1

IDIZING

3
4

ACIDIZING
ACIDIZING

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ACIDIZING
Acid stimulation is a chemical treatment of increasing flow capability to a
well. Acid is used in order to dissolve minerals inside formation rocks,
which results in an increase in formation absolute permeability around the
wellbore. The use of acids to stimulate oil and gas production was first
introduced in 1894. The earlier treatments consisted of dumping raw acid
down the casing without applying pressure on the formation. It was not
until 1930 that improved materials and techniques were developed and the
process gained wide acceptance as an effective way of increasing well
productivity.
The primary purpose for acidizing a producing well is to increase the
drainage efficiency of the reservoir. Acidizing is particularly applicable to
wells producing form formations that are predominantly dolomites,
limestones or clastics in which the cementing material is composed of
carbonates. The acid when forced into the formation through natural or
induced fractures dissolves a portion of the fracture faces. This action plus
the pore enlarging effect of that portion of the acid that leaks-off through
the pores in the fracture faces increase permeability and porosity of the
reservoir rock in the vicinity of the wellbore. Since approximately 50% of
the reservoir energy is expended within a radius of eight feet of the
wellbore, the channelling of the acid into the formation will conserve
reservoir energy and increase ultimate economic recovery.

4.1

TYPES OF ACID TREATMENTS

There are four types of acid treatments:

1. Wellbore cleaning:
Casing, tubular goods and perforations may become clogged up with
deposits over a period of time. The deposits are products of corrosion,
bacteria, scales formed from insoluble salts within formation water, and
asphaltenes or tar components.
2. Acid Washing:
During drilling, cementing and production operations, a skin of damaged
permeability can be formed within a few feet of the wellbore giving a
considerably lowered permeability section, which will allow any relatively
low production rates. Low permeability results from the plugging of
formation pores around the wellbore by solid deposition from these fluids
when entered formation matrix. Low permeability also results from the
precipitation caused by the chemical reaction between these fluids and
formation water.

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3. Matrix acidizing:
Matrix acidizing is used in order to increase the productivity of naturally
low permeability reservoirs by enlarging pore spaces and dissolving
particles plugging these spaces. Matrix acidizing occurs when the injection
pressure is lower than the formation fracture pressure. In this case, Darcys
law describes acid flow into the formation. Usually, the reaction time is
short and only the formation a few feet away from the wellbore is affected.
4. Fracture acidizing:
In this type of treatment, acid is injected at pressure higher than the
formation fracture pressure. The objective is to create deep penetrating
fracture and by etching of the face of the fracture by the acid, no proppant
agent, is needed because of the irregularities on the face of the fracture.
In fracture acidizing, the acid is injected through natural or induced
fractures at pressures, usually exceeding the fracture pressure of the
formation. Stimulation is achieved when a highly conductive flow channel
remains open after the treatment.
This channel is formed by acid injection on the acid- soluble walls of the
fracture. In this process, acid reaction penetration depends on the velocity
of the acid, its reaction rate with the formation, the contact area between
fractures and acid, and the leak-off rate of the acid.
Velocity of the acid in a given fractured formation is determined primarily
by the injection rate. The deepest penetration can be obtained from a rate
that will produce an injection pressure just slightly below the pressure
required to create additional fractures. Any pressure greater than this
optimum, will widen existing fractures and open new ones, decreasing the
fluid velocity. The reaction rate of the acid probably has the greatest effect
on the depth of penetration.

4.2

TYPES OF ACIDS:

The primary requirement of an acid is that it should react with solid

materials to give soluble products.
An acid is defined as a chemical compound containing hydrogen capable of
being replaced by positive elements or radicals to form salts. Many types
of acid are being used in acid stimulation to achieve a variety of effects.
These acids fall into two categories: organic acids and inorganic acids.
All acids react with steel (tubular goods) and it must be possible to inhibit
this reaction at the elevated temperatures associated with acidizing.
.

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1. Hydrochloric acid - HCl

Hydrochloric acid is used to acidize carbonate rocks limestone, calcium
carbonates, Ca CO3, dolomite, calcium and magnesium carbonates, Ca Mg
(CO3) 2. It is usually used as a 15% (by weight) solution of hydrogen
chloride gas in water. In oil wet reservoirs higher acid concentrations can
be used with the aid of improved inhibitors. Higher concentrations have
become practical and they provide increased effectiveness.
Hcl reaction with limestone is:
Hydrochloric acid + calcium carbonate calcium chloride + carbon
dioxide + water
2HCl + CaCO3 CaCl2 + H2 O + CO2
HCl reaction with dolomite is:
Hydrochloric acid + dolomite calcium chloride + magnesium chloride +
carbon dioxide + water
4 HCl + CaMg (CO3)2 CaCl2 + Mg Cl2 + 2H2O + 2CO2
2. Mud Acid - HCl - HF
Mud acid is used as a combination of hydrochloric and hydrofluoric acids.
It is used for sandstone acidizing as 3 % HF and 12 % HCl. Most sandstone
formations are composed of quartz particles bonded together by various
kinds of cementing materials, chiefly carbonates, silica and clay minerals.
HF should not be used in carbonate rocks because of its fast reaction time.
HF can dissolve calcium carbonate, sand, clay and feldspars. HF is used
alone only to remove clay damage near the wellbore caused by drilling,
completion and workover fluids.
Mud acid is capable only of removing damage near the wellbore. Because
of its very shallow penetration depth, it is incapable of providing reservoir
stimulation. If a well that has low productivity is undamaged, a mud acid
treatment will provide no productivity improvement and may, if
improperly conducted reduce productivity. Formations with low natural
permeability are generally better candidates for fracturing rather than
matrix acidizing.

Quartz

4HF + SiO2 SiF4 (silicon tetrafluoride) + 2H2O

SiF4 + 2HF H2SiF6 (fluosililcic acid)

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Albite
(sodium feldspar)

Orthoclase
(potassium feldspar)

NaAlSi3O8 + 14HF + 2H+ Na+ + AlF2+ + 3SiF4 + 8H2O

KAlSi3O8 + 14HF + 2H+ K+ + AlF2+ + 3SiF4 + 8H2O
Al4Si4O10(OH)8 + 24HF + 4H+ 4AlF2+ + 4SiF4 + 18H2O

Kaolinite
Montmorillonite

Al4Si8O20(OH)4 + 40HF + 4H+ 4Alf2+ + 8SiF4 + 24H2O

However, in the presence of sodium or potassium ions, the following

reactions may occur to produce insoluble gelatinous fluorides, which are
damaging to the formation.
2 Na+ + H2 Si F6 Na2 SiF6 + 2H+
2 K+ + H3 Al F6 K3 AlF6 + 3H+
When hydrofluoric acid reacts with either silicates (clay minerals) or silica
(quartz) one of the reaction products is fluosilicic acid (H2SiF6). This acid will
react with sodium or potassium salts according to the following equations:
H2SiF6

H2SiF6

Fluosilicic
Acid

Fluosilicic
Acid

2NaCl

Sodium
Chloride

2KCl
Potassium
Chloride

Na2SiF6

K2SiF6

Sodium
Fluosilicate

Potassium
Fluosilicate

2HCl
Hydrochloric
Acid

2HCl
Hydrochloric
Acid

The sodium and potassium fluosilicates have very limited solubility and
secondary precipitation can occur if the hydrofluoric acid contains sodium or
potassium salts or if the spent or partially spent acid becomes mixed with
solutions containing these salts. This means that salt water should not be used
as mixing water for the acid or for displacing the acid. The acid should not be
weighted with sodium chloride or calcium chloride. When calcium chloride is
added to hydrofluoric acid, calcium fluoride will precipitate immediately.
Diverting aids such as rock salt should not be used because of secondary
precipitates. If additional weight is necessary, it is possible to use ammonium
chloride as the weighting agent.
Furthermore, HF will also react with limestone to produce insoluble
calcium fluoride.
CaCO3 + 2HF CaF2 + H2O + CO2

