, provide scale
samples for further analysis, etc.͒.
Formation Damage Types
Formation damage, or restriction to flow through natural flow
paths in the formation, can be of three basic types. These are
absolute permeability damage, relative permeability changes, and
viscosity effects. Absolute permeability damage is that from par-
ticulate material occupying all or a portion of the formation pore
space. This blockage reduces the permeability and must be re-
moved or bypassed to overcome its effect. Relative permeability
changes often result in reduced permeability to the desired pro-
ducing fluid. This change in relative permeability can occur from
oil wetting a water wet hydrocarbon producing formation and/or
by the change in fluid saturations. These changes can occur from
a previous treatment, a workover, etc. Increased fluid viscosity in
the formation from emulsions, polymers, etc. can result in re-
stricted flow rates.
Two additional mechanisms which may appear as damage but
are not the intent of this work, are pseudo-skin ͑rate sensitive or
non-Darcy skin effect͒ and stress sensitivity, i.e., near wellbore
effects due to increased effective stress related to having drilled
the well and pressure draw down during production.
Significant Formation Characteristics
The formation characteristics which are significant when consid-
ering formation damage potential include:
1. mechanical properties of formation,
2. stress magnitude and orientation,
3. pore pressure,
4. porosity—primary and secondary,
5. permeability,
6. formation fluids,
7. formation temperature,
8. formation mineralogy.
The mechanical properties, stress magnitude and orienta-
tion, and pore pressure all relate to wellbore stability and may
dictate drilling and well completion requirements to maintain a
stable hole and well control, especially in highly deviated and
horizontal wells. Significant overbalance pressure can cause fluid
invasion and damage. In some cases, these formation characteris-
tics may also indicate wells could be drilled underbalanced, pos-
sibly preventing considerable formation damage while drilling
͑thus possibly eliminating the need for acidizing͒. Additionally,
pore pressure is important since it helps restrict fluid invasion and
assists in removing damage, if it has occurred.
Copyright © 1999 Society of Petroleum Engineers
This paper (SPE 56279) was revised for publication from paper SPE 38594, first presented
at the 1997 SPE Annual Technical Conference and Exhibition held in San Antonio, Texas,
5–8 October. Original manuscript received for review 5 October 1997. Revised manuscript
received 27 April 1998. Paper peer approved 12 August 1998.
150 SPE Prod. & Facilities 14 ͑2͒, May 1999 1064-668X/99/14͑2͒/150/9/$3.50ϩ0.15
Primary porosity and pore size distribution influence the
amount and depth of invasion as well as properties of materials
which might be used in the mud or completion fluid to reduce
invasion.
3
Secondary porosity, such as natural fractures, can take
whole mud/completion fluid and may require different materials
in the mud or completion fluid to reduce invasion.
Permeability can also influence depth of invasion and degree
of damage. Relative permeability and formation wettability may
be altered due to invaded fluid. It is generally desirable to build a
low permeability filter cake to prevent loss of drilling and comple-
tion fluids. Laboratory testing with representative formation
samples is desired to assist in designing fluids to control fluid loss
and to select those fluids and filter cakes which are least damaging
and most easily removed.
Formation fluids are potential sources of damage. Connate
water can react with drilling or completion fluids resulting in pre-
cipitates or to cause precipitates ͑as scale͒ during production.
Some oils can have a tendency to emulsify with aqueous drilling
and completion fluids, and paraffins and asphaltenes may be des-
olublized by these same fluids.
Formation temperature is important since it can influence
various fluid–fluid reactions and the reaction rate of various acids
on formation minerals.
The mineralogy of the formation can obviously influence the
amount of damage done by drilling mud, completion and work-
over fluids, and success or failure of matrix acid treatments. For-
mation mineralogy as related to formation damage is discussed
below.
Carbonates, limestone (CaCO
3
) and dolomite ͓CaMg͑CO
3
͔͒
2
are susceptible to formation damage just as are the clastics ͑sili-
cates͒. However, some of the damage mechanisms are different.
Most of the damage occurring in carbonates from drilling,
completion and workover operations relate to particulate invasion
into the matrix or natural fractures, changes in wettability or fluid
saturations and viscosity effects. Particulate invasion is normally
much easier to remove or bypass in carbonates than in silicates
due to the rapid reaction rate of the carbonates in hydrochloric
acid. An exception to this could be dolomites at low formation
temperatures being treated with low temperature hydrochloric
acid. Changes in wettability and adverse fluid saturations caused
by the various well operation fluids may be corrected with surfac-
tants, etc. Also, adverse viscosity effects such as treating fluid
polymers or emulsions can be treated with the standard polymer
breakers and/or surfactant solutions. The carbonate environments
are much more forgiving than the clastic ͑silicate͒ environments
where clays and feldspars are often present. The carbonates can
contain silicate fines and clays but these are usually encapsulated
in the carbonate and will not be disturbed under normal well op-
erations, except for acidizing. During acidizing, these may be re-
leased creating damage. Other potential problems with carbonates
relate to forms other than limestone and dolomite. Carbonates
such as siderite ͑iron carbonate, FeCO
3
͒ and ankerite ͑dolomite
containing manganese and iron͒ will bring iron into solution when
acidized which can then be precipitated if oxidized to the Fe
ϩ3
form causing further damage.
The sandstones can be more easily damaged than carbonates
due to the presence of clays, zeolites, and feldspars ͑alumino-
silicates͒. When alumino-silicates and silicate fines are present in
sandstones, they are often associated with the pores and flow
channels and are susceptible to swelling and/or migration.
The common clays found in sedimentary rock are illite, chlo-
rite, kaolinite, smectite, and mixed layer clays. Of these, the illite,
chlorite, and kaolinite are considered nonswelling, migrating clays
while smectite and mixed layer clays are considered swelling
clays. Silicates have a cation exchange capacity ͑CEC͒ which can
cause these clays to be disturbed and become mobile when ex-
posed to some fluids. Each of the common clay minerals are of
concern when considering formation damage and removal, each
for different reasons. All of these silicates and alumino-silicates
͑clays, zeolites, feldspars͒ can be dissolved with HF acid and can
be reactive to HCl at various temperatures.