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For the reactions between HF and silicate minerals, only the primary reactions
are listed; secondary reactions will consume more HF per mole of mineral, thus
changing the stoichiometry. For the reactions between HF and feldspars, for
example, the primary reactions predict that 14 moles of HF are needed to
consume 1 mole of feldspar. However, Schechter (1992) suggests that about
20 moles of HF are consumed for every mole of feldspar under typical
acidizing conditions.
3. Weak Organic Acids
Acetic (HAC) and formic (HCOOH) are examples of weak organic acids.
These acids are easy to inhibit against corrosion and can usually be left in
contact with tubing or casing for days without danger of serious corrosion.
These acids also are used as a perforating fluid.
Acetic acid reacts with calcium carbonates as follows:
Acetic acid + calcium carbonate calcium acetate + carbon
dioxide + water
2 HCH3CO2 + CaCO3 Ca (CH3 CO2) 2 + H2O + CO2
Acetic acid reacts with dolomite as follows:
Acetic acid + dolomite calcium acetate + magnesium acetate + carbon
dioxide + water
The chemical reaction for formic acid is as follows:
Formic acid + calcium carbonate calcium formate + carbon dioxide +
water
2 HCOOH + CaCO3 Ca (HCO2)2 + H2O + CO2
The reaction rate for formic acid with dolomite as follows:
Formic acid + dolomite calcium formate + magnesium formate + carbon
dioxide + water
4HCH3CO2+CaMg(CO3)2Ca(HCO2)2+Mg(HCO2)2+2CO2+2H2O

4.3 ACID REACTION TIME FACTORS:

There are two important chemical factors that should be taken into account
when selecting a type of acid:

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1. Dissolving power
2. Reaction rate

4.4

Dissolving Power

The acid dissolving power depends on the type of acid used and the acid
concentration. It is proved that the more concentration the acid, the more
the acid dissolving power. The dissolving power is also depend on the type
of acid used, e.g. HCl, a strong acid, will dissolve more than the weaker
organic acids.

4.5

Reaction Rate

Fast reacting acid will spend very near to the wellbore, so may not achieve
deep penetration.
The major factors, which govern the reaction rate, are:
a) Pressure
Reaction rate tends to decrease with pressure in the reaction of HCl with
carbonate (figure 4-1). The reduction in reaction rate is due to the liberation of
CO2, which goes back into solution under pressure and forms carbonic acid.
The formation of this weak acid tends to slow the reaction rate. In practice, the
effect is negligible because we are always dealing with higher pressure.
b) Temperature
The reaction rate varies widely with temperature changes (figure 4-2). The
increase in temperature can be thought of as supplying an increase in
kinetic energy to the system. At elevated temperature the particles of acid
move more quickly and thus contact the sides of the system more
frequently thus the rate of reaction is increased.
d) Acid concentration
The reaction rate of the acid increases with increasing acid concentration
until the acid concentration reaches maximum value figure 4-3). The
ionization effect of HCl in water causes the reaction rate to be at maximum
when the acid concentration is about 28 %. 28 % HCl starts off with a
higher reaction rate than 15 % HCl. Higher acid concentrations more than
the maximum value produce an adverse effect of lowering the reaction rate
of the acid

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c) Flow velocity
The acid reaction rate increases linearly with increasing acid flow velocity
inside formation rocks (figure 4-4).
e) Area-Volume ratio
The most important single factor affecting the penetration of the acid out
from the wellbore is the area-compared to its volume, then the acid
particles volume ratio. If the surface area of the system is higher have an
increased chance of contacting the sides of the system. Hence, acid, in a
large volume wide fracture will react more slowly than acid in a thin
fracture of the same volume. The area-volume ratio will be higher in the
thin fracture and the effective contact rate will be higher. Figures 4-1 to
4-4 illustrate the effect injection acid parameters on the acid reaction rate.
f) Formation composition
Probably the most important factor in determining spending time, and thus,
spending distance, is the chemical and physical composition of the formation
rock. Acid solubility of a formation, the percent of rock sample that is
dissolved by an excess acid, offers a clue to its susceptibility to an acid
treatment. Most limestones react at about the same rate with a given acid, all
other factors remaining constant. Generally, the reaction rate of limestone is
only about 5.5 times that of dolomite. The area-volume ratio is, in part,
controlled by the physical structure. Also, the physical structure is of primary
importance since the solubility and permeability make-up can exist in several
ways. Where does the acid-soluble portion of the rock exist with respect to the
flow patterns in the rock? Is the key to acid response. Two formations having
the same acid solubility and permeability may respond differently to acid
treatment because of variances in physical structure.

4.6

ACID ADDITIVES:

Acidising can cause many problems in the acidised formation; release

fines, create precipitants, form emulsions, create sludge and corrode steel.
1) Inhibitors
Inhibitors are used in order to prevent acid reaction with steel in the well.
Acetylene and organic nitrogen are kinds of inhibitors, which accomplish their
purpose by forming a film on the steel and preventing contact between the steel
and the acid.

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Figure 4-1: Illustrates the effect of injection pressure on acid

reaction rate.

Figure 4-2: Illustrates the effect of reservoir temperature on the acid

reaction rate.

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Figure 4-3: Illustrates the effect of reservoir

pressure on the acid reaction rate.

Figure 4-4: Illustrates the effect of acid velocity on the

acid reaction rate.

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2) Surfactants
Surfactants are used in order to prevent sludge, precipitate, flocculant, and
emulsion formation. Sludge is formed when the acid contacts heavy crude
oil.
3) Sequestering Agents
During acidizing the contact of acid with iron will form ferric hydroxide.
Iron can be present as an ore within the formation, or can come from the
action of acid on steel. However, as the acid is spent, the Fe ferric complex
iron ion (Ferric hydroxide) tends to precipitate and redeposit near the
wellbore causing plugging of formation pores. Sequestering agents such as
citric or latice acids tend to prevent the deposition of the ferric hydroxide
by keeping it in solution.
.
4) Retarders
They are used in order to slow down the acid reaction time but not necessarily
the spending time. In most instances, raw acid tends to react too quickly with
most carbonate formations and penetration depths thus achieved are not
satisfactory for efficient stimulation. It would be desirable, therefore, to retard
the effective reaction rate of the acid with the formation to the extent that
deeper penetration of live acid is realized. There are several formulations
available which will accomplish the desired level of retardation. Some of these
are gelled acids, emulsified acids, mixtures of mineral and organic acids, and
chemically retarded acids. Gelled systems trap the acid in the cellular structure
of gel and thereby interfere with its mobility. Emulsified acid is composed of
acid droplets encased in oil or other organic liquid, which acts as the external
phase. The effective reaction time of the acid in this system is function of the
stability of the emulsion. In a mixed acid system, longer reaction times are
realized due to the fact that organic acids are formed.
5) Diverting Agents
When acid is injected into a low permeability formation or into a damaged
formation, the acid will always follow the path of least resistance, usually
the less permeable or damaged zone. Any permeability variations within
the treated formation will ensure that most of the acid will enter the high
permeability area. Therefore, diverting agents are added to the acid in order
to get the acid into the desired damaged treated zone.
When stimulating a formation in producing or injection wells, it is very
important that the treating fluids be distributed across the entire interval of
interest. Many formations have one or more section, which vary greatly in
permeability. When an acid stimulation treatment is performed on a

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formation with zones that have varying permeabilities, the acid will
normally take the path of least resistance. Therefore, without some type of
diverters, only the most permeable zones will be stimulated, leaving the
remaining zone basically unchanged. There are many different diverting
agents, which can be used to help obtain a uniform treatment of the entire
interval of interest. Some types of diverting agents used are:
a) Mechanical
b) Ball sealers
c) Chemical diverters
a) Mechanical Diverting agents
They are normally used, are bridge plugs, packers and other types of tools.
These tools can be set to isolate the zone of interest. These types of
diverting agents are usually the most effective method for allowing uniform
stimulation over the entire formation. However, due to expense, time and
often-incompatible equipment conditions, these mechanical diverting agents
cannot always be used.
b) Ball Sealers
They are another type of diverting agents, which are often used. These
materials are made of nylon, hard rubber or nylon with hard rubber coating.
These balls are designed to temporarily seal the bullet or jet type
perforations in casing. The balls are generally injected into the treating fluid
at the proper time. As the fluid carrying the ball sealers enters the
perforations, the ball will hopefully seat and block the flow of fluid. Once
the injection of fluid is stopped the force holding the ball is removed and
the ball drops to the bottom of the well. Select-O-Balls come in various
sizes of the perforation to be sealed and the density depends on the type of
treating fluids to be used. However, there are some wells in which the use
of ball sealers would not be recommended, such as a well which has nonuniform perforations, slotted liners, gravel pack wells, and wells with open
hole completions.
c) Chemical Diverting Agents:
This method of diverting actually takes place at the formation face, not
at the perforations, so the problem of a bad cement bond having
channels does not affect the efficiency. Chemicals are added to the
treating fluid, which plug the pores of the formation face, thus diverting
the fluid to other parts of the formation. These can either be benzoic
acid flakes, unibeads (small wax beads) or oil soluble resins, which do
not appreciably dissolve in acid (aqueous solution and naphthalene
paraformaldeyde organic acid, inorganic acid).

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These additives have a low melting point and are soluble in oil so, when
the well is cleaned up, the diverting agent is easily removed as the well
warms up again and oil starts to flow through the perforations. These
diverting agents must also be compatible with all fluids associated with
the well to be treated. In other words diverting materials, which have
undesirable reaction with either the treating fluids or formation fluids
should not be used. Figures 4-5 to 4-7 illustrate the techniques used in
diverting the injected acid to the desired zone or formation.
6) Anti-Sludge Systems.

Acid Oil Sludge:

The formation of asphaltic sludge during acid stimulation is a
serious problem in many areas. The areas where the most severe
sludging occurs are California and Canada. However, other areas
have also encountered sludging problems from time to time.
Usually, but not always, the most severe sludging occurs when
sensitive formation oils come in contact with high strength acid
(20% or higher) systems.
Many experts feel that certain crudes contain a colloidal suspension of
asphaltic material. When these oils encounter an acid environment, some or all
of this colloidal suspension precipitates out. Once the asphaltic material falls
out of solution, it will not redissolve in the formation fluids. A majority of
these precipitated sludge have only limited solubility in most treating fluids.
The formation of this asphaltic sludge can severely restrict or completely plug
the flow channels in the formation to be treated.
These precipitated solids can also stabilize emulsions and can plug screens,
liners and gravel packs.
The formation of sludge can be prevented by the following:
A.

The use of a hydrocarbon solvent preflush ahead of an acid treatment.

The solvent will help displace and dilute the sensitive oil ahead of the
acid. This will minimize the amount of contact between the acid treating
solution and the undiluted crude. The types of solvent preflushes mostly
used are:
a) Diesel
b) Kerosene
c) Xylene
d) Toluene

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Figure 4-5: shows the mechanical

Figure 4-6: Shows the chemical ball

sealers diversion agent

diversion using bridging

Figure 4-7: Shows the chemical Diversion

Using chemical resin

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B.

Stabilizing agents are used in the acid treating solutions. These additives
are effective in stabilizing the colloidal suspensions, which therefore
help to decrease or prevent the precipitation of asphaltic solids when the
oil is contacted by an acid treating solution.

C.

Stabilizing agents are used in solvent acid dispersion solutions. The

solvent which will help to dilute and disperse the asphaltic solids, and
the stabilizing additives, which will help maintain the asphaltic solids in
suspension can be used in a combined treatment.

Formed sludge inside formation can be removed by:

A) Solvent Treatments:
Most acid/oil sludge has only limited solubility. However, solvents
containing surfactants have been used to remove asphaltic sludge from
problem wells. The solvent and surfactant will help disperse and
dissolve the solids, allowing them to be circulated from the well.
B) Mechanical sludge removal:
a)
b)

Swabbing
Jetting and washing

7) Alcohols:
Isopropanol is normally used at a maximum concentration of 20 % by
volume. Methanol is used at various concentrations but typical
concentrations may be 30% by volume. In some cases, methanol is used
entirely to dilute concentrated acid to various acid treating solutions.
Alcohols are used in acid treatment for the following:
A) Removal of Water Blocks:
One problem, which occurs in producing wells, which can severally
decrease production, is blockage of the pore spaces by water. This
problem is commonly known as a water block and it is formed due to
the high capillary forces present in porous rocks.
Another reason why a water block is formed is the reaction of acid
with the wetting phase saturation near the wellbore. The most severe
water block problems occur in formations that have permeabilities
(to gas) less than 120 md. The function of the alcohol in the treating
fluid is to reduce the capillary forces within the reservoir thus
permitting easier removal of the liquid phases.

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B) More Rapid Fluid Recovery:

A problem encountered in treating oil or gas wells is the
recovery of the treating fluids. This is especially true in gas
reservoirs. The high surface tension of water or acid solution
hinders their penetration and recovery. The use of conventional
surface-active agents help slightly but they lose most of their
surface activity very rapidly from adsorption. Because of this
adsorption, the returning treating fluids have a high surface
tension and are difficult to recover.
The addition of alcohols to acid and water reduces the surface
tension of the fluids. The concentrations of alcohols, normally
used to lower surface tension of treating solutions, is of
sufficient quantity that adsorption is not a problem. The alcohols
used in the treating fluids also increases the vaporization rate of
the water portion. This allows for a more rapid desaturation of
water from a gas reservoir.
C) Retarding of Acid Reactivity:
Alcohol has a retarding effect on acid reactivity. The acid reactivity
is reduced proportionally by the type and percent of alcohol added.
D) Decreasing Amount of Water in Acids:
Some formations contain a large amount of water sensitive clays. In
order to minimize the amount of water contained in acid treating
solutions, alcohols are used in place or all of the dilution water.
8) Gelling and Fluid-loss Materials
These materials are generally made up of natural or synthetic polymers. Their
purpose is the same as similar additives for water or brine fracturing. In
addition, some degree of acid retardation is afforded. Gelling agents that are in
common use today are guar gum, gum karya blends and a wide variety of
synthetic polymers.

4.7

Retardation of Acid

To achieve deeper penetration, it may be necessary to use a retarded acid. In

matrix flow, most retarded acids spend quickly and have limited penetration.
Retardation is most effective in fracture acidizing and can be done by:
[1]

Using a slower reacting type acid (acetic or formic)

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[2]

[3]

4.8

Adding chemicals to reduce reaction rate of hydrochloric acid.

[a]

Using additives to introduce barrier on the surface of the rock

preventing normal contact with acid.

[b]

Additives such as calcium chloride introduce a common ion

effect.

Increasing the acid concentration to extend spending time.

Acidizing Techniques Acid Treatment Design

The success of any stimulation treatment depends on the correct analysis of

the well problem so that proper materials and techniques can be selected. Well
problems may be classified into two categories:
[1]
[2]

Damaged permeability
Low natural permeability

Wells with damaged permeability are candidates for matrix treatments. Those
with low natural permeability are candidates for fracturing as well as perhaps a
complementary matrix treatment. Treatment results may be carefully analyzed
to determine how subsequent treatment can be improved or optimized with
respect to treatment cost vs results. The results should be evaluated over a
significantly long period of time to determine the true values and not just a
flush production result.
It is extremely difficult to say that a formation with a certain composition or
solubility will or will not respond to an acid treatment. In carbonate formations
having more than 50% acid solubility, both matrix-type and fracture-type acid
treatments can be applicable. In formations with solubilities less than 50%,
these will generally be sandstone, matrix-type acid treatment using HF/HCl,
CHl or equivalent, however, these formations with limited acid solubility are
stimulated more frequently with water or oil fluid rather than with acid.