4–7
Smectite and mixed layer clays are water swelling clays and
are reactive to hydrochloric acid. They can become unstable in
HCl at temperatures of approximately 150°F. Chlorite is a clay
mineral which typically has iron in its structure. When contacted
with HCl, the iron can be removed, disintegrating the structure,
leaving an amorphous residue and iron in solution which may
precipitate when the pH of the acid increases. The sensitivity of
chlorite clay to HCl begins at approximately 125°F. Additionally,
chlorite has been shown to be approximately 50% destroyed in
10% formic acid at 180°F with basically no sensitivity to acetic
acid at that same temperature.
5
Illite clays are troublesome when
using HF acid due to the potassium usually present in this clay
structure. When dissolved, the potassium is readily available to
react with the HF–alumino-silicate reaction products, forming the
insoluble potassium fluosilicate. Illite is unstable in HCl begin-
ning at approximately 150°F. Illite can also be troublesome since
it often occurs as a needle-like structure making it susceptible to
fluid retention and/or fines migration within the sandstone pore.
Kaolinite clay is considered the most detrimental from a migra-
tion standpoint. It becomes unstable in HCl only at higher tem-
peratures (Ͼϳ200°F).
Zeolites are secondary minerals, hydrated silicates of alumi-
num, calcium, sodium, and potassium. They are occasionally
found in sedimentary rocks, with the most common form being
analcite ͑analcime͒, NaAlSi
2
O
6
–H
2
O. The significance of the zeo-
lites is that they will either decompose and/or gelatinize in hydro-
chloric acid at temperatures above approximately 75°F.
Sandstones containing feldspar can be especially troublesome
when conducting HF acid treatments. Feldspars frequently found
associated with sandstones are orthoclase (KAlSi
3
O
8
) and plagio-
clase ͑NaAlSi
3
O
8
or CaAl
2
Si
2
O
8
͒. As the feldspars are dissolved
with HF acid, the potassium, sodium, and calcium ions are avail-
able for reaction with other reaction products, resulting in precipi-
tation. The feldspars are relatively stable in HCl at most tempera-
tures. However, some sensitivity of feldspars to HCl has been
reported by Simanjuntak and Haynes.
6
All of these alumino-silicates are sensitive to the fluids placed
on the formation and may be disturbed from their original, in situ
position. Aqueous fluids of varying salt concentrations and pH can
adversely affect particle hydration and migration. When using
acid as HF acid preflush fluid ͑suggested͒, care must be taken not
to create damage due to dissolution/movement of formation min-
erals. As the above discussion on sensitivity of alumino-silicates
indicates, less aggressive fluids are needed at higher temperatures.
These less aggressive fluids usually contain organic acids. The
silicates which may migrate can be clay, silt and other small par-
ticles which are normally either in the pore space or adhering to
sand grains. The small particles adhering to sand grains are nor-
mally associated with water coating each grain. As long as the
wetting phase ͑water͒ is not flowing or this water layer is not
disturbed these particles can be relatively stable. However, when
the wetting phase begins to flow or production fluid velocity is
sufficiently high these particles can begin to move and cause
plugging.
8
Damage Removal by Chemical Means
The effective removal of absolute permeability damage involves
the dissolution or dissolution/dispersion of physical material
which is causing the restriction in permeability. If the damaging
G.R. Coulter and A.R. Jennings, Jr.: Matrix Acidizing SPE Prod. & Facilities, Vol. 14, No. 2, May 1999 151
material is acid soluble, an acid based fluid may be effective in
dissolving and removing the material. Both sandstone and carbon-
ate formations can be acidized but the effectiveness of the acidiz-
ing treatment is always directly related to how well the selected
treatment matches the damage. Since this paper deals with the
removal of near-wellbore damage, it is important to recognize that
the objective of conventional sandstone acidizing is to restore
permeability of the sandstone to its undamaged condition. In car-
bonates, matrix acidizing tends to increase near-wellbore perme-
ability by acid dissolution and enlargement of pore throats and
flow channels. Recent work presented by Di Lullo and Rae
9
dis-
cusses a new acid for true stimulation of sandstone formations.
When the damaging material consists of paraffins and asphalt-
enes, organic solvents must be used to help dissolve the material
for restoration of permeability. When acid-soluble scales and sol-
ids are coated with oil, solvents, used as a carefully placed pre-
flush before the acid stages can be useful in helping clean the
surfaces to allow more direct reaction of the acid. Acid should
never be used alone in an attempt to remove paraffin or asphaltene
deposits.
There are many chemicals used in acidizing treatments, devel-
oped to facilitate the use of the acid to allow it to be pumped
through metal tubulars and to contact the damage it has been
designed to remove. Additives included in current acidizing treat-
ments frequently include the following: corrosion inhibitors, sur-
factants and mutual solvents, iron control additives, diverting
agents, and gas.
Corrosion inhibitors are typically strong cationic materials
͑variations of amine derivatives͒ developed to have a strong affin-
ity for metal surfaces. To be effective, inhibitors must have the
capacity to adhere to the inside of the tubing to form a thin pro-
tective coating as acid is being pumped. Even the most effective
inhibitors do not stop acid corrosion on metals. They only slow it
down sufficiently to allow acid fluids to be pumped to the forma-
tion without damaging the integrity and life of the metal. Because
corrosion inhibitors have such strong cationic charges, they must
be used carefully to provide sufficient corrosion inhibition but not
used in such excess that they plate out in the matrix and induce
damage to the relative permeability by causing wettability
changes ͑such as oil wetting sandstones͒. The oil wetting charac-
teristics of corrosion inhibitors should always be a concern in
sandstone acidizing and over treatment with inhibitors should be
avoided.