4.9

Acid Spent Time

The time required for an acid to spend from its initial strength down to the
point that approximately 85 to 90 percent of its dissolving capacity is expended
is an accepted definition of spending time. This is a point at which a plateau is
reached on the spending time curve and the spending of the remaining acid is
very slow due to dilution.
It is a common belief that successful fracture acidizing results are also
dependent upon the depth of penetration of reactive acid. In addition to having
maximum dissolving capacity, we would hope to be able to have good

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dissolving power and conductivity at a considerable distance from the

wellbore. If the acid used spends within a few feet of the wellbore then the
conductivity of that fracture will end, for all practical purposes, at that point.
The longer the spending time is within the possible limits, the better the
opportunity for obtaining maximum and uniform conductivity. Published
literature contains methods for calculating productivity ratios from fracture
conductivity and fracture penetration.
The spending time for an acid depends on the specific surface area of the rock
and it can be measured for a specific acid in the laboratory using natural core
samples obtained from the formation to be acidized. The spending time of an
acid is also affected by pressure, temperature, velocity of acid in the rock, acid
concentration, physical and chemical formation structure and the use of various
retarding additives.

4.10 Solubility of Reaction Products

The reaction of any acid on reservoir rock produces three basic reaction
products, water, carbon dioxide and calcium-magnesium salts of that acid. The
first two reaction products present no problems in acid stimulation. Indeed, the
manufacturing of carbon dioxide is a positive benefit in aiding the return of
spend fluids from the reservoir. The salts of calcium and magnesium can
present problems of solubility with certain acids depending upon the initial acid
strength.
A primary prerequisite of any acid used in reservoir stimulation is that the salts
formed by water soluble so that they can be removed from the formation
without fear of precipitation. In looking for the ideal acid, we would seek one
whose salts were completely soluble over the range of temperatures
encountered in most treatments. Indeed, we would go a step further and say
that his acid must produce a spent solution that was considerable
undersaturated. An acid that produces sufficient reaction salts to be at or near
the saturation point is in danger of forming precipitates if mixed with a near
saturated formation brine. Such precipitates, by reason of volumetric
differences between the compounds involved, could drastically reduce newly
created permeability of conductivity. This factor or solubility presents a
considerable obstacle with many acids.

4.11 MATRIX ACIDIZING:

Matrix stimulation is a well stimulation technique in which an acid solution
is injected into the formation in order to dissolve some of the minerals
present, and hence, recover or increase the permeability in the nearwellbore region. Such treatments are called 'matrix' treatments because the
solvent is injected at pressures below the parting pressure of the formation
so that fractures are not created. The objective is to greatly enhance or

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recover the permeability near the wellbore, rather than affect a large
portion of the reservoir.
The primary purpose of matrix acidizing is to improve flow capacity
through a damaged region near the wellbore. This can be achieved by
dissolving rock through near-wellbore formation damage.
Most matrix acidizing treatments in carbonates use hydrochloric acid
mixtures of one kind or another. Hydrochloric acid dissolves limestone
and dolomite to produce open, conductive channels. If extended, these
channels form wormholes, which can bypass near-wellbore formation
damage. The effective treated zone can become much larger than in
sandstones.
The most common matrix stimulation treatment is acidizing, in which an
acidic solution is injected to dissolve minerals in the formation. However,
other solvents are also used. The next most common fluids are inorganic
solvents aimed at dissolving waxes, paraffins, asphaltenes or other organic
damaging materials. This chapter deals with matrix acidizing but the
reader should keep in mind that many of the theories and calculation
procedures presented here can also be applied to nonacid solvent
treatments.
The most common acids are hydrochloric acid (HCl) used primarily to
dissolve carbonate minerals, and mixtures of HCl and hydrofluoric acid
(HF) which is used to attack silicate minerals such as clays and feldspars.
Other acids, particularly some weak organic acids, are used in special
applications, such as high-temperature wells. Matrix acidizing is a nearwellbore treatment, with all the acid reacting within about 1 ft of the
wellbore in sandstone formations and within a few inches to perhaps as
much as 10ft from the wellbore in carbonates.
Matrix acidizing can significantly enhance the productivity of a well when
near-wellbore formation damage is present and, conversely, is of limited
benefit in an undamaged well. Thus, matrix acidizing generally should be
applied only when a well has a high skin factor that cannot be attributed to
partial penetration, perforation efficiency or other mechanical aspects of
the completion. Two exceptions to this rule may occur. First, in highly
productive wells, the productivity improvement of about 20% that is
possible with matrix stimulation of an undamaged well may be economic.
Second, in naturally fractured or highly vugular carbonate reservoirs, live
acid may penetrate to a sufficient distance to yield a productivity
enhancement greater than that normally expected from a true matrix
treatment.

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An ideal matrix treatment restores the permeability in the near-wellbore

region to a value at least as high as the original undamaged permeability; it
accomplishes this over the entire completed interval and it leaves the
formation in the treated region with high relative permeability to the oil
and/or gas phase. Designing a treatment should strive to achieve this ideal
at the lowest possible cost, which requires consideration of the many
physical and chemical interactions taking place between the injected fluids
and the reservoir minerals and fluids. The most important of these
phenomena are the following:
1.

Mass transfer of acid molecules to the mineral surface and

subsequent reaction at the surface. Acid reactions with minerals are
termed heterogeneous reactions because they occur at a boundary
between the solid and the liquid rather than in the bulk phases.
Before the reaction can occur, acid must be transported to the
mineral surface by convection or diffusion. The overall reaction
rate (i.e. the rate of change of the concentration of one component in
the bulk liquid phase) may depend on both the rate of mass transfer
and the rate of surface reaction. Many times, however, one of these
processes is much slower than the other and controls the overall rate,
in which case the faster process can be ignored.

2.

Changing pore structure The physical change in the pore structure

caused by dissolution of some of the minerals by acid is the
mechanism by which matrix acidizing increases permeability. The
manner in which the pore structure changes is fundamentally
different in sandstones and carbonates, which leads to radically
different approaches to modeling the acidizing process in these two
mineralogies.

3.

precipitation of reaction products Secondary reactions occur in

acidizing , particularly in sandstones, that can result in the
precipitation of reaction products from the bulk liquid phase.
Obviously, precipitation solids may block pore spaces and work
against the goal of matrix acidizing.

4.

acid fluid-reservoir fluid interactions The acid solution injected in

matrix acidizing may interact physically and/or chemically with the
reservoir fluids as well as with the minerals. These interactions can
result in changes in wettability, phase saturation distribution,
precipitation of solids or emulsification.
variations in reservoir permeability or the distribution of damage
A successful acidizing treatment requires contacting all damaged
regions around the well with acid. This is usually complicated by
variations in the injectivity to acid along the wellbore, which leads

5.

4-341

to the use of techniques to affect good acid coverage (acid

diversion).
In considering the many aspects of the matrix acidizing process, the focus
is on the key design variables; to be useful, any model of the process must
aid in optimizing the design. The primary design considerations are:
a.
b.
c.
d.
e.

Fluid selection acid type, concentration and volume

Injection schedule planned rate of schedule and sequence of
injected fluids.
acid coverage and diversion special steps taken to improve
acid contact with the formation
real-time monitoring methods to evaluate the acidizing
process as it occurs.
additives other chemicals included in the acid solution to
enhance the process or to protect tubular goods.

Matrix acidizing is the process of injecting acid into the formation in radial
flow below fracturing pressure to remove damage and restore the
permeability to the original reservoir permeability or higher.
In this type of treatment, the acid enters only the natural pores, and flow
channels, and reacts with the walls of the pores, dissolving the rock and
enlarging the pores.
The acid reaction with formation rock slows down as the acid is spent. The
maximum radial penetration of unspent acid is a function of the acid
velocity in pore space and its spending time. Since the spending time of
acid does not change appreciably during a specific treatment, a maximum
penetration is attained when the first increment of injected acid is
completely spent.
Assuming a constant injection rate and that the spending time remaining
constant for all increments of acid, later increments of acid entering the
pore space will penetrate no deeper before spending than the first
increment. Additional acid injection will only enlarge the cross sectional
area instead of lengthening the treated flow channel.
To obtain maximum penetration with matrix acidizing, the acid should
have a low viscosity and low surface tension. Gelled and emulsified acids
should not be used because their viscosity and interfacial tension greatly
increase the injection pressures.
In carbonate matrix acid treatment, the acid used (usually hydrochloric
acid) is injected at pressure (and rate) low enough to prevent formation
fracturing. The treatment usually involves acid injection followed by a

4-342

sufficient after flush of water or hydrocarbon to clear all acid from well
tubular goods. When acid is pumped into a carbonate formation at pressure
below the fracture pressure, the acid flows preferentially into the highest
permeability regions (that is, largest pores, vugs, or natural fractures). Acid
reaction in the high permeability region causes the formation of large,
highly conductive flow channels called wormholes.
Acids normally used in field treatments are highly reactive at reservoir
conditions and tend to form a limited number of wormholes. Neither
theoretical nor experimental studies can predict the number, size, or length
of wormholes. If the acid reaction rate is very high, the theories predict that
only a few wormholes will form. A low reaction rate favors the formation
of several small diameter wormholes. Wormhole length normally is
controlled by the rate of fluid loss from the wormhole to the formation
matrix. The rate of fluid loss from a wormhole often can be reduced with a
fluid-loss additive thereby increasing wormhole length.
Retarded acid systems can extend the length and number of wormholes.
Such systems include slightly gelled acid, chemically modified acid,
surfactant-retarded acid, emulsified acid and foamed acid. However, the
time it takes for acid to spend is still short in most cases. More often than
not, only the formation near the wellbore can be treated effectively. Thus,
effective uniform matrix treatment beyond several feet from the wellbore is
unusual.
Acid-removable skin, or in the case of carbonates, skin that can be
bypassed by acid, must be present for a matrix acidizing treatment to be
effective, realistically.
After acidizing a clean unplugged flow path must exist from the wellbore
to the fractures, and crevices which have been created. It is therefore most
important that the soluble and reprecipitated reaction products and the
insoluble sands, clay and shales dislodged by the acid should be kept in
suspension by the acid. Acid should be completely removed after acidizing
treatment. Also it is important to both efficient acidizing and good clean
up operations is the matter of maintaining compatibility between the
treating solution and the formation and its fluids.
Damage Bypass
Damage bypass in carbonate formations can be achieved with either of two
methods applicable to carbonate acidizing:
Matrix acidizing
Fracture acidizing

4-343

Matrix acidizing will form wormholes through, and hopefully beyond, the
damage radius, thereby bypassing formation damage. Wormholing can be
influenced by the nature of the acid system used. There are slower-reacting
acids, such as acetic or EDTA, as well as retarded acid systems, such as
chemically (surfactant) retarded HCl. These acid systems will tend to form
relatively shallower, but more branched wormholes under similar
conditions (temperature, injection rate, etc.).
Strong acids, such as HCl, will typically form longer, single wormholes
extending from the perforations. If acid is not effectively diverted, a matrix
treatment with conventional HCl may create only one wormhole. This
wormhole will then accept all acid injected, as it will be the increasingly
conductive path of least resistance for acid as it continues to be injected.
Fracture acidizing also can be used to bypass formation damage in a
carbonate formation. For damage bypass, a long fracture may not be
needed. The purpose would be similar to that of a frac-and-pack procedure
in a sandstone formation. In that case, a propped fracture with length and
conductivity sufficient to effectively extend the wellbore radius beyond a
damage zone is all that is needed not an extensive, propped fracture.
FORMATION STIMULATION
In a carbonate formation, stimulation of the formation itself realistically
can only be achieved with fracture stimulation methods. These fracture
stimulation methods can be either hydraulic fracturing or fracture acidizing
(acid fracturing). To stimulate an undamaged formation, an extensive
conductive flow path deep into the formation must be created. This can
only be accomplished through fracturing.
Two key factors in the success of an acid fracturing treatment are the
resulting etched fracture length and conductivity. The effective fracture
length is influenced by: (1) acid fluid-loss characteristics; (2) acid reaction
rate; and (3) acid flow rate in the fracture. Acid fluid loss is the most
important factor affecting fracture length.
Conductivity is largely dependent on how the fracture faces are etched.
The fracture faces must be etched in a nonuniform manner to create
conductive flow channels that remain open after fracture closure.
Generally, good conductivity results from formation heterogeneity and
flow-induced selective etching.
Although fracture length and conductivity are difficult to predict, acid
fracturing, like hydraulic fracturing, can substantially improved
productivity and, in certain cases, increase field oil and gas reserves.

4-344

4.12 Effect of acid Reaction on formation Mechanical Properties:

In an effort to remove damage completely, whether originally present or
induced by the acid, one may decide to try a larger acid volume. Aside from
the additional cost, there is a physical limitation on the quantity of acid the
formation can tolerate without becoming unconsolidated. Recall that the acid is
dissolving the cementing material; therefore, as acid is injected, the formation
progressively becomes weaker until it finally disintegrates. If a treated
formation is acidized by excessive large acid volumes, the compressive
strength of the formation decreases and it can no longer support the overburden
load and then the compressive strength of the formation is inadequate to
support the overburden load and the formation recompacts to a lower porosity
and permeability.
The amount of acid required to remove formation consolidation varies with
many factors - the formations initial compressive strength; formation depth;
formation mineralogy; and how rapidly the acid dissolves cementation of rock
grains. Field experience usually determines the appropriate acid volume to be
used, although laboratory acid core flow tests can estimate the treatment
volume for initial treatments in the area.
Matrix acidizing is primarily beneficial in removing damage. For lowerpermeability reservoirs, significant stimulation of undamaged wells is generally
possible only with hydraulic fracturing. The goal of a matrix acidizing
treatment is to reduce the nonmechanical skin effect to near zero. Acidizing
beyond the amount required to remove the damage is of little benefit. Among
the design considerations important to matrix acidizing success are the type and
concentration of acid to be used, the amount of acid needed to dissolve
sufficient mineral around the wellbore, the optimal injection rate and the
placement of the acid solution.
The basic mechanisms by which acids and formation minerals interact are
described. This includes the stoichoimetry of the acid-rock reactions, the
amount of rock dissolved for a given amount of acid expended; the reaction
kinetics, the rates at which acids react with various minerals; and diffusion
rates, which control how rapidly acid is transported to the rock surfaces.

4.13 Acid-Mineral Reaction Stoichiometry

The amount of acid needed to dissolve a given amount of mineral is determined
by the stoichiometry of the chemical reaction which describes the number of
moles of each species involved in the reaction. For example, the simple
reaction between hydrochloric acid (HCl) and calcite (CaCO3) can be written
as:
2HCl + CaCO3 CaCl2 + CO2 + H2O

4-345

which shows that 2 moles of HCl are required to dissolve 1 mole of CaCO3.
The numbers 2 and 1 multiplying the species HCl and CaCO3 are the
stoichiometric coefficients, HCl and CaCO , for HCl and CaCo3, respectively.
3

When hydrofluoric acid reacts with silicate minerals, numerous secondary

reactions may occur that influence the overall stoichiometry of the reaction.
For example, when HF reacts with quartz (SiO2), the primary reaction is:
4HF + SiO2 SiF4 + 2H2O
producing silicon tetrafluoride (SiF4) and water.
The stoichiometry of this reactions show that 4 moles of HF are needed to
consume one mole of SiO2. However, the SiF4 produced may also react with
HF to form fluosilicic acid (H2SiF6) according to
SiF4 + 2HF H2SiF6
If this secondary reaction goes to completion, 6 moles of HF, rather than 4, will
be consumed to dissolve 1 mole of quartz. A complication is that the
fluosilicates may exist in various forms (Bryant, 1991), so that the total amount
of HF required to dissolve a given amount of quartz depends on the solution
concentration.
A more convenient way to express reaction stoichiometry is with the dissolving
power, introduced by Williams et al. (1979). The dissolving power expresses
the amount of mineral that can be consumed by a given amount of acid on a
mass or volume basis. First, the gravimetric dissolving power, , the mass of
mineral consumed by a given mass of acid, is defined as:

4.14 Gravimetric Dissolving Power

min eral MWmin eral

acid MWacid

4-1

Where
mineral
acid
MWmin eral
MWacid

=
=
=
=

The stoichiometric coefficient of the mineral

The stoichiometric coefficient of the acid
Molecular weight of the mineral
Molecular weight of the acid

4-346

Thus, for the reaction between 100% HCl and CaCO3,

100 =

lb CaCO 3
(1)(100.1)
= 1.37 m
(2)(36.5)
lb m HCl

where the subscript 100 denotes 100% HCl. The dissolving power of any other
concentration of acid is the 100 times the weight fraction of acid solution. For
the commonly used 15 wt% HCl,.
15 = 0.15(100 ) = 0.15x1.37 = 0.21lbm CaCO3 / lbm HCl .