Surfactants are common to all acidizing treatments. Functions
of surfactants used in acidizing include: nonemulsifying, dispers-
ing, sludge prevention, penetration, and reduction of surface ten-
sion.
Compatibility of the various materials used in matrix acidizing
is always of concern. This is particularly true with surfactants,
where multiple surfactants are used in a treatment for various
reasons. In sandstone acidizing, especially, the incompatibility of
corrosion inhibitors and anionic surfactants can be a problem if
not properly addressed.
Mutual solvents ͑such as ethylene glycol mono butyl ether,
EGMBE, or similar materials͒ represent another additive fre-
quently included in acid systems. Mutual solvents are often se-
lected because of their solubility in both aqueous ͑acid͒ and hy-
drocarbon based fluids such as formation oils. Mutual solvents
were developed several years ago to facilitate acid reaction on oil
coated surfaces because of the ability of the mutual solvent to help
dissolve away the oil coating. Mutual solvents also help lower the
surface tension of the reactive acid which facilitates spent acid
recovery and well cleanup. Because of their properties, mutual
solvents may tend to limit the effectiveness of corrosion inhibitors
and frequently inhibitor concentration must be increased in acid
treatments when mutual solvents are used. There are numerous
opinions related to the successful and unsuccessful use of mutual
solvents. To be effective mutual solvents must be added at con-
centrations of approximately 10% by volume of acid, and there-
fore, may add substantially to the cost of the treatment. The use of
mutual solvent in a particular acid application should be carefully
evaluated prior to the acid treatment.
Acids must be pumped through various metal goods ͑tubing
and pumping equipment, for example͒ on its way to the formation,
and many formations themselves contain siderite, hematite, and
other iron-rich minerals. Therefore, iron sequestering agents are a
common additive for many acid systems. Although iron control
additives may not be necessary on every acidizing treatment, it is
recommended that the need be thoroughly evaluated before omit-
ting the iron control agents from an acidizing treatment. The
chemistry of iron precipitation, however, sometimes leads to con-
fusion and iron control agents may be routinely added ‘‘for insur-
ance.’’ During an acidizing treatment, iron may exist in two
forms: as Fe
ϩ2
͑ferrous iron that begins to precipitate at a pH of
approximately 5.0͒ and as Fe
ϩ3
͑ferric iron that begins to precipi-
tate at a pH of 2.5 and totally precipitates at a pH of 3.5͒. Precipi-
tated iron compounds bring a myriad of problems including for-
mation damage and interference with corrosion inhibitors and
other acid additives.
Effective zone coverage is critical to the success of matrix
acidizing in both sandstones and carbonates. Diversion of matrix
treatments can be accomplished by using one of the following
methods: mechanical diversion by straddle packers and packers
and bridge plugs, perforation ball sealers, chemical solids, foam,
and increasing injection rate below fracturing pressure.
Mechanical diversion is usually considered the most effective
method of treatment diversion and making sure each interval is
being properly acidized. However, since it may take several hours
to cover a large interval ͑which usually leads to concerns about rig
costs and flowback of spent acid returns͒, the method has its limi-
tations.
Perforation ball sealers may be used for matrix diversion, but
the necessity to have sufficient rate/perforation ͑at least 0.25
BPM/perf͒ to hold the balls on the perforations as the acid is
placed can become difficult over extensive intervals. However, the
ball sealers may have application over an interval up to 50 feet or
so thick if the zone has variable permeability or degrees of dam-
age which may limit the acid entry to a few feet at a time. Over
the past several years, buoyant ball sealers, as proposed by
Erbstroesser,
10
have been used successfully for diversion of ma-
trix acidizing treatments. When buoyant ball sealers are used it is
important to recover them all in a ball catcher at the surface prior
to placing a well back on production.
Chemical solids such as a graded rock salt, benzoic acid flakes,
and various oil-soluble resins can be used for diverting acidizing
treatments over extensive intervals. Most of the solids used for
diversion have some solubility in at least one of the fluids it will
be exposed to during the final stages of the acidizing treatment, or
at least during the early stages of well production. It is important
that the solids ͑such as benzoic acid͒ be exposed to a flowing
stream for most effective removal. Several have found that mixing
rock salt and benzoic acid in a 50/50 blend provides a very effec-
tive diverting material. This blend can have good solubility char-
acteristics. The rock salt is soluble in spent acid and some forma-
tion 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 ͑gelled with a polymer
such as HEC or HPG͒. This stage will usually contain 1–2 lbs of
sized diverting agent per gallon for diverting treatments over ex-
152 G.R. Coulter and A.R. Jennings, Jr.: Matrix Acidizing SPE Prod. & Facilities, Vol. 14, No. 2, May 1999
tensive intervals ͑usually attempting to treat 25–50 feet of zone
per acid stage prior to pumping the solid diverter stage͒. Rock salt
would not be used with HF acids due to concerns for secondary
precipitates.
Intermittent stages of gelled acid can also be used to improve
the contact of matrix with acid over extensive intervals. This tech-
nique is especially applicable for carbonate formations since the
hydrochloric ͑or organic͒ acid used for acidizing could be pumped
in stages of ungelled acid and gelled acid. Polymers, such as poly-
acrylates, can be used in this application to form gelled acid suf-
ficiently stable to provide viscosity throughout the acidizing treat-
ment. In this application, ungelled acid would be pumped,
followed by a gelled acid stage to provide sufficient pressure drop
to divert the next increment of ungelled acid. This procedure
could also be modified for sandstone acidizing by gelling a por-
tion of the HCl/HF treatment acid and running the gelled acid as
the last increment prior to pumping preflush for treating the next
segment of a long interval.
Foam is frequently used to help divert matrix acidizing treat-
ments in sandstones and in gravel packed completions. Foam ͑ni-
trogen and fluid͒ has several advantageous characteristics for di-
verting acidizing treatments. The bubbles in the foam can expand
into zones where permeability has been restored to help divert
subsequent acid pumped to other portions of the zone ͑or gravel
pack͒ which has not been contacted by the acid. There is no resi-
due when the foam breaks ͑non-damaging͒ and the gas included in
the foam helps facilitate flowback of spent acid fluids after the
treatment. Experience tends to indicate that when using foam in
diverting stages, it is advantageous to be adding gas ͑500 SCF/bbl
or so͒ to the acid during the treatment to help facilitate the in-
crease in gas rate required for the foam stages ͑as opposed to
trying to bring the nitrogen pumps on line instantaneously to gen-
erate foam for the diverter stage͒.
Paccaloni
11
and others advocate using injection rate for treat-
ment diversion during matrix acidizing treatments. This technique
involves increasing the injection rate as treating pressures de-
crease with improved ͑or restored͒ permeability. The objective is
to pump additional acid at ever increasing rates as skin is removed
to deliver more fluid to a clean zone than its restored permeability
will allow, thus diverting flow to other portions of the zone to
create yet another ‘‘path of least resistance’’ with the acid reac-
tion. Although this technique has advantages as to treatment ef-
fectiveness and no residue with diversion, application of the tech-
nique requires much preplanning and may require substantial
amounts of horsepower and volumes of acid when used in high
permeability formations.
Gas can also be considered an additive for acidizing treat-
ments. Nitrogen can be added to acid to facilitate spent acid re-
covery when acidizing low pressure gas wells and, of course,
when using nitrogen foam as a diverter. Through a patented tech-
nique, Gidley
12
reports advantages of using carbon dioxide as a
preflush ahead of acid in treating oil zones.
Completion Methods
Well completion methods either provide for zone isolation or limit
zone isolation for matrix stimulation work. In many horizontal
wells the attempt is to remove very near wellbore damage ͑filter
cake͒ with a wellbore wash and/or soak. Any attempt at matrix
injection is limited by the ability to isolate individual zones. Zone
isolation in both carbonates and silicates in all wells is critical to
successful matrix stimulation work. Without proper zone isola-
tion, diverting techniques become even more critical. A unique
concept for horizontal well zone isolation was presented by By-
rom and Coulter.
13
Matrix Acidizing in Carbonates
Matrix acidizing in carbonates provides opportunity not only to
remove damage in the vicinity of the wellbore, but to also im-
prove near-wellbore permeability by enlarging pore throats and
flow channels with the acid dissolution. Matrix acidizing in car-
bonates can be generally considered as a much more straightfor-
ward process than acidizing in sandstone formations. This is be-
cause most of the reactant products in both limestones and
dolomites are soluble in the spent acid. Hydrochloric acid ͑HCl͒ is
frequently the acid of choice.
Fig. 1 illustrates the dissolving capacity of various concentra-
tions of hydrochloric acid in limestone and dolomite when the
acid reaction goes to completion. Based upon calculated volume
requirements and field practice, most matrix acid treatments in-
volve the use of 75–250 gallons of acid per foot of pay.
The major concerns with matrix acidizing in carbonates include
the following: effective diversion, limiting wormholing and exces-
sive fluid leak-off, high and low temperature applications, acid
concentration.
Table 1 shows some of the general guidelines and key points
related to matrix acidizing carbonate formations.
Effective diversion of reactive acid is necessary for efficient
matrix acidizing in carbonates. Diversion in carbonates is gener-
ally more difficult than in sandstones because of the ability of acid
to drastically increase permeability in carbonates as it reacts in the
pore spaces and flow channels of the matrix. For example, most
oil soluble resins are not useful for acidizing in carbonates be-
cause the resin particles are not able to bridge the large flow
spaces created by the acid reaction. Other solids, such as benzoic
acid flakes and rock salt also have limited application. Properly
designed, effective diversion can be achieved with a combination
of increasing injection rate and perforation ball sealers. Success
here will relate to perforation density and location with respect to
zones of interest. Perhaps the most effective means of diversion in
matrix acidizing is using stages of gelled acid in conjunction with
ungelled acid. The gelled acid diversion stages provide a means of
slowing acid reaction down and increasing resistance to flow into
a particular interval to allow diversion to another zone. This tech-
nique has been used successfully in diverting matrix acid effec-
tively over 450 ft intervals in massive limestones in Indonesia.
Success has been achieved in controlling fluid loss in carbon-
ates by using special polymer systems which viscosify and weakly
crosslink as the acid spends ͑increased pH͒. The crosslinked gel
thus created is very unstable and then begins to break down as the
acid neutralizes with exposure to excess carbonate. The crosslink
time, however, is generally sufficient to create a resistance for the
crosslinked, partially spent acid to leak off and thus creates suffi-
cient back pressure to send subsequent volumes of acid to other
Fig. 1–Solubility of limestone and dolomite in hydrochloric
acid.
G.R. Coulter and A.R. Jennings, Jr.: Matrix Acidizing SPE Prod. & Facilities, Vol. 14, No. 2, May 1999 153
portions of the interval. These types of polymer systems have
been used successfully in a variety of wellbores, including hori-
zontal wells.
Matrix acidizing has been successfully performed in carbonate
wells with reservoir temperatures approaching 400°F, using or-
ganic acid ͑such as formic or acetic acid͒ or blends of formic and
acetic as reported by Van Domelen and Jennings.
14
Properly se-
lected strengths of organic acids can provide dissolution capacity
approaching that for hydrochloric acid without as much concern
for acid corrosion. It has also been shown that organic acids can
be effectively viscosified using the same viscosifiers used with
hydrochloric acid. With high temperature matrix acidizing in car-
bonates, stages of acid can be gelled using thermally stable gelling
agents to facilitate zonal coverage and to help control fluid leak-
off.
It may be necessary to enhance the reaction of HCl on dolo-
mites at low temperature in matrix acidizing applications because
of the relatively short contact time of the acid with the less reac-
tive dolomite. This can be accomplished by injection rate design,
chemical approaches, and with temperature. Wang et al.