The stoichiometric coefficients for common acidizing reactions are found from
the reaction equations presented in the previous sections while the molecular
weights of the most common species are listed in Table (4-1).

4.15 Volumetric dissolving power:

The volumetric dissolving power, X, similarly defined as the volume of
mineral dissolved by a given volume of acid, is related to the gravimetric
dissolving power by:

X =

acid solution
min eral

4-2

A 15 wt% HCl solution has a specific gravity of about 1.07, and CaCO3 has a
density of 169 lbm/ft3. For the reaction of these species, the volumetric
dissolving power is:

lb m CaCO 3 (1.07) (62.4) (lb m 15%HCl) / (ft 3 15% HCl)

X15 = 0.21

lb m 15% HCl
169(lb m CaCO 3 ) / (ft 3 CaCO 3 )

ft 3CaCO 3
= 0.082
ft 3 15% HCl
4-3
The dissolved powers of various acids limestone and dolomite and for HF with
quartz and albite are given in Tables (4-2 ) and (4-3 ) (Schechter, 1992).

4-347

Table (4-1). Molecular Weights of Species in Acidizing

Species

Molecular Weight (mass/mole)

Elements

Hydrogen, H
Carbon, C
Oxygen, O
Fluorine, F
Sodium, Na
Magnesium, Mg
Aluminum, Al
Silicon, Si
Chlorine, Cl
Potassium, K
Calcium, Ca
Iron, Fe

1
12
16
19
23
24.3
27
28.1
35.5
39.1
40.1
55.8
Molecules

Hydrochloric Acid, HCl

Hydrofluoric Acid, HF
Calcite, CaCO3
Dolomite, CaMg(CO3)2
Siderite, FeCO3
Quartz, SiO2
Albite (sodium feldspar), NaAlSi3O8
Orthoclase (potassium feldspar), KAlSi3O8
Kaolinite, Al4Si4O10
Montmorillonite, Al4Si8O20(OH)4

36.5
20
100.1
184.4
115.8
60.1
262.3
278.4
516.4
720.8

4-348

Table (4-2). Dissolving Power of Various Acids

Formulation

Acid

100

X
5%

Limestone:
CaCO3
CaCO3 = 2.71 g/cm3
Dolomite:
CaMg(CO3)-2
CaMg(CO3)2 = 2.87 g/cm3

Hydrochloric (HCl)
Formic (HCOOH)
Acetic (CH3COOH)
Hydrochloric
Formic
Acetic

1.37
1.09
0.83
1.27
1.00
0.77

0.026
0.020
0.016
0.023
0.018
0.014

Table (4-3). Dissolving Power for Hydrofluoric Acid*

Albite
Quartz (Sio2
(NaAlSi3O8)
Acid Concentration

X
(wt%)
2
0.015
0.006
0.019 0.008
3
0.023
0.010
0.028 0.011
4
0.030
0.018
0.037 0.015
6
0.045
0.019
0.056 0.023
8
0.060
0.025
0.075 0.030
* = Mass of rock dissolved/mass of acid reacted.
X = Volume of rock dissolved/volume of acid reacted.

4-349

10%

15%

30%

0.053
0.041
0.031
0.046
0.036
0.027

0.082
0.062
0.047
0.071
0.054
0.041

0.175
0.129
0.096
0.152
0.112
0.083

4.16 Calculating Minimum Acid Volume Using Dissolving Power

The volume of acid required for a matrix acidizing treatment can be estimated
using the concept of dissolving power. Because the volumetric dissolving
power X is the volume of a particular mineral that is dissolved by a given
volume of a particular acid solution, the minimum acid requirement to remove
that mineral can be calculated with little information other than the dissolving
power. Consider the following problem:
A sandstone formation with a porosity of 0.2 contains 5-vol% albite (sodium
feldspar). What is the minimum volume of 3% HF solution required to
dissolve all the albite a distance of 6 in. beyond a 6-in. diameter wellbore?
Solution:
The minimum acid volume is the amount VHF required to dissolve all the
feldspar plus the amount Vp required to fill the pore space in the region of
feldspar dissolution. These volumes are:

2 r 2 )(1 ) x
2
2
Vfeldspar = (rHF
w
feldspar = (0.75 0.25 )(1 0.2)(0.05)
ft 3
= 0.063
feldspar
ft

VHF =

Vfeldspar
X3

0.063
ft 3 HF
=
= 5.7
0.011
ft

In these equations, rHF is the radial penetration distance of HF, rw is the

wellbore radius, is the porosity and xfeldspar is the volume fraction of the
sandstone that is feldspar. The volume of pore space within 6 in. of the
wellbore after removal of the feldspar is:

2 r 2 )( + x
2
2
Vp = (rHF
w
feldspar (1 )) = (0.75 0.25 )(0.2 + 0.05(1 0.2))
ft 3
= 0.38
ft
So the total of HF required is:

VHF,T = VHF

gal
ft 3 7.48 gal
+ Vp = (5.7 + 0.38)
=
46

ft ft 3
ft

4-350

Thus, the minimum volume of 3% HF solution required to remove all feldspar

in a radial region extending 6 in. beyond the wellbore is 46 gal/ft of reservoir
thickness. In an actual acidizing treatment, the injected acid does not react
with feldspar only, and as shown by examining models of the acidizing
process, the acid is not spent uniformly, as tacitly assumed in this calculation.
Nevertheless, this simple calculation provides a ballpark figure for acid
requirements and is a handy check of more complex models of this process.
The minimum acid volume is the amount of Vacid required to dissolve all the
dissolved minerals in the rock plus the amount of rock pore volume, Vp,
required to fill the pore spaces in the region of rock mineral dissolution. These
volumes are:
2
Vmin eral = (racid
rw2 )(1 ) x min eral

4-4

The volume of acid required is:

Vacid =

Vacid

Vmin eral
x acid

2
(racid
rw2 )(1 ) x min eral
=
x acid

4-5

4-6

The volume of pore space within a distance, racid from the wellbore after the
removal (dissolution) of rock mineral is:
2
Vp = (racid
rw2 ) ( + x min eral (1 ))

4-7

The total volume of acid required is:

Vacid total = Vacid + Vp

4-8

Where
Vmineral
racid
rw

xmineral

= Volume of mineral dissolved by acid to a given acid

penetration radius which his dependent on acid spent time, ft
radial distance of acid penetration inside formation, ft
=
=
wellbore radius, ft
=
formation porosity, fraction
=
the volume fraction of the rock that is soluble in acid

4-351

xacid

Vacid
Vp

=
=

Vr
=
acid total

dissolving power of HCl or HF acids with carbonate or

sandstone rocks, respectively
minimum volume of acid required to dissolve the rock
rock pore volume invaded by acid

2 r 2 ) (1 ) x
(racid
min eral (1 So r )
w
x acid

2 r 2 )( + x
+ (racid
w
min eral (1 ))(1 So r )

4-9
The specific surface area is defined as the surface area of the rock exposed to
acid divided by the volume of acid injected.
S =

The surface area of rock exp osed to acid

Acid injected volume

4-10

The specific surface area can be obtained from Kozeny equation, which is
described as follows:

k=

108
4-11

2F S 2

Where the specific surface area is:

S = 10 4

1
2F k

4-12

Where
K = formation permeability, darcy
F = formation resistivity factor

F=

1
m

4-13

Where
m = cementation factor

4.17 Matrix Acidizing Design of Carbonates:

HCl is generally selected for carbonate acidizing. It can be replaced by organic
acids, mainly to minimize corrosion problems at temperatures greater than
400F [205C]. The purpose of acidizing with HCl is either to bypass the
4-352

damage by creating high-conductivity channels (also called wormholes) or to

etch partially plugged fissures in low-permeability fissured formations.
Although mere permeability restoration is usually targeted for sandstone
formations (zero damage skin effect), carbonate acidizing commonly results in
negative skin effects. This is due to the reopening of natural fissures and
creation of high-permeability wormholes in the near-wellbore area.
HCl can be retarded through the use of emulsions or microemulsions to prevent
rock deconsolidation. In this case, the wormholes are replaces by a more
uniform increase of pore size throughout the stimulation zone. Deep
penetration of live acid is obtained by reducing the contact area between the
acid and the rock.
The design of a matrix acid treatment for a carbonate formation consists of
specifying acid type, concentration and volume, and the maximum injection
rate and pressure that can be used without fracturing the formation.
The mineralogical composition of the carbonate matrix has a substantial effect
on formation response to hydraulic acid. The optimum acid volume and
concentration should be determined prior to the acidizing treatment in order to
obtain maximum acid performance.
Large volume or higher concentrations than the optimum values obtained for a
specific formation could produce adverse effects of lowering the maximum
permeability of the stimulated formation obtained during the treatment.
Further increase of acid injection volume could even lower the permeability of
the formation than the original permeability producing damaging effect to the
treated formation. It is therefore necessary to prepare the acid performance
curves (stimulation ratio ks/ko versus acid pore volumes injected for different
acid concentrations).
The acid performance curves are obtained in the Laboratory using
representative core samples. The permeability of the core sample was
measured before and after injection of increasing volumes of acid at
different concentrations.
The acid injection pore volume is calculated from the following equation:

PVI =

Acid Volume Injected

Core Pore Volume

4-14

The optimum acid injection volume into the core is the value corresponding to
the maximum stimulation ratio. Figure 1-8 represents the acid performance
curve (acid response curve, ARC) obtained in the laboratory. The maximum
stimulated average permeability and corresponding optimum pore volume

4-353

injected into the core sample is read from the peak of the curve. In order to
calculate the stimulated zone permissibility inside the core, the following
average permeability equation is used:

Ks =

Li

Li
Ki

Ls
Ks

L
L Ls
+
Ke

4-15

Where
Ls = length of the stimulated zone inside the core
L = length of the core sample
KS = average permeability of the core sample
KS = the permeability of the core stimulated zone
Ls - Inside core can be calculated from the following equation:

PVI =

VS A L s
=
VP
AL

4-16

The acid injected volume into the reservoir is calculated from the acid
performance curve. The acid performance curve in the core can be converted to
field conditions using appropriate upscaling techniques which will be discussed
in the following section.
The volume of acid required for a matrix acidizing treatment can be estimated
using the concept of dissolving power. Because the volumetrix dissolving
power X is the volume of a particular mineral that is dissolved by a given
volume of a particular acid solution, then minimum acid requirement to remove
that mineral can be calculated with little information other than the dissolving
power.
In order to determine the amount of acid ( Vr

acid total

) required for a specific acid

treatment, the following design procedure should be followed for carbonate

rocks acid design:
1)

A laboratory acid core flow test should be conducted on actual core

samples collected from the reservoir to be acidized (figure 4-8).

2)

From the laboratory acid flood data, an average acid response curve
(ARC) for all the core plugs tested is constructed. The curve represents
the acid stimulation ratio (k s / ke) on the y-axis versus the cumulative
acid pore volume injected (PVI) on the x-axis.

4-354

3)

The laboratory acid response curve is converted to field acid

performance curve using the following technique:
(a)
(b)
(c)

consider different radii (rs) to be acidized

suppose the acid will dissolve different percentages of mineral
volume (x)
calculate the reservoir volume (Vr) invaded by acid to the
assumed different radii (rs) using the equation:
Vr = (r 2
r 2 ) (1 So r )
assumed w

(d)

VHCl

4-17

calculate the volume of acid (Vacid) required to stimulate the

reservoir to the assumed different radii in the previous step using
the following equation:

2
(rHCl
rw2 )(1 ) x min eral (1 So r )
2
=
+ (rHCl
rw2 )( + x min eral (1 ))(1 So r )
x HCl

4-18
Where xHCl = acid dissolving power of HCl acid with either
limestone or dolomite rock read from Table (4-3 ).
In the above equation xmineral were set to equal to one because in
the case of acidizing carbonate rocks, all the limestone or the
dolomite are 100% soluble in HCl acid.
(e)

Calculate the field acid pore volume injected using the following
relationship:
(PVI) =

4)

VHCl
Vr

Calculate the acid pore volume injected in the field (PVI)field using the
following equation:

PVI field =
5)

4-19

Vs
Vr

4-20

Considering the acid injection conditions in the laboratory is the same a

that of the reservoir, then

4-355

Table 4-4: Laboratory acid data

qi
Vs (cc)
(cc/min)
0
0
0.15
7.6
0.16
8
0.16
8
0.16
8
0.15
7.68
0.16
8
0.16
8
0.16
8
0.16
7.92
0.15
7.84

Figure 4-8

4-356

ks/ke
1
1.2
1.4
1.6
1.8
2
2.2
2.4
2.3
1.8
1.4

wt
(gm)
15
14.877
14.769
14.661
14.553
14.445
14.337
14.229
14.121
14.013
13.905

(PVI)field = (PVI)lab
6)

7)

8)

9)

4-21

Entering the laboratory acid response curve (ARC) with the calculated
field acid pore volume (PVI)field and determine the corresponding acid
stimulation ratio k s kc for the field.
Plot the relationship between the field acid stimulation ratio ks K e and
the acid penetration radius (rs) for different assumed acid injection
volumes.
Repeat this procedure by assuming different inject acid volume and
different acid invasion radii. The converging procedure is illustrated in
table (4-4) and the constructed reservoir acid response curve in the
reservoir is illustrated in Figure 4-9.
The average permeability k s and the stimulated zone permeability ks of
the core sample are the same as that of the formation to be acidized.

r
K e K s ln e
rw
Ks =
r
r
K s ln e + K e ln s
rs
rw

4-22

The above equation can be used to calculate the permeability of the

stimulated zone around the wellbore after determining the optimum acid
penetration radius and the corresponding average reservoir stimulation
permeability from the converted field acid response curve.
10)

The productivity ratio of an acidizing treatment can be determined using

the following equation:
q
PR = s
qo

4-23

r
ln e
qs
ke r w
=
1 re 1
r
qo
ln + ln s
k e rs k s r w

4-24

qs ks (pe pwf )
=
q e k e (pe p wf )

4-25

4-357

Figure 4-9: Illustrates the converted acid performance curves for field
conditions.

4-358

4.18 MATRIX ACIDIZING DESIGN OF SANDSTONES:

Sandstone matrix acidizing is distinguished from carbonate acidizing in that it
involves the dissolution of damage that is blocking or bridging the pore throats
in the formation matrix, thus ideally recovering the original reservoir
permeability. The mineral acids required to dissolve the damage are usually
highly reactive with the numerous formation minerals. The resulting chemical
complexes can become insoluble in the environment created and can
precipitate, yielding gelatinous or solid particles. Because the formation and
the damage can have complicated crystalline structures that can yield a variety
of reaction products, sandstone acidizing success requires a significantly better
understanding of chemistry than does carbonate acidizing.
Mud acid treatments do not dissolve much of the formation minerals but rather
dissolve the materials clogging the pore throat. The purpose of sandstone
acidizing is to restore permeability by dissolving away formation damaging
clay-like minerals or other materials. The clay may be inherent in the
formation or may be the result of drilling or workover activities. X-ray
analysis can be used to determine the type and amount of clay present. Not
only the type and amount are important factors, but the physical rock structure
also plays an important role.
The type of acid most often used in sandstones is a mixture of HF and HCl
(Mud Acid). Concentrations of 2 to 6% hydrofluoric acid (HF) and 8 to 12%
hydrochloric acid (HCl) are normally used. If a significant amount of CaCO3 is
present in the formation (5-10%), a spearhead of HCl should be used to react
with it before the HF/HCl is injected. With CaCO3 content above 20%, HF
acid is probably not needed except to give entry through a clay damage.
As in any matrix-type treatment, injection of the HF/HCl should be below
fracturing pressure. Acid fracturing treatments in sandstones are not applicable.
Etching of the fracture faces for development of fracture conductivity normally
does not occur in sandstones. In a few soft, unproppable sandstones, large
fracturing treatments with HF/HCl formulations have been performed to create
a highly permeable matrix lends along the fracture faces.
The design of acid treatment for a sandstone formation should specify the
volume and concentration of acid, the maximum permissible injection rate and
the treating pressure.
1.