15
also
discuss the importance of injection rate of acid in the effective
matrix acidizing of carbonate formations. They point out that with
low temperature dolomite acidizing, larger volumes, lower injec-
tion rates or heated acid may be required to obtain equivalent low
temperature limestone reactions. Two techniques were developed
years ago to enhance the reactivity of HCl and are still in use
today in limited application. The first technique involves adding a
very low concentration of HF ͑about 0.25% by weight͒. This low
concentration enhances the reactivity of the mixture and ensures
that minimum damage from HF reaction products are introduced.
The second process involves adding several gallons of ammonium
hydroxide to HCl just prior to pumping. Temperatures as high as
140°F can be obtained using this method and it has proven ben-
eficial for treating shallow, low temperature dolomites.
Both 15 and 28% HCl are frequently used in matrix acidizing
applications in carbonates. The higher concentration of acid can
dissolve more carbonate ͑3.659 lbs of CaCO
3
per gallon of acid͒
compared to 15% ͑1.845 lbs of CaCO
3
per gallon͒ but the 28%
will require more corrosion inhibitor, may cause wellbore stability
problems and may have a greater tendency to create sludges and
emulsions. Although the reaction rate of HCl on carbonates is fast,
especially at temperatures higher than 150 °F, there are conditions
͑in some dolomites, for example͒ where rapid flowback may allow
unspent acid to be produced back if 28% HCl is used. Matrix
acidizing involves treating the near wellbore area and restoring
and enhancing the permeability in that region. Generally 15%
works well in this application without the potential difficulties
associated with higher strength acids.
Matrix Acidizing in Sandstones
Matrix acidizing of sandstones requires special attention. Various
reactions take place when HF acid contacts silicates, alumino-
silicates and other minerals in the formation. Commonly, sand-
stone acidizing consists of pumping a preflush fluid to remove
any calcium carbonate, condition clays, maintain low pH and to
push formation fluids away from the area where the HF acid may
react with remaining minerals. The preflush is followed by the HF
acid system and this is followed by an overflush. The overflush
continues to push the HF acid out into the formation until it is
spent, damage removed, and the near wellbore treated to remove
corrosion inhibitor, etc. The common approach over the years has
been to pump approximately 100 gallons per foot ͑gpf͒ of 5 to
15% HCl as a preflush fluid, followed by 100–200 gpf 12%HCl–
3%HF. This was followed by an overflush of HCl or ammonium
chloride (NH
4
Cl) water and the well returned to production. Re-
sults were not always as expected. The work presented by
McLeod
2
brought to the industry the idea that the HF acid con-
centration should be related to the amount of clay in the forma-
154 G.R. Coulter and A.R. Jennings, Jr.: Matrix Acidizing SPE Prod. & Facilities, Vol. 14, No. 2, May 1999
tion, with an inverse relationship between the amount of clay and
the HF acid concentration. The higher the clay content the lower
the HF acid concentration should be. The work McLeod presented
was updated in 1991
16
and included the effects of formation tem-
perature on acid selection.
Work reported by Gdanski and Peavy
17
based upon analysis of
returned samples following a HF acid treatment in the Gulf of
Mexico, showed there were probably numerous reactions going
on during the injection of HF acid. This information prompted
considerable research in the area of HF reactions and preflush
fluid reactions on alumino-silicates. This work, reported in several
technical papers
7,18–25
provides insight into many of the problems
associated with HF acidizing over the years. The work reported
sights primary through tertiary reactions taking place when pump-
ing HF fluids on sandstone formations containing alumino-
silicates. The primary reaction is that of the HF on alumino-
silicates resulting in silicon fluorides. These reaction products can
continue to react on alumino-silicates, a secondary reaction, at
temperatures above ϳ100°F. During this secondary reaction, clay
material is brought into solution and any sodium and potassium
ions present can react with any unreacted silicon fluorides causing
a precipitate of sodium or potassium fluorosilicate. Additionally,
as the reaction continues with all the silicon fluoride reacted, alu-
minum fluoride complexes are formed which react on alumino-
silicates, a tertiary reaction. At this point, as the HCl is consumed
or the reaction products are diluted with formation water and the
pH elevated, an aluminum fluoride precipitate can be formed cre-
ating damage.
To prevent these problems, two approaches are taken. One is
to design a preflush such that the formation is preconditioned,
removing calcium carbonate, formation water and sodium associ-
ated with clays, such that the HF acid or the reaction products do
not come in contact with calcium or sodium. Additionally, by this
preflush fluid being acidic, it can keep the pH low in the area
where HF acid or reaction products may come in contact. It is also
important that the preflush fluid does not create damage. Where
the dominant alumino-silicates are sensitive to HCl, less aggres-
sive preflush fluids should be chosen, as shown in Fig. 2. The
second approach is to design the HF acid system such that it will
have less tendency to cause precipitates but will adequately re-
move the damage. Other work
6,26,27
discusses design of preflush
and HF acid fluids to assist in the optimum fluid design for a
given set of conditions. The design of both the preflush fluid and
HF fluid composition should depend primarily on the mineralogy
and temperature of the formation to be treated. Others have con-
sidered the effect of the formation permeability and it can be
important as it relates to injectivity and the reaction rate of the
acid as compared to the injection time. In general, the lower the
sandstone formation permeability the more clay and feldspar con-
tained in the formation and the more sensitive it will be to high
HF acid concentrations. However, formation permeability is not
considered in the work presented here, although that would be an
anticipated extension of this work.
Options for preflush and HF acid fluids are numerous. In gen-
eral, preflush fluids can be HCl with concentrations from 5 to
15%, organic acid, organic acid/HCl blends, with the organic acid
normally being formic or acetic acid at 10%. When organic acid is
used as the preflush fluid, Gdanski
19
has shown that 5% NH
4
Cl
should be included. This is based upon laboratory testing showing
that organic acids do not provide ion exchange and have the same
effect as placing fresh water on the formation. The 5% NH
4
Cl
provides clay protection. ͑Based upon metal type and tempera-
tures, these fluids should always be evaluated for corrosivity.͒
Shuchart and Gdanski
21
have shown that formic and acetic HF
acids can result in aluminum fluoride precipitates and different
organic acids are needed in the organic HF acids. The main reason
for using organic HF is due to the sensitivity of some alumino-
silicates to HCl. The work presented by Simanjuntak and Haynes
6
showed that with citric acid at 0.3% added to acetic HF, the alu-
minum was sequestered and this approach would allow the use of
acetic HF.
Table 2 gives general guidelines and key points for consider-
ation when dealing with sandstone formations. This table also
addresses similar information for scale. Based upon formation
temperature and dominant alumino-silicate type, Figs. 2 and 3
were prepared as guidelines to give an idea of the types of pre-
flush and HF acid fluids best suited for the reservoir conditions.
Dominant alumino-silicate would be defined as the major
alumino-silicate mineral͑s͒ which would be sensitive to the vari-
ous fluids being considered and is causing damage. In these fig-
ures, the various fluids would be used up to the maximum tem-
peratures shown. At higher temperatures, the next fluid would be
used until a formation temperature greater than that maximum
temperature is reached, etc. Fig. 3 does not show an application
for the previous industry standard of 12% HCl/3% HF. Addition-
ally, concentrations of acid or organic acid types are not shown.
The objective with these figures is to look at generally safe acid
systems for alumino-silicate damage removal. HCl/HF blends can
create early damage in formations.
28–30
In general, the lower the
HF concentration in the blend, the less chance there is for damage
creation. Where organic HF is being used, careful evaluation of
aluminum precipitates needs to be conducted. In certain situations
the 12/3 blend could be used successfully. Laboratory tests should
be conducted to confirm these situations.
The preflush volume should be equal to or greater than the HF
acid volume. The minimum preflush volume should condition the
formation out to a radius of 24 in. The concentration of acid in the
preflush would be varied based upon the amount of calcium car-
bonate in the formation and alumino-silicate sensitivity. The
maximum calcium carbonate concentration in the formation for
HF acidizing is generally accepted at 15–20%. However, at these
higher concentrations, it is very difficult to maintain adequate low
pH so the advancing HF acid and HF acid reaction products do
not result in precipitation. Therefore, the maximum acceptable
calcium carbonate concentration for HF acidizing may be less
than 15–20%.
The overflush fluids can help in maintaining low pH in the
vicinity of the reactions which have taken place with the HF acid
and can be used to remove corrosion inhibitor from the near-
wellbore area. Commonly, the same type of fluids used in the
preflush is used in the overflush at approximately the same vol-
umes. Additional additives, such as mutual solvents, may be used
to assist in fluid recovery, removing corrosion inhibitor, etc.
Fig. 2–Suggested preflush fluid for matrix-acidizing sand-
stones.
G.R. Coulter and A.R. Jennings, Jr.: Matrix Acidizing SPE Prod. & Facilities, Vol. 14, No. 2, May 1999 155
Sandstone acidizing can be very successful, however, as the
above discussion points out, there are many variables to consider
before selecting the sandstone acidizing approach. It is always
recommended that formation samples be evaluated and damage
mechanisms determined prior to acidizing.
Matrix Acidizing Applications in Horizontal and
Multilateral Wellbores
Effective acidizing treatments have been conducted in a variety of
formations under a wide range of reservoir and producing condi-
tions. The key to successful stimulation with matrix treatments
involves two important criteria: ͑1͒ the selected matrix treatment
system must match the problem it is being used to solve, and ͑2͒
even if very effective, the injected treatment fluids must be able to
efficiently contact the source of permeability reduction. As has
been discussed in this paper, some control of acid placement can
be achieved by completion techniques and perforation placement
in cased wells and through the use of diverting agents in cased
͑and in some open hole completions͒. However, with sandstone
acidizing, the importance of the sequence of preflush/treatment
acid/overflush to minimize acid induced damage has been stressed
and is very important.
Acid pumped through coiled tubing has provided a means for
effective matrix acidizing in many deviated and horizontal
wellbores.
31,32
However, most experience to date has been using
HCl or organic acids in carbonate formations, or using HCl to
remove mud cake containing calcium carbonate in sandstone for-
mations. Therefore, isolation tools and placement techniques are
needed to provide the ability to conduct a sandstone acidizing
treatment in horizontal and multilateral wells. It is believed that
much additional productivity could be achieved if a means is de-
veloped to strategically place the incremental preflush/HF acid/
overflush in many horizontal wells and multilateral wellbores in
sandstone formations.
When matrix acidizing treatments can be successfully per-
formed ͑horizontal wells in carbonates, e.g.͒, guidelines are
needed in the industry for effective ranges of gallons per foot of
zone. Generally, 7.5–10 gal of 15% HCl per foot has been effec-
tive in removing wellbore damage in carbonates and in cleaning
up calcium carbonate mudcake in horizontal wells in sandstone
reservoirs in sections of 2,000 ft or more. When it becomes nec-
essary to perform a matrix stimulation treatment in horizontal and
multilateral wellbores, the selection of treatment techniques and
methodology is currently limited.
Future Implications
Well stimulation treatments with acid are successfully used to
improve production in oil and gas wells completed in various
Fig. 3–Suggested HF acid for matrix-acidizing sandstones. „K-
Sp: potassium feldspar; Na-Sp: sodium feldspar; C, S, Z: chlo-
rite, smectite, and zeolites.…
156 G.R. Coulter and A.R. Jennings, Jr.: Matrix Acidizing SPE Prod. & Facilities, Vol. 14, No. 2, May 1999
types of carbonate and sandstone reservoirs. However, there is
still room for improvement. Fortunately, the major service com-
panies realize this as evidenced by the recent research efforts and
development of new matrix acidizing systems for sandstone for-
mations. Better understanding of the science involved in a well
stimulation process should lead to improvements in applications
using that process. This is especially true for matrix acidizing.