Determine the fracture gradient for the well. This can be determined
from a pressure integrity test or from theoretical considerations.

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4.917 10 6 Kh [FG D Ps P res]

q max =
r

B o ln s + S
rw

4-26

Where
qmax
K
h

Ps
FG
D
Pres
rs
rw
s
2.

= acid injection rate, bbl/mi

= average permeability, md
= net thickness of formation, ft
= viscosity of treating fluid at reservoir temperature, cp
= safety margin (200-500 psi)
= fracture gradient, psi/ft
= depth, ft
= reservoir pressure, psi
= radius of injected acid or damaged zone radius, ft
= wellbore radius, ft
= skin factor

Calculate the maximum injection rate without fracturing the

formation, using the following equation:

Pmax = ( G f Acid hydro. grad.) depth

4-27

Calculate the maximum surface pressure at which fluids can be injected

into the formation without fracturing it.

4.

Determine the volume of HCl - HF solution to use the minimum HF

acid solution for the treatment is calculated from the following acid
volume equation. Considering that xmineral should be volume of fraction
of feldspar or quartz or kaolinite or montmorillonite present in the
sandstone rock.

Vracid =

2 r 2 )(1 ) x
(rHF
w
min eral (1 So r )
x acid

2 r 2 )( + x
+ (rHF
w
min eral (1 ))(1 So r )

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The converting procedure steps of acid response curve in the laboratory
is the same as outlined in the carbonate design procedure.
5.

The purpose of sandstone acidizing is to restore permeability by

dissolving away formation damaging clay. The clay may be inherent
in the formation, or may be the result of drilling or workover
activities. X-ray analysis can be used to determine the type and
amount of clay present inside the damaged formation. Not only the

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type and amount are important factors, but the physical rock
structure also plays an important role.
6.

The volume of acid required depends on the depth of damage and degree
of damage. 50 to 150 gallons of acid per foot of interval is normal
treatment volume if damage is not extensive.

A core flow test with the acid gives a more realistic picture of the response
of the formation will have to acid. The acid response coefficient (ARC) is
a measure of the relative change in permeability of a core caused by acid
injection.
Although some of these formations have approximately the same acid (HF/
HCl) solubility, permeability and porosity, the response to acid is quite
different from one formation to another. Each formation requires a
different amount of acid. Figures 4-10 and 4-11 show the flow
improvement ratio (kf / ki) after acidizing for different sand formations.

4.19 Placement Techniques:

1. Preflush fluids:
A preflush of HCl acid should be pumped ahead of the HF acid mixture.
The preflush serves to:
a)

Provide a spacer between HF acid mixture and formation

fluids. This minimizes the possibility of forming insoluble

b)

Dissolve carbonates in the formation so that the HF acid will

not be wasted on the carbonates, but remain active to dissolve
clays and silicates.

The preflush fluids should include:

1. Ammonium chloride
2. Diesel oil
3. Kerosene
4. Lease oil (clean)
2. HCl-HF acid treating fluid
HCl-HF acid blend is designed to dissolve clay and sand and to remove
formation damage. HF concentration can vary from one to ten percent
by weight. However, three to four percent is commonly used.

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The physical and chemical properties of sandstone will dictate the acid
concentration and treating volumes best suited.
3. After-flush
In oil wells, inject a volume of after flush of diesel oil or hydrochloric
acid equal to the mud acid volume. In gas wells and water injection
wells, the after flush is normally 15 percent Hcl. Diesel oil is not to be
used in either gas or water injection wells because of its adverse effect
on the relative permeability to either fluid.
4. Acid swabbing (shut-in time)
No soaking time is required for this treatment to be effective; as soon as
possible after injection is complete the well should be put back on
production. Prolonged waiting periods with spent acid in the formation
reduce the effectiveness of the treatment.
The rate of reaction of hydrofluoric acid with silica and clays is
quite fast. Return of the stimulation fluids should begin as soon as
possible. This reduces the possibility of forming insoluble
secondary precipitates, which may reduce the effectiveness of the
acid treatment.
There are precautions and placement techniques which should be observed in
order to maximize the benefits obtained from HF Acid treatments. First, always
dilute or mix the acid with fresh water rather than brine or salt water. This will
help prevent the precipitation of sodium fluosilicate and potassium fluisilicate
as the hydrofluoric acid spends in the formation.
In general, a pad volume or spearhead of dilute hydrochloric acid should be
pumped ahead of the hydrofluoric-hydrochloric acid (HF acid) for two reasons.
The preflush of hydrochloric acid will dissolve any carbonate material in the
formation. This will prevent using the more expensive hydrofluoric acid for
limestone removal and will also minimize the formation of the insoluble
calcium fluoride. The second benefit is that the hydrochloric acid spearhead
will serve as a buffer between the formation fluids and the hydrofluoric acid.
This will minimize the precipitation of sodium fluosilicate and potassium
fluosilicate by preventing mixing of the spent hydrofluoric acid with the
formation brine.
The HF Acid step consists of injecting the normal HF Acid ( 3%HF 12% HCl
) in combination with any additives deemed necessary. The hydrofluorichydrochloric acid mixture (HF acid) may be spotted to the formation with one
of several solutions. One such solution is kerosene or diesel oil. Generally, this
displacement fluid does not enter the formation; the oil-surfactant mixture will

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minimize any chance of damage. Hydrochloric acid mixture reduces surface

tension and interfacial tension characteristics of well fluid to extremely low
values and this property aids in breaking emulsions which can result in
decreased production.

4.20 Productivity after sandstone acidizing:

A matrix acid treatment in a sandstone formation should remove flow restrictions near
the wellbore and allow the well to produce at an undamaged rate (figures4-10 and 411). However, the production rate after treatment is sometimes lower than expected.
Figure 4-12 illustrates the comparison between different stimulation techniques.

Flow restrictions after treatment are believed to occur most often because
of precipitation of acid reaction products, a change in the wettability of the
rock from water to oil wet, or the formation of an emulsion between the
reacted acid and formation oil.
The following steps will minimize the chance for damaging the formation
by precipitation:
(1)

An acid preflush should be used.

(2)

An afterflush compatible with the reacted acid should be used, and mostly
hydrochloric acid.
The acid should be produced back out of the formation within a few hours of
treatment completion.

(3)

Both oil wetting of the formation matrix and fine particles released by acid
reaction can potentially reduce productivity. The formation of solids may
be oil wet because the corrosion inhibitor or other additives absorb strongly
on clay particles or clean silica surfaces. Oil wetting of these can reduce
the relative permeability to oil.
Productivity impairment also can occur if an emulsion is formed between
the reservoir oil and the reacted acid. Often these emulsions are stabilized
by fines that are partially oil wet and partially water wet.
pH, oil composition can influence emulsion formation and stabilization.
The emulsified liquid can exhibit an extremely high viscosity and very
poor flow characteristics. Therefore, emulsion impedes the flow of spent
mud acid from the formation to the wellbore and reduces the effectiveness
of the stimulation treatment by occupying pore spaces near the wellbore.
Productivity restrictions caused by oil wetting of formation and fines often can be
removed by making the solids water wet. This may be done with surface-active agents
provided they contact the solid surface and replace the agent making the surface oil
wet.

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Figure 4-10: productivity improvement after sandstone acidizing

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Figure 4-11: productivity improvement after sandstone acidizing

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Figure 4-12: Illustrates the comparison between different

stimulation techniques.

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