Several in our industry have participated in joint industry
efforts
33,34
to develop the formation damage expert systems and
software to help provide a systematic approach to successful
acidizing and formation damage removal. In addition to other fea-
tures, these models provide the capability to evaluate well char-
acteristics and make assessments as to potential for improvement.
Hopefully, these developments will help provide impetus toward
more complete evaluation of well stimulation candidates before
and after acidizing treatments and will help improve understand-
ing of acidizing applications.
Conclusions
1. Current acid types and additives being used in matrix acidiz-
ing are presented.
2. The three types of formation damage are presented with
emphasis on absolute permeability damage removal.
3. Significant formation characteristics related to acid types
necessary for successful matrix acidizing are presented.
4. Of the formation characteristics discussed, formation tem-
perature and mineralogy are the two most important characteris-
tics to be considered in acid selection for damage removal.
5. General guidelines/key points for matrix acidizing are pre-
sented. Laboratory testing of core and fluid samples from the well
and interval of interest is recommended.
6. These guidelines do not include formation permeability
which can affect matrix acidizing success.
7. Proper well completion and zone isolation techniques are
very important in the success of matrix acidizing. This is espe-
cially true with horizontal and multilateral wells.
8. Individual and joint industry research efforts continue which
should assist in further improvements in matrix acidizing.
Acknowledgments
The authors wish to express their appreciation to BJ, Dowell-
Schlumberger, and Halliburton Energy Services personnel for
candid discussions and input concerning the contents of this pa-
per.
References
1. ‘‘A Great Discovery,’’ Oil City Derrick ͑Oct. 10, 1895͒, as referenced
in the SPE Monograph, Vol. 6, ‘‘Acidizing Fundamentals.’’
2. McLeod, Jr., H. O.: ‘‘Matrix Acidizing,’’ Distinguished Author Se-
ries, J. Pet. Technol. 2055–2069 ͑December 1984͒.
3. Abrams, A.: ‘‘Mud Design To Minimize Rock Impairment Due To
Particle Invasion,’’ J. Pet. Technol. 586–592 ͑May 1977͒.
4. Gdanski, R.D. and Shuchart, C.E.: ‘‘Advanced Sandstone Acidizing
Designs Using Improved Radial Models,’’ SPE paper 38597, Pre-
sented at the 1997 SPE ATCE, San Antonio, TX, 6–8 October.
5. Simon, D.E. and Anderson, M.S.: ‘‘Stability of Clay Minerals in
Acid,’’ SPE paper 19422, Presented at the Formation Damage Con-
trol Symposium, Lafayette, LA, 22–23 February 1990.
6. Simanjuntak, A.B.M. and Haynes, L.L.: ‘‘ESEM Observations
Coupled With Coreflood Tests Improve Matrix Acidizing Designs,’’
SPE paper 27405, Presented at the International Symposium on For-
mation Damage Control, Lafayette, LA, 7–10 February 1994.
7. Gdanski, R.D.: ‘‘Kinetics of Tertiary Reaction of HF on Almino-
Silicates,’’ SPE paper 31076, Presented at the International Sympo-
sium on Formation Damage Control, Lafayette, LA, 14–15 February
1996.
8. Muecke, T.W.: ‘‘Formation Fines and Factors Controlling Their
Movement in Porous Media,’’ J. Polym. Sci., Polym. Phys. Ed. 144–
150 ͑February 1979͒.
9. Di Lullo, G. and Rae, P.: ‘‘A New Acid for True Stimulation of
Sandstone Reservoirs,’’ Presented at the 1996 SPE International Sixth
Asia Pacific Oil and Gas Conference, Adelaide, Australia, 28–31 Oc-
tober.
10. Erberstrosser, S.R.: ‘‘Improved Ball Sealer Diversion,’’ J. Pet. Tech-
nol. 1903–1910 ͑November 1980͒.
11. Paccaloni, G.: ‘‘A New Effective matrix Stimulation Diversion Tech-
nique,’’ SPE paper 24781, Presented at the 1992 ATCE in Washing-
ton DC, 4–7 October.
12. Gidley, J.L.: ‘‘The Future of Acidizing?’’ J. Pet. Technol. 230
͑March, 1997͒.
13. Byrom, T.G. and Coulter, G.R.: ‘‘Some Mechanical Aspects of For-
mation Damage and Removal in Horizontal Wells,’’ SPE paper
31145, Presented at the International Symposium on Formation Dam-
age Control, Lafayettte, LA, 14–15 February 1996.
14. Van Domelen, M.S. and Jennings, Jr., A.R.: ‘‘Alternate Acid Blends
for HPHT Applications,’’ SPE paper 30419, Presented at the Offshore
Europe Conference, Aberdeen, Scotland, 5–8 September 1995.
15. Wang, Y., Hill, A.D., and Schechter, R.S.: ‘‘The Optimum Injection
Rate for Matrix Acidizing of Carbonate Formations,’’ SPE paper
26578, Presented at the 68th ATCE of SPE in Houston, Texas, 3–6
October 1993.
16. Perthuis, H. and Thomas, R.: Fluid Selection Guide for Matrix Treat-
ments, 3rd ed., Dowell-Schlumberger, Tulsa, Oklahoma ͑1991͒.
17. Gdanski, R.D. and Peavy, M.A.: ‘‘Well Returns Analysis Causes Re-
evaluation of HCl Theories,’’ SPE paper 14825, Presented at the For-
mation Damage Control Symposium, Lafayette, LA, 26–27 February
1986.
18. Gdanski, R.D.: ‘‘Fluosilicate Solubilities Impact HF Acid Composi-
tions,’’ SPE paper 27404, Presented at the International Symposium
on Formation Damage Control, Lafayette, LA, 7–10 February 1994.
19. Gdanski, R.D.: ‘‘Fractional Pore Volume Acidizing Flow Experi-
ments,’’ SPE paper 30100, Presented at the 1995 SPE European For-
mation Damage Symposium, The Hague, The Netherlands, 15–16
May.
20. Shuchart, C.E.: ‘‘HF Acidizing Returns Analysis Provide Under-
standing of HF Reactions’’ SPE paper 30099, Presented at the 1995
SPE European Formation Damage Symposium, The Hague, The
Netherlands, 15–16 May.
21. Gdanski, R.D. and Shuchart, C.: ‘‘HF Acid Blends Based On Forma-
tion Conditions Eliminate Precipitation Problems,’’ Pet. Eng. Int.
63–66 ͑March 1997͒.
22. Shuchart, C.E. and Gdanski, R.D.: ‘‘Improved Success in Acid
Stimulation with a New Organic HF System,’’ SPE paper 36907,
Presented at the SPE European Petroleum Conference, Milan, Italy,
22–24 October 1996.
23. Gdanski, R.D.: ‘‘Kinetics of the Secondary Reaction of HF on
Alumino-Silicates,’’ SPE paper 37214, Presented at the 1997 SPE
International Symposium on Oilfield Chemistry, Houston, TX, 18–21
February 1997.
24. Shuchart, C.E.: ‘‘Chemical Study of Organic HF Blends Leads to
Improved Fluids,’’ SPE paper 37281, Presented at the 1997 SPE In-
ternational Symposium on Oilfield Chemistry, Houston, TX, 18–21
February 1997.
25. Gdanski, R.D.: ‘‘Kinetics of the Primary Reaction of HF on Alumino-
Silicates,’’ SPE paper 37459, Presented at the 1997 SPE Production
Operations Symposium, Oklahoma City, OK, 9–11 March.
26. Hill, A.D., Sepehrnoori, K., and Wu, P.Y.: ‘‘Design of the HCl Pre-
flush in Sandstone Acidizing,’’ SPE Prod. Facil. 9, 115–120 ͑1994͒.
27. Da Motta, E.P., Plavnik, B., Schechter, R.S., and Hill, A.D.: ‘‘Ac-
counting for Silica Precipitation in the Design of Sandstone Acidiz-
ing’’ SPE Prod. Facil. 8, 138–144 ͑1993͒.
28. Guin, J.A.: ‘‘Chemically Induced Changes in Porous Media,’’ PhD
dissertation, U. of Texas ͑January 1970͒, and as reported in SPE
Monograph Acidizing Fundamentals.
29. Smith, C.F. and Hendrickson, A.R.: ‘‘Hydrofluoric Acid Stimulation
of Sandstone Reservoirs,’’ J. Pet. Technol. 215–222 ͑February 1965͒;
Trans., AIME 234.
G.R. Coulter and A.R. Jennings, Jr.: Matrix Acidizing SPE Prod. & Facilities, Vol. 14, No. 2, May 1999 157
30. Smith, C.F., Ross, W.M., and Hendrickson, A.R.: ‘‘Hydrofluoric
Acid Stimulation—Developments for Field Application,’’ SPE paper
1284, Presented at the ATCE, Denver, CO, 3–6 October 1965.
31. Bunnell, F.D. and Duad, M.M.: ‘‘Coiled Tubing Stimulation Elimi-
nate Hole Failures and Condensate Losses in Arun Field,’’ SPE paper
30681, Presented at the 1995 SPE ATCE in Dallas, TX, 22–25 Oc-
tober.
32. Jennings, A.R. and Chambers, M.R.: ‘‘Method for Enhanced Cleanup
of Horizontal Wells,’’ U.S. Patent No. 5,462,118, 31 October 1995.
33. Bartko, K.M., Montgomery, C.T., Bonney, C.L., and Ward, V.L.:
‘‘Development of a Stimulation Treatment Integrated Model,’’ SPE
paper 35991, Presented at the SPE Petroleum Computer Conference
in Dallas, TX, 2–5 June 1996.
34. Xiong, H. and Holditch, S.A.: ‘‘An Investigation into the Application
of Fuzzy Logic to Well Stimulation Treatment Design,’’ SPE Com-
put. Applicat. 18 ͑February 1995͒.
Gerald R. Coulter is a consulting petroleum engineer and
president of Coulter Energy Intl. in Plano, Texas. He has over 35
years of experience in well completions and formation evalu-
ation. Coulter holds a BS degree in geology and a BA degree
in chemistry, both from Oklahoma State U. He also holds an
MS degree in petroleum engineering from the U. of Okla-
homa. A member of the Twenty-Five Year Club, Coulter was a
1985–90 member of the Editorial Review Committee, a
1990–92 member of the International Meeting on Petroleum
Engineering Committee, 1991–92 chairman of the Forum Series
Steering Committee, and a 1991–93 member of the Forum Se-
ries Implementation Committee. Coulter was SPE Distinguished
Lecturer 1992–93. Alfred R. Jennings, Jr. is a well stimulation
consultant with Enhanced Well Stimulation Inc. in Plano, Texas.
He provides assistance with well stimulation applications
throughout the world. Jennings holds a BS degree in chemistry
and an MS degree in petroleum engineering both from the U.
of Oklahoma. A member of a 1998–99 Annual Meeting tech-
nical committee, he was a 1982–84 member of the Editorial
Review Committee, a 1991–94 member of the Distinguished
Author Series Committee, a 1992–93 member of the Forum Se-
ries Steering Committee, a 1995–96 member of the Interna-
tional Formation Damage Symposium Committee, and
1997–98 chairman of the Annual Meeting Program Commit-
tee.
158 G.R. Coulter and A.R. Jennings, Jr.: Matrix Acidizing SPE Prod. & Facilities, Vol. 14, No. 2, May 1999